Extracellular ice phase transitions in insects.

PubMed

Hawes, T C

2014-01-01

At temperatures below their temperature of crystallization (Tc), the extracellular body fluids of insects undergo a phase transition from liquid to solid. Insects that survive the transition to equilibrium (complete freezing of the body fluids) are designated as freeze tolerant. Although this phenomenon has been reported and described in many Insecta, current nomenclature and theory does not clearly delineate between the process of transition (freezing) and the final solid phase itself (the frozen state). Thus freeze tolerant insects are currently, by convention, described in terms of the temperature at which the crystallization of their body fluids is initiated, Tc. In fact, the correct descriptor for insects that tolerate freezing is the temperature of equilibrium freezing, Tef. The process of freezing is itself a separate physical event with unique physiological stresses that are associated with ice growth. Correspondingly there are a number of insects whose physiological cryo-limits are very specifically delineated by this transitional envelope. The distinction also has considerable significance for our understanding of insect cryobiology: firstly, because the ability to manage endogenous ice growth is a fundamental segregator of cryotype; and secondly, because our understanding of internal ice management is still largely nascent.

Evaluation of Spaceborne L-band Radiometer Measurements for Terrestrial Freeze/Thaw Retrievals in Canada

NASA Technical Reports Server (NTRS)

Roy, A.; Royer, A.; Derksen, C.; Brucker, L.; Langlois, A.; Mailon, A.; Kerr, Y.

2015-01-01

The landscape freeze/thaw (FT) state has an important impact on the surface energy balance, carbon fluxes, and hydrologic processes; the timing of spring melt is linked to active layer dynamics in permafrost areas. L-band (1.4 GHz) microwave emission could allow the monitoring of surface state dynamics due to its sensitivity to the pronounced permittivity difference between frozen and thawed soil. The aim of this paper is to evaluate the performance of both Aquarius and Soil Moisture and Ocean Salinity (SMOS) L-band passive microwave measurements using a polarization ratio-based algorithm for landscape FT monitoring. Weekly L-band satellite observations are compared with a large set of reference data at 48 sites across Canada spanning three environments: tundra, boreal forest, and prairies. The reference data include in situ measurements of soil temperature (Tsoil) and air temperature (Tair), and Moderate Resolution Imaging Spectroradiometer (MODIS) land surface temperature (LST) and snow cover area (SCA) products. Results show generally good agreement between Lband FT detection and the surface state estimated from four reference datasets. The best apparent accuracies for all seasons are obtained using Tair as the reference. Aquarius radiometer 2 (incidence angle of 39.6) data gives the best accuracies (90.8), while for SMOS the best results (87.8 of accuracy) are obtained at higher incidence angles (55- 60). The FT algorithm identifies both freeze onset and end with a delay of about one week in tundra and two weeks in forest and prairies, when compared to Tair. The analysis shows a stronger FT signal at tundra sites due to the typically clean transitions between consistently frozen and thawed conditions (and vice versa) and the absence of surface vegetation. Results in the prairies were poorer because of the influence of vegetation growth in summer (which decreases the polarization ratio) and the high frequency of ephemeral thaw events during winter. Freeze onset and end maps created from the same algorithm applied to SMOS and Aquarius measurements characterize similar FT patterns over Canada. This study shows the potential of using L-band spaceborne observations for FT monitoring, but underlines some limitations due to ice crusts in the snowpack, liquid water content in snow cover during the spring freeze to thaw transition, and vegetation growth.

Suppressing Ice Nucleation of Supercooled Condensate with Biphilic Topography

NASA Astrophysics Data System (ADS)

Hou, Youmin; Yu, Miao; Shang, Yuhe; Zhou, Peng; Song, Ruyuan; Xu, Xiaonan; Chen, Xuemei; Wang, Zuankai; Yao, Shuhuai

2018-02-01

Preventing or minimizing ice formation in supercooled water is of prominent importance in many infrastructures, transportation, and cooling systems. The overall phase change heat transfer on icephobic surfaces, in general, is intentionally sacrificed to suppress the nucleation of water and ice. However, in a condensation frosting process, inhibiting freezing without compromising the water condensation has been an unsolved challenge. Here we show that this conflict between anti-icing and efficient condensation cooling can be resolved by utilizing biphilic topography with patterned high-contrast wettability. By creating a varying interfacial thermal barrier underneath the supercooled condensate, the biphilic structures tune the nucleation rates of water and ice in the sequential condensation-to-freezing process. Our experimental and theoretical investigation of condensate freezing dynamics further unravels the correlation between the onset of droplet freezing and its characteristic radius, offering a new insight for controlling the multiphase transitions among vapor, water, and ice in supercooled conditions.

Suppressing Ice Nucleation of Supercooled Condensate with Biphilic Topography.

PubMed

Hou, Youmin; Yu, Miao; Shang, Yuhe; Zhou, Peng; Song, Ruyuan; Xu, Xiaonan; Chen, Xuemei; Wang, Zuankai; Yao, Shuhuai

2018-02-16

Preventing or minimizing ice formation in supercooled water is of prominent importance in many infrastructures, transportation, and cooling systems. The overall phase change heat transfer on icephobic surfaces, in general, is intentionally sacrificed to suppress the nucleation of water and ice. However, in a condensation frosting process, inhibiting freezing without compromising the water condensation has been an unsolved challenge. Here we show that this conflict between anti-icing and efficient condensation cooling can be resolved by utilizing biphilic topography with patterned high-contrast wettability. By creating a varying interfacial thermal barrier underneath the supercooled condensate, the biphilic structures tune the nucleation rates of water and ice in the sequential condensation-to-freezing process. Our experimental and theoretical investigation of condensate freezing dynamics further unravels the correlation between the onset of droplet freezing and its characteristic radius, offering a new insight for controlling the multiphase transitions among vapor, water, and ice in supercooled conditions.

State transitions and physicochemical aspects of cryoprotection and stabilization in freeze-drying of Lactobacillus rhamnosus GG (LGG).

PubMed

Pehkonen, K S; Roos, Y H; Miao, S; Ross, R P; Stanton, C

2008-06-01

The frozen and dehydrated state transitions of lactose and trehalose were determined and studied as factors affecting the stability of probiotic bacteria to understand physicochemical aspects of protection against freezing and dehydration of probiotic cultures. Lactobacillus rhamnosus GG was frozen (-22 or -43 degrees C), freeze-dried and stored under controlled water vapour pressure (0%, 11%, 23% and 33% relative vapour pressure) conditions. Lactose, trehalose and their mixture (1 : 1) were used as protective media. These systems were confirmed to exhibit relatively similar state transition and water plasticization behaviour in freeze-concentrated and dehydrated states as determined by differential scanning calorimetry. Ice formation and dehydrated materials were studied using cold-stage microscopy and scanning electron microscopy. Trehalose and lactose-trehalose gave the most effective protection of cell viability as observed from colony forming units after freezing, dehydration and storage. Enhanced cell viability was observed when the freezing temperature was -43 degrees C. State transitions of protective media affect ice formation and cell viability in freeze-drying and storage. Formation of a maximally freeze-concentrated matrix with entrapped microbial cells is essential in freezing prior to freeze-drying. Freeze-drying must retain a solid amorphous state of protectant matrices. Freeze-dried matrices contain cells entrapped in the protective matrices in the freezing process. The retention of viability during storage seems to be controlled by water plasticization of the protectant matrix and possibly interactions of water with the dehydrated cells. Highest cell viability was obtained in glassy protective media. This study shows that physicochemical properties of protective media affect the stability of dehydrated cultures. Trehalose and lactose may be used in combination, which is particularly important for the stabilization of probiotic bacteria in dairy systems.

Electroperturbation of human stratum corneum fine structure by high voltage pulses: a freeze-fracture electron microscopy and differential thermal analysis study.

PubMed

Jadoul, A; Tanojo, H; Préat, V; Bouwstra, J A; Spies, F; Boddé, H E

1998-08-01

Application of high voltage pulses (HVP) to the skin has been shown to promote the transdermal drug delivery by a mechanism involving skin electroporation. The aim of this study was to detect potential changes in lipid phase and ultrastructure induced in human stratum corneum by various HVP protocols, using differential thermal analysis and freeze-fracture electron microscopy. Due to the time involved between the moment the electric field is switched off and the analysis, only "secondary" phenomena rather than primary events could be observed. A decrease in enthalpies for the phase transitions observed at 70 degrees C and 85 degrees C was detected by differential thermal analysis after HVP treatment. No changes in transition temperature could be seen. The freeze-fracture electron microscopy study revealed a dramatic perturbation of the lamellar ordering of the intercellular lipid after application of HVP. Most of the planes displayed rough surfaces. The lipid lamellae exhibited rounded off steps or a vanished stepwise order. There was no evidence for perturbation of the corneocytes content. In conclusion, the freeze-fracture electron microscopy and differential thermal analysis studies suggest that HVP application induces a general perturbation of the stratum corneum lipid ultrastructure.

Cooling rate dependence of the glass transition at free surfaces

NASA Astrophysics Data System (ADS)

Streit-Nierobisch, S.; Gutt, C.; Paulus, M.; Tolan, M.

2008-01-01

In situ x-ray reflectivity measurements are used to determine the cooling rate dependent freezing of capillary waves on the oligomer poly(propylene glycol). Only above the glass transition temperature TG can the surface roughness σ be described by the capillary wave model for simple liquids, whereas the surface fluctuations are frozen-in at temperatures below TG . As the state of a glass forming liquid strongly depends on its thermal history, this effect occurs for fast cooling rates already at a higher temperature than for slow cooling. For the fastest cooling rates a very large shift of TG up to 240K compared to the bulk value of 196K was observed.

Activating the Microscale Edge Effect in a Hierarchical Surface for Frosting Suppression and Defrosting Promotion

PubMed Central

Chen, Xuemei; Ma, Ruiyuan; Zhou, Hongbo; Zhou, Xiaofeng; Che, Lufeng; Yao, Shuhuai; Wang, Zuankai

2013-01-01

Despite extensive progress, current icephobic materials are limited by the breakdown of their icephobicity in the condensation frosting environment. In particular, the frost formation over the entire surface is inevitable as a result of undesired inter-droplet freezing wave propagation initiated by the sample edges. Moreover, the frost formation directly results in an increased frost adhesion, posing severe challenges for the subsequent defrosting process. Here, we report a hierarchical surface which allows for interdroplet freezing wave propagation suppression and efficient frost removal. The enhanced performances are mainly owing to the activation of the microscale edge effect in the hierarchical surface, which increases the energy barrier for ice bridging as well as engendering the liquid lubrication during the defrosting process. We believe the concept of harnessing the surface morphology to achieve superior performances in two opposite phase transition processes might shed new light on the development of novel materials for various applications. PMID:23981909

Snowmelt and Surface Freeze/Thaw Timings over Alaska derived from Passive Microwave Observations using a Wavelet Classifier

NASA Astrophysics Data System (ADS)

Steiner, N.; McDonald, K. C.; Dinardo, S. J.; Miller, C. E.

2015-12-01

Arctic permafrost soils contain a vast amount of organic carbon that will be released into the atmosphere as carbon dioxide or methane when thawed. Surface to air greenhouse gas fluxes are largely dependent on such surface controls as the frozen/thawed state of the snow and soil. Satellite remote sensing is an important means to create continuous mapping of surface properties. Advances in the ability to determine soil and snow freeze/thaw timings from microwave frequency observations improves upon our ability to predict the response of carbon gas emission to warming through synthesis with in-situ observation, such as the 2012-2015 Carbon in Arctic Reservoir Vulnerability Experiment (CARVE). Surface freeze/thaw or snowmelt timings are often derived using a constant or spatially/temporally variable threshold applied to time-series observations. Alternately, time-series singularity classifiers aim to detect discontinuous changes, or "edges", in time-series data similar to those that occur from the large contrast in dielectric constant during the freezing or thaw of soil or snow. We use multi-scale analysis of continuous wavelet transform spectral gradient brightness temperatures from various channel combinations of passive microwave radiometers, Advanced Microwave Scanning Radiometer (AMSR-E, AMSR2) and Special Sensor Microwave Imager (SSM/I F17) gridded at a 10 km posting with resolution proportional to the observational footprint. Channel combinations presented here aim to illustrate and differentiate timings of "edges" from transitions in surface water related to various landscape components (e.g. snow-melt, soil-thaw). To support an understanding of the physical basis of observed "edges" we compare satellite measurements with simple radiative transfer microwave-emission modeling of the snow, soil and vegetation using in-situ observations from the SNOw TELemetry (SNOTEL) automated weather stations. Results of freeze/thaw and snow-melt timings and trends are reported for Alaska and the North-West Canadian Arctic for the period 2002 to 2015.

A practical method to detect the freezing/thawing onsets of seasonal frozen ground in Alaska

NASA Astrophysics Data System (ADS)

Chen, Xiyu; Liu, Lin

2017-04-01

Microwave remote sensing can provide useful information about freeze/thaw state of soil at the Earth surface. An edge detection method is applied in this study to estimate the onsets of soil freeze/thaw state transition using L band space-borne radiometer data. The Soil Moisture Active Passive (SMAP) mission has a L band radiometer and can provide daily brightness temperature (TB) with horizontal/vertical polarizations. We use the normalized polarization ratios (NPR) calculated based on the Level-1C TB product of SMAP (spatial resolution: 36 km) as the indicator for soil freeze/thaw state, to estimate the freezing and thawing onsets in Alaska in the year of 2015 and 2016. NPR is calculated based on the difference between TB at vertical and horizontal polarizations. Therefore, it is strongly sensitive to liquid water content change in the soil and independent with the soil temperature. Onset estimation is based on the detection of abrupt changes of NPR in transition seasons using edge detection method, and the validation is to compare estimated onsets with the onsets derived from in situ measurement. According to the comparison, the estimated onsets were generally 15 days earlier than the measured onsets in 2015. However, in 2016 there were 4 days in average for the estimation earlier than the measured, which may be due to the less snow cover. Moreover, we extended our estimation to the entire state of Alaska. The estimated freeze/thaw onsets showed a reasonable latitude-dependent distribution although there are still some outliers caused by the noisy variation of NPR. At last, we also try to remove these outliers and improve the performance of the method by smoothing the NPR time series.

Mutual Influence of Mannitol and Trehalose on Crystallization Behavior in Frozen Solutions.

PubMed

Jena, Sampreeti; Suryanarayanan, Raj; Aksan, Alptekin

2016-06-01

Phase separation of trehalose during freeze-drying could render it ineffective as a lyoprotectant. The bulking agent, mannitol, on the other hand, should crystallize readily upon freezing. It is therefore imperative to understand the mutual interaction of these sugars during freezing to ensure preservation of the API during freeze-drying. We investigated the effect of mannitol to trehalose ratio (R) on the crystallization behavior of both solutes using Differential Scanning Calorimetry, X-Ray Crystallography and FTIR Spectrosopy during controlled freezing and annealing. When R = 1, crystallization of both mannitol (as hemihydrate) and trehalose (as α-anhydrate) were observed. When R ≥ 1, extent of mannitol crystallization was directly proportional to the value of R. When R < 1, trehalose completely suppressed mannitol crystallization. At R > 1, the freeze concentrate was heterogeneous and characterized by two glass transitions - the lower temperature transition (Tg") attributed to systems containing "extra" unfrozen water. When heated above Tg", crystallization of mannitol and the associated unfrozen water resulted in Tg' (glass transition temperature of the freeze-concentrate). R and not the total solute concentration, dictates the composition of the freeze concentrate as well as the physical stability of the excipients.

"Freezing" of nanoconfined fluids under an electric field.

PubMed

Xie, Guoxin; Luo, Jianbin; Liu, Shuhai; Guo, Dan; Zhang, Chenhui

2010-02-02

The problem of the solidlike transition of fluids in a nanogap has drawn much fundamental and practical attention. Here, we directly observed the disappearance of the fluidity of liquids confined within a gap with a surface separation of >10 nm under an EF in a ball-plate system, which is called the "freezing" of liquids. The flow of the nanoconfined liquid became very weak as the EF intensity was increased to a critical value and was correlated with the liquid polarity and the film thickness. It is deduced that the EF can induce more liquid molecules to be aligned to form more ordered layers in the nanogap.

Porosity and water activity effects on stability of crystalline β-carotene in freeze-dried solids.

PubMed

Harnkarnsujarit, Nathdanai; Charoenrein, Sanguansri; Roos, Yrjö H

2012-11-01

Stability of entrapped crystalline β-carotene as affected by water activity, solids microstructure, and composition of freeze-dried systems was investigated. Aliquots (1000 mm(3) , 20% w/w solids) of solutions of maltodextrins of various dextrose equivalents (M040:DE6, M100:DE11, and M250:DE25.5), M100-sugars (1:1 glucose, fructose and sucrose), and agar for gelation with dispersed β-carotene were frozen at -20, -40, or -80 °C and freeze-dried. Glass transition and α-relaxation temperatures were determined with differential scanning calorimetry and dynamic mechanical analysis, respectively. β-Carotene contents were monitored spectrophotometrically. In the glassy solids, pore microstructure had a major effect on β-carotene stability. Small pores with thin walls and large surface area allowed β-carotene exposure to oxygen which led to a higher loss, whereas structural collapse enhanced stability of β-carotene by decreasing exposure to oxygen. As water plasticized matrices, an increase in molecular mobility in the matrix enhanced β-carotene degradation. Stability of dispersed β-carotene was highest at around 0.2 a(w) , but decreasing structural relaxation times above the glass transition correlated well with the rate of β-carotene degradation at higher a(w) . Microstructure, a(w) , and component mobility are important factors in the control of stability of β-carotene in freeze-dried solids. β-Carotene expresses various nutritional benefits; however, it is sensitive to oxygen and the degradation contributes to loss of nutritional values as well as product color. To increase stability of β-carotene in freeze-dried foods, the amount of oxygen penetration need to be limited. The modification of freeze-dried food structures, for example, porosity and structural collapse, components, and humidity effectively enhance the stability of dispersed β-carotene in freeze-dried solids. © 2012 Institute of Food Technologists®

Surface freezing of water.

PubMed

Pérez-Díaz, J L; Álvarez-Valenzuela, M A; Rodríguez-Celis, F

2016-01-01

Freezing, melting, evaporation and condensation of water are essential ingredients for climate and eventually life on Earth. In the present work, we show how surface freezing of supercooled water in an open container is conditioned and triggered-exclusively-by humidity in air. Additionally, a change of phase is demonstrated to be triggered on the water surface forming surface ice crystals prior to freezing of bulk. The symmetry of the surface crystal, as well as the freezing point, depend on humidity, presenting at least three different types of surface crystals. Humidity triggers surface freezing as soon as it overpasses a defined value for a given temperature, generating a plurality of nucleation nodes. An evidence of simultaneous nucleation of surface ice crystals is also provided.

Freezing-induced uptake of trehalose into mammalian cells facilitates cryopreservation.

PubMed

Zhang, Miao; Oldenhof, Harriëtte; Sieme, Harald; Wolkers, Willem F

2016-06-01

The aim of this study was to investigate if membrane-impermeable molecules are taken up by fibroblasts when exposing the cells to membrane phase transitions and/or freezing-induced osmotic forces. The membrane-impermeable fluorescent dye lucifer yellow (LY) was used to visualize and quantify uptake during endocytosis, and after freezing-thawing. In addition, trehalose uptake after freezing and thawing was studied. Fourier transform infrared spectroscopic studies showed that fibroblasts display a minor non-cooperative phase transition during cooling at suprazero temperatures, whereas cells display strong highly cooperative fluid-to-gel membrane phase transitions during freezing, both in the absence and presence of protectants. Cells do not show uptake of LY upon passing the suprazero membrane phase transition at 30-10°C, whereas after freezing and thawing cells show intracellular LY equally distributed within the cell. Both, LY and trehalose are taken up by fibroblasts after freezing and thawing with loading efficiencies approaching 50%. When using 250 mM extracellular trehalose during cryopreservation, intracellular concentrations greater than 100 mM were determined after thawing. A plot of cryosurvival versus the cooling rate showed a narrow inverted-'U'-shaped curve with an optimal cooling rate of 40°C min(-1). Diluting cells cryopreserved with trehalose in isotonic cell culture medium resulted in a loss of cell viability, which was attributed to intracellular trehalose causing an osmotic imbalance. Taken together, mammalian cells can be loaded with membrane-impermeable compounds, including the protective agent trehalose, by subjecting the cells to freezing-induced osmotic stress. Copyright © 2016 Elsevier B.V. All rights reserved.

Non-equilibrium freezing behaviour of aqueous systems.

PubMed

MacKenzie, A P

1977-03-29

The tendencies to non-equilibrium freezing behaviour commonly noted in representative aqueous systems derive from bulk and surface properties according to the circumstances. Supercooling and supersaturation are limited by heterogeneous nucleation in the presence of solid impurities. Homogeneous nucleation has been observed in aqueous systems freed from interfering solids. Once initiated, crystal growth is ofter slowed and, very frequently, terminated with increasing viscosity. Nor does ice first formed always succeed in assuming its most stable crystalline form. Many of the more significant measurements on a given systeatter permitting the simultaneous representation of thermodynamic and non-equilibrium properties. The diagram incorporated equilibrium melting points, heterogeneous nucleation temperatures, homogeneous nucleation temperatures, glass transition and devitrification temperatures, recrystallization temperatures, and, where appropriate, solute solubilities and eutectic temperatures. Taken together, the findings on modle systems aid the identification of the kinetic and thermodynamic factors responsible for the freezing-thawing survival of living cells.

Immersion Freezing of Aluminas: The Effect of Crystallographic Properties on Ice Nucleation

NASA Astrophysics Data System (ADS)

King, M.; Chong, E.; Freedman, M. A.

2017-12-01

Atmospheric aerosol particles serve as the nuclei for heterogeneous ice nucleation, a process that allows for ice to form at higher temperatures and lower supersaturations with respect to ice. This process is essential to the formation of ice in cirrus clouds. Heterogeneous ice nucleation is affected by many factors including the composition, crystal structure, porosity, and surface area of the particles. However, these factors are not well understood and, as such, are difficult to account for in climate models. To test the effects of crystal structure on ice nucleation, a system of transition aluminas (Al2O3) that differ only in their crystal structure, despite being compositionally similar, were tested using immersion freezing. Particles were immersed in water and placed into a temperature controlled chamber. Freezing events were then recorded as the chamber was cooled to negative 30 °. Alpha-alumina, which is a member of the hexagonal crystal system, showed a significantly higher temperature at which all particles froze in comparison to other samples. This supports the hypothesis that, since a hexagonal crystal structure is the lowest energy state for ice, hexagonal surface structures would best facilitate ice nucleation. However, a similar sample of hexagonal chi-alumina did not show the same results. Further analysis of the samples will be done to characterize surface structures and composition. These conflicting data sets raise interesting questions about the effect of other surface features, such as surface area and porosity, on ice nucleation.

Freeze Tolerance of Nine Zoysiagrass Cultivars Using Natural Cold Acclimation and Freeze Chambers

USDA-ARS?s Scientific Manuscript database

Winter hardiness of zoysiagrass (Zoysia spp.) cultivars is an important attribute throughout the biogeographical transition zone, thus the inability to withstand freezing temperatures may limit the use of these cultivars. The objective of this research was to determine the freeze tolerance (LT50) of...

High Resolution Freeze and Thaw States Detection Using Combination of Sentinel 1A SAR and Passive Microwave Measurements

NASA Astrophysics Data System (ADS)

Azarderakhsh, M.; McDonald, K. C.; Norouzi, H.; Rebolledo, M. A.; Prakash, S.

2017-12-01

The freeze and thaw (FT) cycles in high-latitude regions have great impact on many biogeochemical transitions, hydrology and ecosystem especially in wetland areas. Passive and active microwave remote sensing data from satellite observations have been deployed in the past to define the status of the surface in terms of freeze and thaw. While many progresses have been made in this field, the limitations attached to such observations have hindered our ability to fully predict the change of surface state in the scale that is appropriate for the aforementioned applications. The transition between freeze and thaw states may occur frequently (even within a day) especially during shifts from cold to warm seasons and vice versa. Passive microwave sensors have different acquisition times, and data fusion of these sensors may provide a complete diurnal variation estimate of FT states. However, the coarse spatial resolution of these measurements may undermine their applicability. However, active microwave backscatter measurements from sensors such as Sentinel 1A and the Advanced Land Observing Satellite Phased Array L-Band SAR (ALOS PALSAR) can deliver high resolution information about wetlands and FT status. In this project, Synthetic Aperture Radar (SAR) c-band backscatter data from Sentinel 1 from April 2014 to June 2017 are deployed to detect high resolution freeze/thaw states and wetland areas. The contrasts between frozen and thawed seasons are used to define FT states after performing required radiometric corrections and calibrations. A method based on phase changes in polarized images is developed for different land cover types to maximize the accuracy of the detections. The aggregated (up-scaled) estimates from active measurements are compared to passive microwave-based FT product. The results of this method reveal that the estimates are relatively in good agreement with SNOw TELemetry (SNOTEL) ground measurements. Finally, a downscaling method is tried to link passive emissivity-based FT product to high resolution active FT estimates to increase the temporal frequency of the high-resolution Sentinel data. The results of this study contribute to better understanding sources of positive carbon and methane (CH4) feedback to the atmosphere.

Springtime microwave emissivity changes in the southern Kara Sea

NASA Technical Reports Server (NTRS)

Crane, Robert G.; Anderson, Mark R.

1994-01-01

Springtime microwave brightness temperatures over first-year ice are examined for the southern Kara Sea. Snow emissivity changes are revealed by episodic drops in the 37- to 18-GHz brightness temperature gradient ratio measured by the Nimbus 7 scanning multichannel microwave radiometer. We suggest that the negative gradient ratios in spring 1982 result from increased scatter at 37 GHz due to the formation of a near-surface hoar layer. This interpretation is supported by the results of a surface radiation balance model that shows the melt signature occurring at below freezing temperatures but under clear-sky conditions with increased solar input to the surface. Published observations from the Greenland ice cap show a surface hoar layer forming under similar atmospheric conditions owing to the increased penetration and absorption of solar radiation just below the surface layer. In spring/early summer 1984 similar gradient ratio signatures occur. They appear to be due to several days of freeze-thaw cycling following the movement of a low-pressure system through the region. These changes in surface emissivity represent the transition from winter to summer conditions (as defined by the microwave response) and are shown to be regional in extent and to vary with the synoptic circulations.

Protein electron transfer: Dynamics and statistics

NASA Astrophysics Data System (ADS)

Matyushov, Dmitry V.

2013-07-01

Electron transfer between redox proteins participating in energy chains of biology is required to proceed with high energetic efficiency, minimizing losses of redox energy to heat. Within the standard models of electron transfer, this requirement, combined with the need for unidirectional (preferably activationless) transitions, is translated into the need to minimize the reorganization energy of electron transfer. This design program is, however, unrealistic for proteins whose active sites are typically positioned close to the polar and flexible protein-water interface to allow inter-protein electron tunneling. The high flexibility of the interfacial region makes both the hydration water and the surface protein layer act as highly polar solvents. The reorganization energy, as measured by fluctuations, is not minimized, but rather maximized in this region. Natural systems in fact utilize the broad breadth of interfacial electrostatic fluctuations, but in the ways not anticipated by the standard models based on equilibrium thermodynamics. The combination of the broad spectrum of static fluctuations with their dispersive dynamics offers the mechanism of dynamical freezing (ergodicity breaking) of subsets of nuclear modes on the time of reaction/residence of the electron at a redox cofactor. The separation of time-scales of nuclear modes coupled to electron transfer allows dynamical freezing. In particular, the separation between the relaxation time of electro-elastic fluctuations of the interface and the time of conformational transitions of the protein caused by changing redox state results in dynamical freezing of the latter for sufficiently fast electron transfer. The observable consequence of this dynamical freezing is significantly different reorganization energies describing the curvature at the bottom of electron-transfer free energy surfaces (large) and the distance between their minima (Stokes shift, small). The ratio of the two reorganization energies establishes the parameter by which the energetic efficiency of protein electron transfer is increased relative to the standard expectations, thus minimizing losses of energy to heat. Energetically efficient electron transfer occurs in a chain of conformationally quenched cofactors and is characterized by flattened free energy surfaces, reminiscent of the flat and rugged landscape at the stability basin of a folded protein.

Protein electron transfer: Dynamics and statistics.

PubMed

Matyushov, Dmitry V

2013-07-14

Electron transfer between redox proteins participating in energy chains of biology is required to proceed with high energetic efficiency, minimizing losses of redox energy to heat. Within the standard models of electron transfer, this requirement, combined with the need for unidirectional (preferably activationless) transitions, is translated into the need to minimize the reorganization energy of electron transfer. This design program is, however, unrealistic for proteins whose active sites are typically positioned close to the polar and flexible protein-water interface to allow inter-protein electron tunneling. The high flexibility of the interfacial region makes both the hydration water and the surface protein layer act as highly polar solvents. The reorganization energy, as measured by fluctuations, is not minimized, but rather maximized in this region. Natural systems in fact utilize the broad breadth of interfacial electrostatic fluctuations, but in the ways not anticipated by the standard models based on equilibrium thermodynamics. The combination of the broad spectrum of static fluctuations with their dispersive dynamics offers the mechanism of dynamical freezing (ergodicity breaking) of subsets of nuclear modes on the time of reaction/residence of the electron at a redox cofactor. The separation of time-scales of nuclear modes coupled to electron transfer allows dynamical freezing. In particular, the separation between the relaxation time of electro-elastic fluctuations of the interface and the time of conformational transitions of the protein caused by changing redox state results in dynamical freezing of the latter for sufficiently fast electron transfer. The observable consequence of this dynamical freezing is significantly different reorganization energies describing the curvature at the bottom of electron-transfer free energy surfaces (large) and the distance between their minima (Stokes shift, small). The ratio of the two reorganization energies establishes the parameter by which the energetic efficiency of protein electron transfer is increased relative to the standard expectations, thus minimizing losses of energy to heat. Energetically efficient electron transfer occurs in a chain of conformationally quenched cofactors and is characterized by flattened free energy surfaces, reminiscent of the flat and rugged landscape at the stability basin of a folded protein.

Perspective: Surface freezing in water: A nexus of experiments and simulations

NASA Astrophysics Data System (ADS)

Haji-Akbari, Amir; Debenedetti, Pablo G.

2017-08-01

Surface freezing is a phenomenon in which crystallization is enhanced at a vapor-liquid interface. In some systems, such as n-alkanes, this enhancement is dramatic and results in the formation of a crystalline layer at the free interface even at temperatures slightly above the equilibrium bulk freezing temperature. There are, however, systems in which the enhancement is purely kinetic and only involves faster nucleation at or near the interface. The first, thermodynamic, type of surface freezing is easier to confirm in experiments, requiring only the verification of the existence of crystalline order at the interface. The second, kinetic, type of surface freezing is far more difficult to prove experimentally. One material that is suspected of undergoing the second type of surface freezing is liquid water. Despite strong indications that the freezing of liquid water is kinetically enhanced at vapor-liquid interfaces, the findings are far from conclusive, and the topic remains controversial. In this perspective, we present a simple thermodynamic framework to understand conceptually and distinguish these two types of surface freezing. We then briefly survey fifteen years of experimental and computational work aimed at elucidating the surface freezing conundrum in water.

Spaceborne Microwave Remote Sensing of Seasonal Freeze-Thaw Processes in the Terrestrial High Latitudes: Relationships with Land-Atmosphere CO2 exchange

NASA Technical Reports Server (NTRS)

McDonald, Kyle C.; Kimball, John S.; Zhao, Maosheng; Njoku, Eni; Zimmermann, Reiner; Running, Steven W.

2004-01-01

Landscape transitions between seasonally frozen and thawed conditions occur each year over roughly 50 million square kilometers of Earth's Northern Hemisphere. These relatively abrupt transitions represent the closest analog to a biospheric and hydrologic on/off switch existing in nature, affecting surface meteorological conditions, ecological trace gas dynamics, energy exchange and hydrologic activity profoundly. We utilize time series satellite-borne microwave remote sensing measurements from the Special Sensor Microwave Imager (SSM/I) to examine spatial and temporal variability in seasonal freeze/thaw cycles for the pan-Arctic basin and Alaska. Regional measurements of spring thaw timing are derived using daily brightness temperature measurements from the 19 GHz, horizontally polarized channel, separately for overpasses with 6 AM and 6 PM equatorial crossing times. Spatial and temporal patterns in regional freeze/thaw dynamics show distinct differences between North America and Eurasia, and boreal forest and Arctic tundra biomes. Annual anomalies in the timing of thawing in spring also correspond closely to seasonal atmospheric CO2 concentration anomalies derived from NOAA CMDL arctic and subarctic monitoring stations. Classification differences between AM and PM overpass data average approximately 5 days for the region, though both appear to be effective surrogates for monitoring annual growing seasons at high latitudes.

Spaceborne microwave remote sensing of seasonal freeze-thaw processes in theterrestrial high l atitudes : relationships with land-atmosphere CO2 exchange

NASA Technical Reports Server (NTRS)

McDonald, Kyle C.; Kimball, John S.; Zhao, Maosheng; Njoku, Eni; Zimmermann, Reiner; Running, Steven W.

2004-01-01

Landscape transitions between seasonally frozen and thawed conditions occur each year over roughly 50 million square kilometers of Earth's Northern Hemisphere. These relatively abrupt transitions represent the closest analog to a biospheric and hydrologic on/off switch existing in nature, affecting surface meteorological conditions, ecological trace gas dynamics, energy exchange and hydrologic activity profoundly. We utilize time series satellite-borne microwave remote sensing measurements from the Special Sensor Microwave Imager (SSM/I) to examine spatial and temporal variability in seasonal freeze/thaw cycles for the pan-Arctic basin and Alaska. Regional measurements of spring thaw timing are derived using daily brightness temperature measurements from the 19 GHz, horizontally polarized channel, separately for overpasses with 6 AM and 6 PM equatorial crossing times. Spatial and temporal patterns in regional freeze/thaw dynamics show distinct differences between North America and Eurasia, and boreal forest and Arctic tundra biomes. Annual anomalies in the timing of thawing in spring also correspond closely to seasonal atmospheric CO2 concentration anomalies derived from NOAA CMDL arctic and subarctic monitoring stations. Classification differences between AM and PM overpass data average approximately 5 days for the region, though both appear to be effective surrogates for monitoring annual growing seasons at high latitudes.

Mannitol/l-Arginine-Based Formulation Systems for Freeze Drying of Protein Pharmaceuticals: Effect of the l-Arginine Counter Ion and Formulation Composition on the Formulation Properties and the Physical State of Mannitol.

PubMed

Stärtzel, Peter; Gieseler, Henning; Gieseler, Margit; Abdul-Fattah, Ahmad M; Adler, Michael; Mahler, Hanns-Christian; Goldbach, Pierre

2016-10-01

Previous studies have shown that protein storage stability in freeze-dried l-arginine-based systems improved in the presence of chloride ions. However, chloride ions reduced the glass transition temperature of the freeze concentrate (Tg') and made freeze drying more challenging. In this study, l-arginine was freeze dried with mannitol to obtain partially crystalline solids that can be freeze dried in a fast process and result in elegant cakes. We characterized the effect of different l-arginine counter ions on physicochemical properties of mannitol compared with mannitol/sucrose systems. Thermal properties of formulations with different compositions were correlated to thermal history during freeze drying and to physicochemical properties (cake appearance, residual moisture, reconstitution time, crystallinity). Partially crystalline solids were obtained even at the highest l-arginine level (mannitol:l-arginine of 2:1) used in this study. All l-arginine-containing formulations yielded elegant cakes. Only cakes containing l-arginine chloride and succinate showed a surface "crust" formed by phase separation. X-ray powder diffraction showed that inhibition of mannitol crystallization was stronger for l-arginine compared with sucrose and varied with the type of l-arginine counter ion. The counter ion affected mannitol polymorphism and higher levels of mannitol hemi-hydrate were obtained at high levels of l-arginine chloride. Copyright © 2016 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

Advances in heterogeneous ice nucleation research: Theoretical modeling and measurements

NASA Astrophysics Data System (ADS)

Beydoun, Hassan

In the atmosphere, cloud droplets can remain in a supercooled liquid phase at temperatures as low as -40 °C. Above this temperature, cloud droplets freeze via heterogeneous ice nucleation whereby a rare and poorly understood subset of atmospheric particles catalyze the ice phase transition. As the phase state of clouds is critical in determining their radiative properties and lifetime, deficiencies in our understanding of heterogeneous ice nucleation poses a large uncertainty on our efforts to predict human induced global climate change. Experimental challenges in properly simulating particle-induced freezing processes under atmospherically relevant conditions have largely contributed to the absence of a well-established model and parameterizations that accurately predict heterogeneous ice nucleation. Conversely, the sparsity of reliable measurement techniques available struggle to be interpreted by a single consistent theoretical or empirical framework, which results in layers of uncertainty when attempting to extrapolate useful information regarding ice nucleation for use in atmospheric cloud models. In this dissertation a new framework for describing heterogeneous ice nucleation is developed. Starting from classical nucleation theory, the surface of an ice nucleating particle is treated as a continuum of heterogeneous ice nucleating activity and a particle specific distribution of this activity g is derived. It is hypothesized that an individual particle species exhibits a critical surface area. Above this critical area the ice nucleating activity of a particle species can be described by one g distribution, g, while below it g expresses itself expresses externally resulting in particle to particle variability in ice nucleating activity. The framework is supported by cold plate droplet freezing measurements for dust and biological particles in which the total surface area of particle material available is varied. Freezing spectra above a certain surface area are shown to be successfully fitted with g while a process of random sampling from g can predict the freezing behavior below the identified critical surface area threshold. The framework is then extended to account for droplets composed of multiple particle species and successfully applied to predict the freezing spectra of a mixed proxy for an atmospheric dust-biological particle system. The contact freezing mode of ice nucleation, whereby a particle induces freezing upon collision with a droplet, is thought to be more efficient than particle initiated immersion freezing from within the droplet bulk. However, it has been a decades' long challenge to accurately measure this ice nucleation mode, since it necessitates reliably measuring the rate at which particles hit a droplet surface combined with direct determination of freezing onset. In an effort to remedy this longstanding deficiency a temperature controlled chilled aerosol optical tweezers capable of stably isolating water droplets in air at subzero temperatures has been designed and implemented. The new temperature controlled system retains the powerful capabilities of traditional aerosol optical tweezers: retrieval of a cavity enhanced Raman spectrum which could be used to accurately determine the size and refractive index of a trapped droplet. With these capabilities, it is estimated that the design can achieve ice supersaturation conditions at the droplet surface. It was also found that a KCl aqueous droplet simultaneously cooling and evaporating exhibited a significantly higher measured refractive index at its surface than when it was held at a steady state temperature. This implies the potential of a "salting out" process. Sensitivity of the cavity enhanced Raman spectrum as well as the visual image of a trapped droplet to dust particle collisions is shown, an important step in measuring collision frequencies of dust particles with a trapped droplet. These results may pave the way for future experiments of the exceptionally poorly understood contact freezing mode of ice nucleation.

Near-Surface Profiles of Water Stable Isotope Components and Indicated Transitional History of Ice-Wedge Polygons Near Barrow

NASA Astrophysics Data System (ADS)

Iwahana, G.; Wilson, C.; Newman, B. D.; Heikoop, J. M.; Busey, R.

2017-12-01

Wetlands associated with ice-wedge polygons are commonly distributed across the Arctic Coastal Plain of northern Alaska, a region underlain by continuous permafrost. Micro-topography of the ice-wedge polygons controls local hydrology, and the micro-topography could be altered due to factors such like surface vegetation, wetness, freeze-thaw cycles, and permafrost degradation/aggradation under climate change. Understanding status of the wetlands in the near future is important because it determines biogeochemical cycle, which drives release of greenhouse gases from the ground. However, transitional regime of the ice-wedge polygons under the changing climate is not fully understood. In this study, we analyzed geochemistry of water extracted from frozen soil cores sampled down to about 1m depth in 2014 March at NGEE-Arctic sites in the Barrow Environmental Observatory. The cores were sampled from troughs/rims/centers of five different low-centered or flat-centered polygons. The frozen cores are divided into 5-10cm cores for each location, thawed in sealed plastic bags, and then extracted water was stored in vials. Comparison between the profiles of geochemistry indicated connection of soil water in the active layer at different location in a polygon, while it revealed that distinctly different water has been stored in permafrost layer at troughs/rims/centers of some polygons. Profiles of volumetric water content (VWC) showed clear signals of freeze-up desiccation in the middle of saturated active layers as low VWC anomalies at most sampling points. Water in the active layer and near-surface permafrost was classified into four categories: ice wedge / fresh meteoric / transitional / highly fractionated water. The overall results suggested prolonged separation of water in the active layer at the center of low-centered polygons without lateral connection in water path in the past.

Critical viewpoints on the methods of realizing the metal freezing points of the ITS-90

NASA Astrophysics Data System (ADS)

Ma, C. K.

1995-08-01

The time-honored method for realizing the freezing point tf of a metal (in practice necessarily a dilute alloy) is that of continuous, slow freezing where the plateau temperature (which is the result of solidifying material's being so pure that its phase-transition temperature is observably constant) is measured. The freezing point being an equilibrium temperature, Ancsin considers this method to be inappropriate in principle: equilibrium between the solid and liquid phases cannot be achieved while the solid is being cooled to dispose of the releasing latent heat and while it is accreting at the expense of the liquid. In place of the continuous freezing method he has employed the pulse-heating method (in which the sample is allowed to approach equilibrium after each heat pulse) in his study of Ag; his measurements suggest that freezing can produce non-negligible errors. Here we examine both methods and conclude that the freezing method, employing an inside solid-liquid interface thermally isolated by an outside interface, can provide realizations of the highest accuracy; in either method, perturbation, by inducing solid-liquid phase transition continuously or intermittently, is essential for detecting equilibrium thermally. The respective merits and disadvantages of these two methods and also of the inner-melt method are discussed. We conclude that in a freezing-point measurement what is being measured is in effect the however minutely varying phase transition, and nonconstitutional equilibrium, temperature ti at the solid-liquid interface. The objective is then to measure the ti that is the best measure of tf, which is, normally, the plateau temperature.

Free volume distribution of branched poly(methyl methacrylates): Conformational probes study

NASA Astrophysics Data System (ADS)

Kamalova, D. I.; Remizov, A. B.

2016-12-01

In this work we studied the free volume distribution of the branched poly (methylmethacrylates) by the method of conformational probes. The freezing temperatures of the conformational transitions of the probes introduced into branched polymers were determined by FTIR spectra. The influence of covalently connected fullerene С60 on the freezing temperatures of conformational transitions was shown.

Effects of molecular elongation on liquid crystalline phase behaviour: isotropic-nematic transition

NASA Astrophysics Data System (ADS)

Singh, Ram Chandra; Ram, Jokhan

2003-08-01

We present the density-functional approach to study the isotropic-nematic transitions and calculate the values of freezing parameters of the Gay-Berne liquid crystal model, concentrating on the effects of varying the molecular elongation, x0. For this, we have solved the Percus-Yevick integral equation theory to calculate the pair-correlation functions of a fluid the molecules of which interact via a Gay-Berne pair potential. These results have been used in the density-functional theory as an input to locate the isotropic-nematic transition and calculate freezing parameters for a range of length-to-width parameters 3.0⩽ x0⩽4.0 at reduced temperatures 0.95 and 1.25. We observed that as x0 is increased, the isotropic-nematic transition is seen to move to lower density at a given temperature. We find that the density-functional theory is good to study the freezing transitions in such fluids. We have also compared our results with computer simulation results wherever they are available.

The Interdependence of Lake Ice and Climate in Central North America. [correlation between freeze/than cycles of lakes and regional weather variations

NASA Technical Reports Server (NTRS)

Jelacic, A. J. (Principal Investigator)

1973-01-01

The author has identified the following significant results. A comparison of lake freeze transition zone migration with the movement of large pressure centers reveals the following consistencies: (1) polar continental cyclones originate within and/or travel along the trend of the transition zone; (2) polar continental anticyclones fail to cross the transition zone; (3) polar outbreak anticyclones pass through the transition zone, apparently unaffected. In addition, storm centers associated with the transition zone undergo significant intensification manifest by a deepening of the pressure through and increased precipitation outside the zone.

Response of seasonal soil freeze depth to climate change across China

NASA Astrophysics Data System (ADS)

Peng, Xiaoqing; Zhang, Tingjun; Frauenfeld, Oliver W.; Wang, Kang; Cao, Bin; Zhong, Xinyue; Su, Hang; Mu, Cuicui

2017-05-01

The response of seasonal soil freeze depth to climate change has repercussions for the surface energy and water balance, ecosystems, the carbon cycle, and soil nutrient exchange. Despite its importance, the response of soil freeze depth to climate change is largely unknown. This study employs the Stefan solution and observations from 845 meteorological stations to investigate the response of variations in soil freeze depth to climate change across China. Observations include daily air temperatures, daily soil temperatures at various depths, mean monthly gridded air temperatures, and the normalized difference vegetation index. Results show that soil freeze depth decreased significantly at a rate of -0.18 ± 0.03 cm yr-1, resulting in a net decrease of 8.05 ± 1.5 cm over 1967-2012 across China. On the regional scale, soil freeze depth decreases varied between 0.0 and 0.4 cm yr-1 in most parts of China during 1950-2009. By investigating potential climatic and environmental driving factors of soil freeze depth variability, we find that mean annual air temperature and ground surface temperature, air thawing index, ground surface thawing index, and vegetation growth are all negatively associated with soil freeze depth. Changes in snow depth are not correlated with soil freeze depth. Air and ground surface freezing indices are positively correlated with soil freeze depth. Comparing these potential driving factors of soil freeze depth, we find that freezing index and vegetation growth are more strongly correlated with soil freeze depth, while snow depth is not significant. We conclude that air temperature increases are responsible for the decrease in seasonal freeze depth. These results are important for understanding the soil freeze-thaw dynamics and the impacts of soil freeze depth on ecosystem and hydrological process.

Bulk water freezing dynamics on superhydrophobic surfaces

NASA Astrophysics Data System (ADS)

Chavan, S.; Carpenter, J.; Nallapaneni, M.; Chen, J. Y.; Miljkovic, N.

2017-01-01

In this study, we elucidate the mechanisms governing the heat-transfer mediated, non-thermodynamic limited, freezing delay on non-wetting surfaces for a variety of characteristic length scales, Lc (volume/surface area, 3 mm < Lc < 6 mm) using carefully designed freezing experiments in a temperature-controlled, zero-humidity environment on thin water slabs. To probe the effect of surface wettability, we investigated the total time for room temperature water to completely freeze into ice on superhydrophilic ( θaapp→ 0°), hydrophilic (0° < θa < 90°), hydrophobic (90° < θa < 125°), and superhydrophobic ( θaapp→ 180°) surfaces. Our results show that at macroscopic length scales, heat conduction through the bulk water/ice layer dominates the freezing process when compared to heat conduction through the functional coatings or nanoscale gaps at the superhydrophobic substrate-water/ice interface. In order to verify our findings, and to determine when the surface structure thermal resistance approaches the water/ice resistance, we fabricated and tested the additional substrates coated with commercial superhydrophobic spray coatings, showing a monotonic increase in freezing time with coating thickness. The added thermal resistance of thicker coatings was much larger than that of the nanoscale superhydrophobic features, which reduced the droplet heat transfer and increased the total freezing time. Transient finite element method heat transfer simulations of the water slab freezing process were performed to calculate the overall heat transfer coefficient at the substrate-water/ice interface during freezing, and shown to be in the range of 1-2.5 kW/m2K for these experiments. The results shown here suggest that in order to exploit the heat-transfer mediated freezing delay, thicker superhydrophobic coatings must be deposited on the surface, where the coating resistance is comparable to the bulk water/ice conduction resistance.

Delay in the Freezing of Supercooled Water Drops on Superhydrophobic Surfaces of Silicone Rubber at Negative Temperatures

NASA Astrophysics Data System (ADS)

Bezdomnikov, A. A.; Emel'yanenko, A. M.; Emel'yanenko, K. A.; Boinovich, L. B.

2018-01-01

A method is proposed for fabricating textured superhydrophobic surfaces of silicone rubber with mechanical resistance toward liquid or freezing aqueous solutions. The anti-icing characteristics of silicone rubber samples that differ in the wetting characteristics and mechanical stability of their micro- and nanotextures are derived by analyzing the delays in the freezing of supercooled sessile water drops deposited on the sample surface. The longest delay in freezings are observed for sessile water drops on superhydrophobic surfaces prepared by laser texturing with subsequent application of a layer of a hydrophobic agent to consolidate the textural elements. Delay in freezings can be as long as tens of hours on such surfaces at T = -18°C. The prepared superhydrophobic surfaces exhibit greater anti-icing ability with respect to aqueous salt solutions than to deionized water.

Dynamic freeze-in: impact of thermal masses and cosmological phase transitions on dark matter production

NASA Astrophysics Data System (ADS)

Baker, Michael J.; Breitbach, Moritz; Kopp, Joachim; Mittnacht, Lukas

2018-03-01

The cosmological abundance of dark matter can be significantly influenced by the temperature dependence of particle masses and vacuum expectation values. We illustrate this point in three simple freeze-in models. The first one, which we call kinematically induced freeze-in, is based on the observation that the effective mass of a scalar temporarily becomes very small as the scalar potential undergoes a second order phase transition. This opens dark matter production channels that are otherwise forbidden. The second model we consider, dubbed vev-induced freeze-in, is a fermionic Higgs portal scenario. Its scalar sector is augmented compared to the Standard Model by an additional scalar singlet, S, which couples to dark matter and temporarily acquires a vacuum expectation value (a two-step phase transition or "vev flip-flop"). While < S> ≠ 0, the modified coupling structure in the scalar sector implies that dark matter production is significantly enhanced compared to the < S> = 0 phases realised at very early times and again today. The third model, which we call mixing-induced freeze-in, is similar in spirit, but here it is the mixing of dark sector fermions, induced by non-zero < S>, that temporarily boosts the dark matter production rate. For all three scenarios, we carefully dissect the evolution of the dark sector in the early Universe. We compute the DM relic abundance as a function of the model parameters, emphasising the importance of thermal corrections and the proper treatment of phase transitions in the calculation.

Characterization of freezing precipitation events through other meteorological variables and their recent changes over Northern Extratropics

NASA Astrophysics Data System (ADS)

Groisman, P. Y.; Yin, X.; Bulygina, O.

2017-12-01

Freezing precipitation events intertwine with agriculture, recreation, energy consumption, and seasonal transportation cycles of human activities. Using supplementary synoptic reports at 1,500 long-term stations of North America and Northern Eurasia, we created climatology of freezing precipitation near the surface and found significant changes (increases) in these occurrences in the past decade at high latitudes/elevations (Groisman et al. 2016; updated). Firstly, we document narrow boundaries of near surface temperature and humidity fields when freezing precipitation events occur; these are necessary but insufficient conditions of their occurrence. Secondly, using the upper air data at the sites collocated with in situ observations of freezing events, we quantify the typical pattern of lower troposphere temperature anomalies during freezing events: At the same locations and Julian days, the presence of freezing event at the surface is associated with significantly warmer temperatures in the lower troposphere; comparison of temperatures at nearest days before and after the freezing events with days during these events also shows statistically significant positive temperature anomalies in the lower troposphere to 500 hPa (on average, +3 to 4 °C) In the days with freezing events, vertical air temperature gradients between surface and 850 hPa become less than usual with frequent inversions, when the tropospheric air is warmer than at the surface. The above features of the lower tropospheric temperature, near-surface temperature and humidity represent a combination of weather conditions conducive for precipitation, if it happens, falling in the freezing rain form. The in situ reports of freezing events at synoptic stations allow us to estimate temporary and spatial distributions of such "special weather conditions". Thus, a posteriori high probability of freezing events under these weather conditions invokes similar probabilities of freezing rain over the ungauged terrain, where we do not have special synoptic reports but can reproduce these "special weather conditions" from less sophisticated observational networks and/or reanalyses. Reference: Groisman et al. 2016: Recent changes in the frequency of freezing precipitation in North America and Northern Eurasia. Environ Res Lett 11 045007.

Dynamic Melting of Freezing Droplets on Ultraslippery Superhydrophobic Surfaces.

PubMed

Chu, Fuqiang; Wu, Xiaomin; Wang, Lingli

2017-03-08

Condensed droplet freezing and freezing droplet melting phenomena on the prepared ultraslippery superhydrophobic surface were observed and discussed in this study. Although the freezing delay performance of the surface is common, the melting of the freezing droplets on the surface is quite interesting. Three self-propelled movements of the melting droplets (ice- water mixture) were found including the droplet rotating, the droplet jumping, and the droplet sliding. The melting droplet rotating, which means that the melting droplet rotates spontaneously on the superhydrophobic surface like a spinning top, is first reported in this study and may have some potential applications in various engineering fields. The melting droplet jumping and sliding are similar to those occurring during condensation but have larger size scale and motion scale, as the melting droplets have extra-large specific surface area with much more surface energy available. These self-propelled movements make all the melting droplets on the superhydrophobic surface dynamic, easily removed, which may be promising for the anti-icing/frosting applications.

Induction of DREB2A pathway with repression of E2F, Jasmonic acid biosynthetic and photosynthesis pathways in cold acclimation specific freeze resistant wheat crown

USDA-ARS?s Scientific Manuscript database

Winter wheat lines can achieve cold acclimation (development of tolerance to freezing temperatures) and vernalization (delay in transition from vegetative to reproductive phase) in response to low non-freezing temperatures. To describe cold acclimation specific processes and pathways, we utilized co...

Effect of particle surface area on ice active site densities retrieved from droplet freezing spectra

NASA Astrophysics Data System (ADS)

Beydoun, Hassan; Polen, Michael; Sullivan, Ryan C.

2016-10-01

Heterogeneous ice nucleation remains one of the outstanding problems in cloud physics and atmospheric science. Experimental challenges in properly simulating particle-induced freezing processes under atmospherically relevant conditions have largely contributed to the absence of a well-established parameterization of immersion freezing properties. Here, we formulate an ice active, surface-site-based stochastic model of heterogeneous freezing with the unique feature of invoking a continuum assumption on the ice nucleating activity (contact angle) of an aerosol particle's surface that requires no assumptions about the size or number of active sites. The result is a particle-specific property g that defines a distribution of local ice nucleation rates. Upon integration, this yields a full freezing probability function for an ice nucleating particle. Current cold plate droplet freezing measurements provide a valuable and inexpensive resource for studying the freezing properties of many atmospheric aerosol systems. We apply our g framework to explain the observed dependence of the freezing temperature of droplets in a cold plate on the concentration of the particle species investigated. Normalizing to the total particle mass or surface area present to derive the commonly used ice nuclei active surface (INAS) density (ns) often cannot account for the effects of particle concentration, yet concentration is typically varied to span a wider measurable freezing temperature range. A method based on determining what is denoted an ice nucleating species' specific critical surface area is presented and explains the concentration dependence as a result of increasing the variability in ice nucleating active sites between droplets. By applying this method to experimental droplet freezing data from four different systems, we demonstrate its ability to interpret immersion freezing temperature spectra of droplets containing variable particle concentrations. It is shown that general active site density functions, such as the popular ns parameterization, cannot be reliably extrapolated below this critical surface area threshold to describe freezing curves for lower particle surface area concentrations. Freezing curves obtained below this threshold translate to higher ns values, while the ns values are essentially the same from curves obtained above the critical area threshold; ns should remain the same for a system as concentration is varied. However, we can successfully predict the lower concentration freezing curves, which are more atmospherically relevant, through a process of random sampling from g distributions obtained from high particle concentration data. Our analysis is applied to cold plate freezing measurements of droplets containing variable concentrations of particles from NX illite minerals, MCC cellulose, and commercial Snomax bacterial particles. Parameterizations that can predict the temporal evolution of the frozen fraction of cloud droplets in larger atmospheric models are also derived from this new framework.

A comparative study of spray-dried and freeze-dried hydrocortisone/polyvinyl pyrrolidone solid dispersions.

PubMed

Dontireddy, Rakesh; Crean, Abina M

2011-10-01

Poor water solubility of new chemical entities (NCEs) is one of the major challenges the pharmaceutical industry currently faces. The purpose of this study was to investigate the feasibility of freeze-drying as an alternative technique to spray-drying to produce solid dispersions of poorly water-soluble drugs. Also investigated was the use of aqueous solvent mixtures in place of pure solvent for the production of solid dispersions. Aqueous solvent systems would reduce the environmental impact of pure organic solvent systems. Spray-dried and freeze-dried hydrocortisone/polyvinyl pyrrolidone solid dispersions exhibited differences in dissolution behavior. Freeze-dried dispersions exhibited faster dissolution rates than the corresponding spray-dried dispersions. Spray-dried systems prepared using both solvent systems (20% v/v and 96% v/v ethanol) displayed similar dissolution performance despite displaying differences in glass transition temperatures (T(g)) and surface areas. All dispersions showed drug/polymer interactions indicated by positive deviations in T(g) from the predicted values calculated using the Couchman-Karasz equation. Fourier transform infrared (FTIR) spectroscopic results confirmed the conversion of crystalline drug to the amorphous in the dispersions. Stability studies were preformed at 40°C and 75% relative humidity to investigate the physical stability of prepared dispersions. Recrystallization was observed after a month and the resultant dispersions were tested for their dissolution performance to compare with the dissolution performance of the dispersions prior to the stability study. The dissolution rate of the freeze-dried dispersions remained higher than both spray-dried dispersions after storage.

Annealing to optimize the primary drying rate, reduce freezing-induced drying rate heterogeneity, and determine T(g)' in pharmaceutical lyophilization.

PubMed

Searles, J A; Carpenter, J F; Randolph, T W

2001-07-01

In a companion paper we show that the freezing of samples in vials by shelf-ramp freezing results in significant primary drying rate heterogeneity because of a dependence of the ice crystal size on the nucleation temperature during freezing.1 The purpose of this study was to test the hypothesis that post-freezing annealing, in which the product is held at a predetermined temperature for a specified duration, can reduce freezing-induced heterogeneity in sublimation rates. In addition, we test the impact of annealing on primary drying rates. Finally, we use the kinetics of relaxations during annealing to provide a simple measurement of T(g)', the glass transition temperature of the maximally freeze-concentrated amorphous phase, under conditions and time scales most appropriate for industrial lyophilization cycles. Aqueous solutions of hydroxyethyl starch (HES), sucrose, and HES:sucrose were either frozen by placement on a shelf while the temperature was reduced ("shelf-ramp frozen") or by immersion into liquid nitrogen. Samples were then annealed for various durations over a range of temperatures and partially lyophilized to determine the primary drying rate. The morphology of fully dried liquid nitrogen-frozen samples was examined using scanning electron microscopy. Annealing reduced primary drying rate heterogeneity for shelf-ramp frozen samples, and resulted in up to 3.5-fold increases in the primary drying rate. These effects were due to increased ice crystal sizes, simplified amorphous structures, and larger and more numerous holes on the cake surface of annealed samples. Annealed HES samples dissolved slightly faster than their unannealed counterparts. Annealing below T(g)' did not result in increased drying rates. We present a simple new annealing-lyophilization method of T(g)' determination that exploits this phenomenon. It can be carried out with a balance and a freeze-dryer, and has the additional advantage that a large number of candidate formulations can be evaluated simultaneously.

Freezing of soft spheres: A critical test for weighted-density-functional theories

NASA Astrophysics Data System (ADS)

Laird, Brian B.; Kroll, D. M.

1990-10-01

We study the freezing properties of systems with inverse-power and Yukawa interactions (soft spheres), using recently developed weighted-density-functional theories. We find that the modified weighted-density-functional approximation (MWDA) of Denton and Ashcroft yields results for the liquid to face-centered-cubic (fcc) structure transition that represent a significant improvement over those of earlier ``second-order'' density-functional freezing theories; however, this theory, like the earlier ones, fails to predict any liquid to body-centered-cubic (bcc) transition, even under conditions where the computer simulations indicate that this should be the equilibrium solid structure. In addition, we show that both the modified effective-liquid approximation (MELA) of Baus [J. Phys. Condens. Matter 2, 2111 (1990)] and the generalized effective-liquid approximation of Lutsko and Baus [Phys. Rev. Lett. 64, 761 (1990)], while giving excellent results for the freezing of hard spheres, fail completely to predict freezing into either fcc or bcc solid phases for soft inverse-power potentials. We also give an alternate derivation of the MWDA that makes clearer its connection to earlier theories.

Topological transitions and freezing in XY models and Coulomb gases with quenched disorder: renormalization via traveling waves

NASA Astrophysics Data System (ADS)

Carpentier, David; Le Doussal, Pierre

2000-11-01

We study the two dimensional XY model with quenched random phases and its Coulomb gas formulation. A novel renormalization group (RG) method is developed which allows to study perturbatively the glassy low temperature XY phase and the transition at which frozen topological defects (vortices) proliferate. This RG approach is constructed both from the replicated Coulomb gas and, equivalently without the use of replicas, using the probability distribution of the local disorder (random defect core energy). By taking into account the fusion of environments (i.e., charge fusion in the replicated Coulomb gas) this distribution is shown to obey a Kolmogorov's type (KPP) non linear RG equation which admits traveling wave solutions and exhibits a freezing phenomenon analogous to glassy freezing in Derrida's random energy models. The resulting physical picture is that the distribution of local disorder becomes broad below a freezing temperature and that the transition is controlled by rare favorable regions for the defects, the density of which can be used as the new perturbative parameter. The determination of marginal directions at the disorder induced transition is shown to be related to the well studied front velocity selection problem in the KPP equation and the universality of the novel critical behaviour obtained here to the known universality of the corrections to the front velocity. Applications to other two dimensional problems are mentioned at the end.

Freeze-cast alumina pore networks: Effects of freezing conditions and dispersion medium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Miller, S. M.; Xiao, X.; Faber, K. T.

Alumina ceramics were freeze-cast from water- and camphene-based slurries under varying freezing conditions and examined using X-ray computed tomography (XCT). Pore network characteristics, i.e., porosity, pore size, geometric surface area, and tortuosity, were measured from XCT reconstructions and the data were used to develop a model to predict feature size from processing conditions. Classical solidification theory was used to examine relationships between pore size, temperature gradients, and freezing front velocity. Freezing front velocity was subsequently predicted from casting conditions via the two-phase Stefan problem. Resulting models for water-based samples agreed with solidification-based theories predicting lamellar spacing of binary eutectic alloys,more » and models for camphene-based samples concurred with those for dendritic growth. Relationships between freezing conditions and geometric surface area were also modeled by considering the inverse relationship between pore size and surface area. Tortuosity was determined to be dependent primarily on the type of dispersion medium. (C) 2015 Elsevier Ltd. All rights reserved.« less

Theory of freezing in simple systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cerjan, C.; Bagchi, B.

The transition parameters for the freezing of two one-component liquids into crystalline solids are evaluated by two theoretical approaches. The first system considered is liquid sodium which crystallizes into a body-centered-cubic (bcc) lattice; the second system is the freezing of adhesive hard spheres into a face-centered-cubic (fcc) lattice. Two related theoretical techniques are used in this evaluation: One is based upon a recently developed bifurcation analysis; the other is based upon the theory of freezing developed by Ramakrishnan and Yussouff. For liquid sodium, where experimental information is available, the predictions of the two theories agree well with experiment and eachmore » other. The adhesive-hard-sphere system, which displays a triple point and can be used to fit some liquids accurately, shows a temperature dependence of the freezing parameters which is similar to Lennard-Jones systems. At very low temperature, the fractional density change on freezing shows a dramatic increase as a function of temperature indicating the importance of all the contributions due to the triplet direction correlation function. Also, we consider the freezing of a one-component liquid into a simple-cubic (sc) lattice by bifurcation analysis and show that this transition is highly unfavorable, independent of interatomic potential choice. The bifurcation diagrams for the three lattices considered are compared and found to be strikingly different. Finally, a new stability analysis of the bifurcation diagrams is presented.« less

Process Analytical Technology in Freeze-Drying: Detection of the Secondary Solute + Water Crystallization with Heat Flux Sensors.

PubMed

Wang, Qiming; Shalaev, Evgenyi

2018-04-01

In situ and non-invasive detection of solute crystallization during freeze-drying would facilitate cycle optimization and scale-up from the laboratory to commercial manufacturing scale. The objective of the study is to evaluate heat flux sensor (HFS) as a tool for monitoring solute crystallization and other first-order phase transitions (e.g., onset of freezing). HFS is a thin-film differential thermopile, which acts as a transducer to generate an electrical signal proportional to the total heat applied to its surface. In this study, HFS is used to detect both primary (ice formation) and secondary (also known as eutectic) solute + water crystallization during cooling and heating of solutions in a freeze-dryer. Binary water-solute mixtures with typical excipients concentrations (e.g., 0.9% of NaCl and 5% mannitol) and fill volumes (1 to 3 ml/vial) are studied. Secondary crystallization is detected by the HFS during cooling in all experiments with NaCl solutions, whereas timing of mannitol crystallization depends on the cooling conditions. In particular, mannitol crystallization takes place during cooling, if the cooling rate is lower than the critical value. On the other hand, if the cooling rate exceeds the critical cooling rate, mannitol crystallization during cooling is prevented, and crystallization occurs during subsequent warming or annealing. It is also observed that, while controlled ice nucleation allows initiation of the primary freezing event in different vials simultaneously, there is a noticeable vial-to-vial difference in the timing of secondary crystallization. The HFS could be a valuable process monitoring tool for non-invasive detection of various crystallization events during freeze-drying manufacturing.

Topological Spin Glass in Diluted Spin Ice

NASA Astrophysics Data System (ADS)

Sen, Arnab; Moessner, R.

2015-06-01

It is a salient experimental fact that a large fraction of candidate spin liquid materials freeze as the temperature is lowered. The question naturally arises whether such freezing is intrinsic to the spin liquid ("disorder-free glassiness") or extrinsic, in the sense that a topological phase simply coexists with standard freezing of impurities. Here, we demonstrate a surprising third alternative, namely, that freezing and topological liquidity are inseparably linked. The topological phase reacts to the introduction of disorder by generating degrees of freedom of a new type (along with interactions between them), which in turn undergo a freezing transition while the topological phase supporting them remains intact.

Topological Spin Glass in Diluted Spin Ice.

PubMed

Sen, Arnab; Moessner, R

2015-06-19

It is a salient experimental fact that a large fraction of candidate spin liquid materials freeze as the temperature is lowered. The question naturally arises whether such freezing is intrinsic to the spin liquid ("disorder-free glassiness") or extrinsic, in the sense that a topological phase simply coexists with standard freezing of impurities. Here, we demonstrate a surprising third alternative, namely, that freezing and topological liquidity are inseparably linked. The topological phase reacts to the introduction of disorder by generating degrees of freedom of a new type (along with interactions between them), which in turn undergo a freezing transition while the topological phase supporting them remains intact.

Satellite remote sensing of landscape freeze/thaw state dynamics for complex Topography and Fire Disturbance Areas Using multi-sensor radar and SRTM digital elevation models

NASA Technical Reports Server (NTRS)

Podest, Erika; McDonald, Kyle; Kimball, John; Randerson, James

2003-01-01

We characterize differences in radar-derived freeze/thaw state, examining transitions over complex terrain and landscape disturbance regimes. In areas of complex terrain, we explore freezekhaw dynamics related to elevation, slope aspect and varying landcover. In the burned regions, we explore the timing of seasonal freeze/thaw transition as related to the recovering landscape, relative to that of a nearby control site. We apply in situ biophysical measurements, including flux tower measurements to validate and interpret the remotely sensed parameters. A multi-scale analysis is performed relating high-resolution SAR backscatter and moderate resolution scatterometer measurements to assess trade-offs in spatial and temporal resolution in the remotely sensed fields.

Phase equilibrium in argon films stabilized by homogeneous surfaces and thermodynamics of two-stage melting transition.

PubMed

Ustinov, E A

2014-02-21

Freezing of gases adsorbed on open surfaces (e.g., graphite) and in narrow pores is a widespread phenomenon which is a subject of a large number of publications. Modeling of the gas/liquid-solid transition is usually accomplished with a molecular simulation technique. However, quantitative analysis of the gas/liquid-solid coexistence and thermodynamic properties of the solid layer still encounters serious difficulties. This is mainly due to the effect of simulation box size on the lattice constant. Since the lattice constant is a function of loading and temperature, once the ordering transition has occurred, the simulation box size must be corrected in the course of simulation according to the Gibbs-Duhem equation. A significant problem is also associated with accurate prediction of the two-dimensional liquid-solid coexistence because of a small difference in densities of coexisting phases. The aim of this study is thermodynamic analysis of the two-dimensional phase coexistence in systems involving crystal-like free of defects layers in narrow slit pores. A special attention was paid to the determination of triple point temperatures. It is shown that intrinsic properties of argon monolayer adsorbed on the graphite surface are similar to those of isolated monolayer accommodated in the slit pore having width of two argon collision diameters. Analysis of the latter system is shown to be clearer and less time-consuming than the former one, which has allowed for explanation of the experimentally observed two-stage melting transition of argon monolayer on graphite without invoking the periodic surface potential modulation and orientational transition.

Phase equilibrium in argon films stabilized by homogeneous surfaces and thermodynamics of two-stage melting transition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ustinov, E. A., E-mail: eustinov@mail.wplus.net

Freezing of gases adsorbed on open surfaces (e.g., graphite) and in narrow pores is a widespread phenomenon which is a subject of a large number of publications. Modeling of the gas/liquid–solid transition is usually accomplished with a molecular simulation technique. However, quantitative analysis of the gas/liquid–solid coexistence and thermodynamic properties of the solid layer still encounters serious difficulties. This is mainly due to the effect of simulation box size on the lattice constant. Since the lattice constant is a function of loading and temperature, once the ordering transition has occurred, the simulation box size must be corrected in the coursemore » of simulation according to the Gibbs–Duhem equation. A significant problem is also associated with accurate prediction of the two-dimensional liquid–solid coexistence because of a small difference in densities of coexisting phases. The aim of this study is thermodynamic analysis of the two-dimensional phase coexistence in systems involving crystal-like free of defects layers in narrow slit pores. A special attention was paid to the determination of triple point temperatures. It is shown that intrinsic properties of argon monolayer adsorbed on the graphite surface are similar to those of isolated monolayer accommodated in the slit pore having width of two argon collision diameters. Analysis of the latter system is shown to be clearer and less time-consuming than the former one, which has allowed for explanation of the experimentally observed two-stage melting transition of argon monolayer on graphite without invoking the periodic surface potential modulation and orientational transition.« less

Spontaneous De-Icing Phenomena on Extremely Cold Surfaces

NASA Astrophysics Data System (ADS)

Song, Dong; Choi, Chang-Hwan

2017-11-01

Freezing of droplets on cold surfaces is universal phenomenon, while the mechanisms are still inadequately understood. Here we report spontaneous de-icing phenomena of an impacting droplet which occur on extreme cold surfaces. When a droplet impacts on cold surfaces lower than -80°, it takes more than two times longer for the droplet to freeze than the ones at -50°. Moreover, the frozen droplet below -80° breaks up into several large parts spontaneously in the end. When a droplet impacts on the extreme cold surfaces, evaporation and condensation occur immediately as the droplet approaches the substrate. A thick layer of frost forms between the droplet and substrate, decreasing the contact area of the droplet with substrate. It leads to impede the heat transfer and hence extends the freezing time significantly. On the extremely cold substrate, the droplet freezes from the center to the edge area, in contrast to a typical case freezing from the bottom to the top. This novel from-center-to-edge freezing process changes the internal tension of the frozen droplet and results in the instantaneous breakup and release eventually, which can be taken advantage of for effective deicing mechanisms.

Correlation of Water Frost Porosity in Laminar Flow over Flat Surfaces

NASA Technical Reports Server (NTRS)

Kandula, Max

2011-01-01

A dimensionless correlation has been proposed for water frost porosity expressing its dependence on frost surface temperature and Reynolds number for laminar forced flow over a flat surface. The correlation is presented in terms of a dimensionless frost surface temperature scaled with the cold plate temperature, and the freezing temperature. The flow Reynolds number is scaled with reference to the critical Reynolds number for laminar-turbulent transition. The proposed correlation agrees satisfactorily with the simultaneous measurements of frost density and frost surface temperature covering a range of plate temperature, ambient air velocity, humidity, and temperature. It is revealed that the frost porosity depends primarily on the frost surface and the plate temperatures and the flow Reynolds number, and is only weakly dependent on the relative humidity. The results also point out the general character of frost porosity displaying a decrease with an increase in flow Reynolds number.

Wigner time-delay distribution in chaotic cavities and freezing transition.

PubMed

Texier, Christophe; Majumdar, Satya N

2013-06-21

Using the joint distribution for proper time delays of a chaotic cavity derived by Brouwer, Frahm, and Beenakker [Phys. Rev. Lett. 78, 4737 (1997)], we obtain, in the limit of the large number of channels N, the large deviation function for the distribution of the Wigner time delay (the sum of proper times) by a Coulomb gas method. We show that the existence of a power law tail originates from narrow resonance contributions, related to a (second order) freezing transition in the Coulomb gas.

Observation of glassy state relaxation during annealing of frozen sugar solutions by X-ray computed tomography.

PubMed

Nakagawa, Kyuya; Tamiya, Shinri; Do, Gabsoo; Kono, Shinji; Ochiai, Takaaki

2018-06-01

Glassy phase formation in a frozen product determines various properties of the freeze-dried products. When an aqueous solution is subjected to freezing, a glassy phase forms as a consequence of freeze-concentration. During post-freezing annealing, the relaxation of the glassy phase and the ripening of ice crystals (i.e. Ostwald ripening) spontaneously occur, where the kinetics are controlled by the annealing and glass transition temperatures. This study was motivated to observe the progress of glassy state relaxation separate from ice coarsening during annealing. X-ray computed tomography (CT) was used to observe a frozen and post-freezing annealed solutions by using monochromatized X-ray from the synchrotron radiation. CT images were successfully obtained, and the frozen matrix were analyzed based on the gray level values that were equivalent to the linear X-ray attenuation coefficients of the observed matters. The CT images obtained from rapidly frozen sucrose and dextrin solutions with different concentrations gave clear linear relationships between the linear X-ray attenuation coefficients values and the solute concentrations. It was confirmed that the glassy state relaxation progressed as increasing annealing time, and this trend was larger in the order of the glass transition temperature of the maximally freeze-concentrated phase. The sucrose-water system required nearly 20 h of annealing time at -5 °C for the completion of the glassy phase relaxation, whereas dextrin-water systems required much longer periods because of their higher glass transition temperatures. The trends of ice coarsening, however, did not perfectly correspond to the trends of the relaxation, suggesting that the glassy phase relaxation and Ostwald ripening would jointly control the ice crystal growth/ripening kinetics, and the dominant mechanism differed by the annealing stage. Copyright © 2018 Elsevier B.V. All rights reserved.

Aluminum Fixed Point: Impact of the Time Spent in the Liquid Phase on the Liquid-Solid Transition and Obviousness of the Pollution of the Ingot

NASA Astrophysics Data System (ADS)

Renaot, E.; Martin, C.

2011-08-01

In order to improve the uncertainty on the aluminum fixed point, a study was launched by Laboratoire Commun de Métrologie LNE-CNAM in the frame of the EURAMET Project 732 "Toward more accurate temperature fixed points" (coordinating laboratory: France, 17 partner countries). An earlier study completed in this laboratory showed that in regular realization of the melting-freezing plateaus, there is no diffusion of impurities in the thickness of the ingot, or the diffusion is excessively slow and cannot allow a uniform distribution of the impurities. On the other hand, it is frequently noticed that the experimental conditions before the freezing plateau have an impact on its characteristics (value, slope,…). Up to now, no systematic study was performed on the influence of this parameter. So, the objective of the task started recently in this laboratory is to investigate the influence of the time spent in the liquid phase on the phase transition. As a final result, it is demonstrated that in order to reach the equilibrium of the concentration of impurities, it is necessary to ensure that the metal remains in the liquid phase at least 24 h before initiating the freeze. At the end of the process, the aluminum ingot was chemically analyzed. The analyses reveal large contaminations of the surface of the ingot (sodium, sulfur, and phosphorus). One of the important outputs of this study is that the conditions of usage of the cells should be given important attention since large contaminations can be brought by the furnace.

Spacecraft Radiator Freeze Protection Using a Regenerative Heat Exchanger with Bypass Setpoint Temperature Control

NASA Technical Reports Server (NTRS)

Ungar, Eugene K.

2008-01-01

Spacecraft radiators are sized for their maximum heat load in their warmest thermal environment, but must operate at reduced heat loads and in colder environments. For systems where the radiator environment can be colder than the working fluid freezing temperature, radiator freezing becomes an issue. Radiator freezing has not been a major issue for the Space Shuttle and the International Space Station (ISS) active thermal control systems (ATCSs) because they operate in environments that are warm relative to the freezing point of their external coolants (Freon-21 and ammonia, respectively). For a vehicle that lands at the Lunar South Pole, the design thermal environment is 215K, but the radiator working fluid must also be kept from freezing during the 0 K sink of transit. A radiator bypass flow control design such as those used on the Space Shuttle and ISS requires more than 30% of the design heat load to avoid radiator freezing during transit - even with a very low freezing point working fluid. By changing the traditional ATCS architecture to include a regenerating heat exchanger inboard of the radiator and by using a regenerator bypass flow control valve to maintain system setpoint, the required minimum heat load can be reduced by more than half. This gives the spacecraft much more flexibility in design and operation. The present work describes the regenerator bypass ATCS setpoint control methodology. It includes analytical results comparing the performance of this system to the traditional radiator bypass system. Finally, a summary of the advantages of the regenerator bypass system are presented.

Two Glass Transitions Associated to Different Dynamic Disorders in the Nematic Glassy State of a Non-Symmetric Liquid Crystal Dimer Dopped with γ-Alumina Nanoparticles

PubMed Central

Diez-Berart, Sergio; López, David O.; Salud, Josep; Diego, José Antonio; Sellarès, Jordi; Robles-Hernández, Beatriz; de la Fuente, María Rosario; Ros, María Blanca

2015-01-01

In the present work, the nematic glassy state of the non-symmetric LC dimer α-(4-cyanobiphenyl-4′-yloxy)-ω-(1-pyrenimine-benzylidene-4′-oxy) undecane is studied by means of calorimetric and dielectric measurements. The most striking result of the work is the presence of two different glass transition temperatures: one due to the freezing of the flip-flop motions of the bulkier unit of the dimer and the other, at a lower temperature, related to the freezing of the flip-flop and precessional motions of the cyanobiphenyl unit. This result shows the fact that glass transition is the consequence of the freezing of one or more coupled dynamic disorders and not of the disordered phase itself. In order to avoid crystallization when the bulk sample is cooled down, the LC dimer has been confined via the dispersion of γ-alumina nanoparticles, in several concentrations.

Homogeneous Freezing of Water Droplets and its Dependence on Droplet Size

NASA Astrophysics Data System (ADS)

Schmitt, Thea; Möhler, Ottmar; Höhler, Kristina; Leisner, Thomas

2014-05-01

The formulation and parameterisation of microphysical processes in tropospheric clouds, such as phase transitions, is still a challenge for weather and climate models. This includes the homogeneous freezing of supercooled water droplets, since this is an important process in deep convective systems, where almost pure water droplets may stay liquid until homogeneous freezing occurs at temperatures around 238 K. Though the homogeneous ice nucleation in supercooled water is considered to be well understood, recent laboratory experiments with typical cloud droplet sizes showed one to two orders of magnitude smaller nucleation rate coefficients than previous literature results, including earlier results from experiments with single levitated water droplets and from cloud simulation experiments at the AIDA (Aerosol Interaction and Dynamics in the Atmosphere) facility. This motivated us to re-analyse homogeneous droplet freezing experiments conducted during the previous years at the AIDA cloud chamber. This cloud chamber has a volume of 84m3 and operates under atmospherically relevant conditions within wide ranges of temperature, pressure and humidity, whereby investigations of both tropospheric mixed-phase clouds and cirrus clouds can be realised. By controlled adiabatic expansions, the ascent of an air parcel in the troposphere can be simulated. According to our new results and their comparison to the results from single levitated droplet experiments, the homogeneous freezing of water droplets seems to be a volume-dependent process, at least for droplets as small as a few micrometers in diameter. A contribution of surface induced freezing can be ruled out, in agreement to previous conclusions from the single droplet experiments. The obtained volume nucleation rate coefficients are in good agreement, within error bars, with some previous literature data, including our own results from earlier AIDA experiments, but they do not agree with recently published lower volume nucleation rate coefficients. This contribution will show the results from the re-analysis of AIDA homogeneous freezing experiments with pure water droplets and will discuss the comparison to the literature data.

String-like collective atomic motion in the melting and freezing of nanoparticles.

PubMed

Zhang, Hao; Kalvapalle, Pranav; Douglas, Jack F

2011-12-08

The melting of a solid represents a transition between a solid state in which atoms are localized about fixed average crystal lattice positions to a fluid state that is characterized by relative atomic disorder and particle mobility so that the atoms wander around the material as a whole, impelled by the random thermal impulses of surrounding atoms. Despite the fundamental nature and practical importance of this particle delocalization transition, there is still no fundamental theory of melting and instead one often relies on the semi-phenomenological Lindemann-Gilvarry criterion to estimate roughly the melting point as an instability of the crystal lattice. Even the earliest simulations of melting in hexagonally packed hard discs by Alder and Wainwright indicated the active role of nonlocal collective atomic motions in the melting process, and here we utilize molecular dynamics (MD) simulation to determine whether the collective particle motion observed in melting has a similar geometrical form as those in recent studies of nanoparticle (NP) interfacial dynamics and the molecular dynamics of metastable glass-forming liquids. We indeed find string-like collective atomic motion in NP melting that is remarkably similar in form to the collective interfacial motions in NPs at equilibrium and to the collective motions found in the molecular dynamics of glass-forming liquids. We also find that the spatial localization and extent of string-like motion in the course of NP melting and freezing evolves with time in distinct ways. Specifically, the collective atomic motion propagates from the NP surface and from within the NP in melting and freezing, respectively, and the average string length varies smoothly with time during melting. In contrast, the string-like cooperative motion peaks in an intermediate stage of the freezing process, reflecting a general asymmetry in the dynamics of NP superheating and supercooling. © 2011 American Chemical Society

Freezing and melting of water in a single cylindrical pore: The pore-size dependence of freezing and melting behavior

NASA Astrophysics Data System (ADS)

Morishige, Kunimitsu; Kawano, Keiji

1999-03-01

In order to clarify the origin of the hysteresis between freezing and melting of pore water, we performed x-ray diffraction measurements of water confined inside the cylindrical pores of seven kinds of siliceous MCM-41 (a member of ordered mesoporous materials denoted by Mobil Oil researchers) with different pore radii (1.2-2.9 nm) and the interconnected pores of Vycor glass as a function of temperature. The hysteresis effect depends markedly on the size of the cylindrical pores: the hysteresis is negligibly small in smaller pores and becomes remarkable in larger pores. This strongly suggests that the hysteresis is arisen from size-dependent supercooling of water confined to the mesopores. For the water confined to the mesopores with pore radius of 1.2 nm, a continuous transition between a liquid and a solid precedes the first-order freezing transition of the pore water which would occur by the same mechanism as in bulk water.

ERS-1 Investigations of Southern Ocean Sea Ice Geophysics Using Combined Scatterometer and SAR Images

NASA Technical Reports Server (NTRS)

Drinkwater, M.; Early, D.; Long, D.

1994-01-01

Coregistered ERS-1 SAR and Scatterometer data are presented for the Weddell Sea, Antarctica. Calibrated image backscatter statistics are extracted from data acquired in regions where surface measurements were made during two extensive international Weddell Sea experiments in 1992. Changes in summer ice-surface conditions, due to temperature and wind, are shown to have a large impact on observed microwave backscatter values. Winter calibrated backscatter distributions are also investigated as a way of describing ice thickness conditions in different location during winter. Coregistered SAR and EScat data over a manned drifting ice station are used to illustrate the seasonal signature changes occurring during the fall freeze-up transition.

The effect of plant root system on temperature and moisture of road cutting slope in seasonal frozen regions

NASA Astrophysics Data System (ADS)

Shan, W.; Guo, Y.

2009-04-01

In recent years, in the seasonal frozen regions of Northeast China, the construction of highway improved enormously people's journey condition, but also brought a series of environmental question. In order to meet the route requirement, it is inevitable to excavate the mountain slope, which damage the surface vegetation and cut off the runoff passage of groundwater, cause the outcrop of underground water on the cutting slope and affecte the intrinsic ground stress equilibrium of the slope body, lead to the redistribution of ground stress and the heat balance change in near-surface of the cutting slope. Under influence of rainfall in autumn and the cold climate in winter, the moisture transfer to frozen zone of cutting slope and lead to the frost heave in shallow depth of the slope. During the thawing period in spring, with effect of integrated factors including rainfall and increasing temperature, ice kernels both on the surface and near the surface of cut slope thaw quickly. The water melting from frozen soil, will hampered by frozen layer in process of infiltration. As a result, the water content of the intersection between the freezing and melting layer is high enough to be saturation or even over-saturation, and accordingly cause the intrinsic effective stress on the slope body decreased. Under the function of gravity, near-surface slope collapses partially or entirely. As experience of highway construction accumulated, and the consciousness of environmental protection strengthen, the efficiency and the rationality of plant protection slope was realized gradually, slope protection method has transited gradually from masonry body to combined with plant protection, or complete plant protection. Adopted the method combined field test and lab test, this article analyzed the effect of plant system on the temperature and moisture of soil body, especially the root-soil system in freezing process. The results showed that compared with non plant, the soil body protected by plant had lower moisture content and freeze slowly, which indicated the plant could made the condition of moisture and temperature in the slope better, then reduced the destruction of freezing and thawing to the road slope. The study result could provide theory support for the design of plant protection in the slope of seasonal frozen regions. Key words: road slope, season frozen regions, plant protection, temperature, moisture

Heat and mass transfer scale-up issues during freeze-drying, III: control and characterization of dryer differences via operational qualification tests.

PubMed

Rambhatla, S; Tchessalov, S; Pikal, Michael J

2006-04-21

The objective of this research was to estimate differences in heat and mass transfer between freeze dryers due to inherent design characteristics using data obtained from sublimation tests. This study also aimed to provide guidelines for convenient scale-up of the freeze-drying process. Data obtained from sublimation tests performed on laboratory-scale, pilot, and production freeze dryers were used to evaluate various heat and mass transfer parameters: nonuniformity in shelf surface temperatures, resistance of pipe, refrigeration system, and condenser. Emissivity measurements of relevant surfaces such as the chamber wall and the freeze dryer door were taken to evaluate the impact of atypical radiation heat transfer during scale-up. "Hot" and "cold" spots were identified on the shelf surface of different freeze dryers, and the impact of variation in shelf surface temperatures on the primary drying time and the product temperature during primary drying was studied. Calculations performed using emissivity measurements on different freeze dryers suggest that a front vial in the laboratory lyophilizer received 1.8 times more heat than a front vial in a manufacturing freeze dryer operating at a shelf temperature of -25 degrees C and a chamber pressure of 150 mTorr during primary drying. Therefore, front vials in the laboratory are much more atypical than front vials in manufacturing. Steady-state heat and mass transfer equations were used to study a combination of different scale-up issues pertinent during lyophilization cycles commonly used for the freeze-drying of pharmaceuticals.

Representative Values of Icing-Related Variables Aloft in Freezing Rain and Freezing Drizzle

DOT National Transportation Integrated Search

1996-03-01

Radiosonde and surface observations in freezing rain (ZR) and freezing drizzle (ZL), and a limited number of aircraft measurements in ZR, have been examined for information on the magnitude and altitude dependence of meteorological variables associat...

Chloride ions induce order-disorder transition at water-oxide interfaces

NASA Astrophysics Data System (ADS)

Deshmukh, Sanket; Kamath, Ganesh; Ramanathan, Shriram; Sankaranarayanan, Subramanian K. R. S.

2013-12-01

Water can form quasi-two-dimensional ordered layers near a solid interface. The solvation dynamics and ionic transport phenomena through this ordered water structure is of direct relevance to a variety of problems in interface science. Molecular dynamics simulations are used to study the impact of local fluctuation of the chloride ion density in the vicinity of an oxide surface on the structure and dynamics of water layers. We demonstrate that local increase in chloride ions beyond a threshold concentration near the water-MgO (100) interface introduces an order-disorder transition of this two-dimensional layered network into bulklike water, leading to increased diffusional characteristics and reduced hydrogen bonding lifetimes. We find that the extent of this order-disorder transition can be tuned by modifying the defect chemistry and nature of the underlying substrate. The kinetic fluidity resulting from order-disorder transition at high chloride ion concentration has significance for a broad range of phenomena, ranging from freezing point depression of brine to onset of aqueous corrosion.

Two-dimensional freezing criteria for crystallizing colloidal monolayers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang Ziren; Han Yilong; Alsayed, Ahmed M.

Video microscopy was employed to explore crystallization of colloidal monolayers composed of diameter-tunable microgel spheres. Two-dimensional (2D) colloidal liquids were frozen homogenously into polycrystalline solids, and four 2D criteria for freezing were experimentally tested in thermal systems for the first time: the Hansen-Verlet freezing rule, the Loewen-Palberg-Simon dynamical freezing criterion, and two other rules based, respectively, on the split shoulder of the radial distribution function and on the distribution of the shape factor of Voronoi polygons. Importantly, these freezing criteria, usually applied in the context of single crystals, were demonstrated to apply to the formation of polycrystalline solids. At themore » freezing point, we also observed a peak in the fluctuations of the orientational order parameter and a percolation transition associated with caged particles. Speculation about these percolated clusters of caged particles casts light on solidification mechanisms and dynamic heterogeneity in freezing.« less

Rapid freezing of water under dynamic compression

NASA Astrophysics Data System (ADS)

Myint, Philip C.; Belof, Jonathan L.

2018-06-01

Understanding the behavior of materials at extreme pressures is a central issue in fields like aerodynamics, astronomy, and geology, as well as for advancing technological grand challenges such as inertial confinement fusion. Dynamic compression experiments to probe high-pressure states often encounter rapid phase transitions that may cause the materials to behave in unexpected ways, and understanding the kinetics of these phase transitions remains an area of great interest. In this review, we examine experimental and theoretical/computational efforts to study the freezing kinetics of water to a high-pressure solid phase known as ice VII. We first present a detailed analysis of dynamic compression experiments in which water has been observed to freeze on sub-microsecond time scales to ice VII. This is followed by a discussion of the limitations of currently available molecular and continuum simulation methods in modeling these experiments. We then describe how our phase transition kinetics models, which are based on classical nucleation theory, provide a more physics-based framework that overcomes some of these limitations. Finally, we give suggestions on future experimental and modeling work on the liquid–ice VII transition, including an outline of the development of a predictive multiscale model in which molecular and continuum simulations are intimately coupled.

Rapid freezing of water under dynamic compression.

PubMed

Myint, Philip C; Belof, Jonathan L

2018-06-13

Understanding the behavior of materials at extreme pressures is a central issue in fields like aerodynamics, astronomy, and geology, as well as for advancing technological grand challenges such as inertial confinement fusion. Dynamic compression experiments to probe high-pressure states often encounter rapid phase transitions that may cause the materials to behave in unexpected ways, and understanding the kinetics of these phase transitions remains an area of great interest. In this review, we examine experimental and theoretical/computational efforts to study the freezing kinetics of water to a high-pressure solid phase known as ice VII. We first present a detailed analysis of dynamic compression experiments in which water has been observed to freeze on sub-microsecond time scales to ice VII. This is followed by a discussion of the limitations of currently available molecular and continuum simulation methods in modeling these experiments. We then describe how our phase transition kinetics models, which are based on classical nucleation theory, provide a more physics-based framework that overcomes some of these limitations. Finally, we give suggestions on future experimental and modeling work on the liquid-ice VII transition, including an outline of the development of a predictive multiscale model in which molecular and continuum simulations are intimately coupled.

Comparing the ice nucleation efficiencies of ice nucleating substrates to natural mineral dusts

NASA Astrophysics Data System (ADS)

Steinke, Isabelle; Funk, Roger; Höhler, Kristina; Haarig, Moritz; Hoffmann, Nadine; Hoose, Corinna; Kiselev, Alexei; Möhler, Ottmar; Leisner, Thomas

2014-05-01

Mineral dust particles in the atmosphere may act as efficient ice nuclei over a wide range of temperature and relative humidity conditions. The ice nucleation capability of dust particles mostly depends on the particle surface area and the associated physico-chemical surface properties. It has been observed that the surface-related ice nucleation efficiency of different dust particles and mineral species can vary by several orders of magnitude. However, the relation between aerosol surface properties and observed ice nucleation efficiency is still not completely understood due to the large variability of chemical compositions and morphological features. In order to gain a better understanding of small scale freezing processes, we investigated the freezing of several hundreds of small droplets (V=0.4 nl) deposited on materials with reasonably well defined surfaces such as crystalline silicon wafers, graphite and freshly cleaved mica sheets under atmospherically relevant conditions. These substrates are intended to serve as simple model structures compared to the surface of natural aerosol particles. To learn more about the impact of particle morphology on ice nucleation processes, we also investigated micro-structured silicon wafers with prescribed trenches. The ice nucleation efficiencies deduced from these experiments are expressed as ice nucleation active surface site density values. With this approach, the freezing properties of the above-described substrates could be compared to those of natural mineral dusts such as agricultural soil dusts, volcanic ash and fossil diatoms, which have been investigated in AIDA cloud chamber experiments. All tested ice nucleating substrates were consistently less efficient at nucleating ice than the natural mineral dusts. Crystalline silicon only had a negligible influence on the freezing of small droplets, leading to freezing near the homogeneous freezing temperature threshold. Applying surface structures to silicon led to a shift towards heterogeneous freezing. However, the measured ice nucleation active surface site densities were still smaller than those of mineral dusts.

A freeze-dried injectable form of ibuprofen: development and optimisation using response surface methodology.

PubMed

Kagkadis, K A; Rekkas, D M; Dallas, P P; Choulis, N H

1996-01-01

In this study a complex of Ibuprofen and b-Hydroxypropylcyclodextrin was prepared employing a freeze drying method. The production parameters and the final specifications of this product were optimized by using response surface methodology. The results show that the freeze dried complex meets the requirements for solubility to be considered as a possible injectable form.

Freeze-Testing in St. Augustinegrass II: Evaluation of acclimation effects

USDA-ARS?s Scientific Manuscript database

Winter survivability is a major-limiting factor for St. Augustinegrass (Stenotaphrum secundatum [Walt.] Kuntze) grown in the transition zone of the United States as cold winters can result in high levels of winterkill. In addition to field studies, lab-based freeze tests mimicking field winter survi...

Fundamental Boiling and RP-1 Freezing Experiments

NASA Technical Reports Server (NTRS)

Goode, Brian

2002-01-01

The prestart thermal conditioning of the hardware in LOX (liquid oxygen) systems involve heat transfer between LOX and metal where boiling plays a large role. Information is easily found on nucleate boiling, maximum heat flux, minimum heat flux and film boiling for common fluids like water. After looking at these standard correlations it was felt more data was needed for the cool down side transition boiling for the LN2 and LOX. In particular interest is the film boiling values, the temperature at which transition begins and the slope as peak heat flux is approached. The ultimate goal is an array of boiling heat transfer coefficient as a function of surface temperature which can be used in the chilldown model of the feed system, engine and bleed system for X-34. The first experiment consisted of an actual MC-1 LOX Impeller which had been machined backwards, that was instrumented with 17 surface thermocouples and submerged in liquid nitrogen. The thermocouples were installed on metal thicknesses varying from the thin inducer to the thick hub.

Potential weathering by freeze-thaw action in alpine rocks in the European Alps during a nine year monitoring period

NASA Astrophysics Data System (ADS)

Kellerer-Pirklbauer, Andreas

2017-11-01

A quantification of rock weathering by freeze-thaw processes in alpine rocks requires at least rock temperature data in high temporal resolution, in high quality, and over a sufficient period of time. In this study up to nine years of rock temperature data (2006-2015) from eleven rock monitoring sites in two of the highest mountain ranges of Austria were analyzed. Data were recorded at a half-hourly or hourly logging interval and at rock depths of 3, 10, and 30-40 cm. These data have been used to quantify mean conditions, ranges, and relationships of the potential near-surface weathering by freeze-thaw action considering volumetric-expansion of ice and ice segregation. For the former, freeze-thaw cycles and effective freeze-thaw cycles for frost shattering have been considered. For the latter, the intensity and duration of freezing events as well as time within the 'frost cracking window' have been analyzed. Results show that the eleven sites are in rather extreme topoclimatic positions and hence represent some of the highest and coolest parts of Austria and therefore the Eastern Alps. Only four sites are presumably affected by permafrost. Most sites are influenced by a long-lasting seasonal snow cover. Freeze-thaw cycles and effective freeze-thaw cycles for frost shattering are mainly affecting the near-surface and are unimportant at few tens of centimeters below the rock surface. The lowest temperatures during freezing events and the shortest freezing events have been quantified at all eleven monitoring sites very close to the surface. The time within the frost cracking window decreases in most cases from the rock surface inwards apart from very cold years/sites with very low temperatures close to the surface. As shown by this study and predicted climate change scenarios, assumed warmer rock temperature conditions in the future at alpine rock walls in Austria will lead to less severe freezing events and to shorter time periods within the frost-cracking window. Statistical correlation analyses showed furthermore that the longer the duration of the seasonal snow cover, the fewer are freeze-thaw cycles, the fewer are effective freeze-thaw cycles, the longer is the mean and the maximum duration of freezing events, and the lower is the mean annual ground temperature. The interaction of the winter snow cover history and the winter thermal regime has a complex effect on the duration of the frost cracking window but also on the number of freeze-thaw cycles as shown by a conceptual model. Predicted future warmer and snow-depleted winters in the European Alps will therefore have a complex impact on the potential weathering of alpine rocks by frost action which makes potential weathering predictions difficult. Neglecting rock moisture and rock properties in determining rock weathering limits the usefulness of solely rock temperature data. However, rock temperature data allow getting an estimate about potential weathering by freeze-thaw action which is often substantially more than previously known.

Contrasting sea-ice and open-water boundary layers during melt and freeze-up seasons: Some result from the Arctic Clouds in Summer Experiment.

NASA Astrophysics Data System (ADS)

Tjernström, Michael; Sotiropoulou, Georgia; Sedlar, Joseph; Achtert, Peggy; Brooks, Barbara; Brooks, Ian; Persson, Ola; Prytherch, John; Salsbury, Dominic; Shupe, Matthew; Johnston, Paul; Wolfe, Dan

2016-04-01

With more open water present in the Arctic summer, an understanding of atmospheric processes over open-water and sea-ice surfaces as summer turns into autumn and ice starts forming becomes increasingly important. The Arctic Clouds in Summer Experiment (ACSE) was conducted in a mix of open water and sea ice in the eastern Arctic along the Siberian shelf during late summer and early autumn 2014, providing detailed observations of the seasonal transition, from melt to freeze. Measurements were taken over both ice-free and ice-covered surfaces, offering an insight to the role of the surface state in shaping the lower troposphere and the boundary-layer conditions as summer turned into autumn. During summer, strong surface inversions persisted over sea ice, while well-mixed boundary layers capped by elevated inversions were frequent over open-water. The former were often associated with advection of warm air from adjacent open-water or land surfaces, whereas the latter were due to a positive buoyancy flux from the warm ocean surface. Fog and stratus clouds often persisted over the ice, whereas low-level liquid-water clouds developed over open water. These differences largely disappeared in autumn, when mixed-phase clouds capped by elevated inversions dominated in both ice-free and ice-covered conditions. Low-level-jets occurred ~20-25% of the time in both seasons. The observations indicate that these jets were typically initiated at air-mass boundaries or along the ice edge in autumn, while in summer they appeared to be inertial oscillations initiated by partial frictional decoupling as warm air was advected in over the sea ice. The start of the autumn season was related to an abrupt change in atmospheric conditions, rather than to the gradual change in solar radiation. The autumn onset appeared as a rapid cooling of the whole atmosphere and the freeze up followed as the warm surface lost heat to the atmosphere. While the surface type had a pronounced impact on boundary-layer structure in summer, the surface was often warmer than the atmosphere in autumn, regardless of surface type. Hence the autumn boundary-layer structure was more dependent on synoptic scale meteorology.

Some observations on soil freezing in forest and range lands of the Pacific Northwest.

Treesearch

Charles E. Hale

1950-01-01

It is well known that freezing and thawing of the surface soil and humus greatly affect their capacity to absorb water. Post and Dreibelbis (1) in Ohio reported that percolation was materially reduced or ceased entirely when the frost depth was three inches or greater. They also stated that "freezing of the surface soil undoubtedly has considerable influence on...

Characterizing the freezing behavior of liposomes as a tool to understand the cryopreservation procedures.

PubMed

Siow, Lee Fong; Rades, Thomas; Lim, Miang Hoong

2007-12-01

Freezing behaviors of egg yolk l-alpha-phosphatidylcholine (EPC) and 1,2-dipalmitoyl-rac-glycero-3-phosphocholine (DPPC) large unilamellar vesicles (LUV) were quantitatively characterized in relation to freezing temperatures, cooling rates, holding time, presence of sodium chloride and phospholipid phase transition temperature. Cooling of the EPC LUV showed an abrupt increase in leakage of the encapsulated carboxyfluorescein (CF) between -5 degrees C and -10 degrees C, which corresponded with the temperatures of the extraliposomal ice formation at around -7 degrees C. For the DPPC LUV, CF leakage started at -10 degrees C, close to the temperature of the extraliposomal ice formation; followed by a subsequent rapid increase in leakage between -10 degrees C and -25 degrees C. Scanning electron microscopy showed that both of these LUV were freeze-concentrated and aggregated at sub-freezing temperatures. We suggest that the formation of the extraliposomal ice and the decrease of the unfrozen fraction causes freeze-injury and leakage of the CF. The degree of leakage, however, differs between EPC LUV and DPPC LUV that inherently vary in their phospholipid phase transition temperatures. With increasing holding time, the EPC LUV were observed to have higher leakage when they were held at -15 degrees C compared to at -30 degrees C whilst leakage of the DPPC LUV was higher when holding at -40 degrees C than at -15 degrees C and -50 degrees C. At slow cooling rates, osmotic pressure across the bilayers may cause an additional stress to the EPC LUV. The present work elucidates freeze-injury mechanisms of the phospholipid bilayers through the liposomal model membranes.

Generalized Dynamic Equations Related to Condensation and Freezing Processes

NASA Astrophysics Data System (ADS)

Wang, Xingrong; Huang, Yong

2018-01-01

The generalized thermodynamic equation related to condensation and freezing processes was derived by introducing the condensation and freezing probability function into the dynamic framework based on the statistical thermodynamic fluctuation theory. As a result, the physical mechanism of some weather phenomena covered by using δ(0,1) can in turn be studied and uncovered. From the generalized dynamic equations, the tendency equation of the generalized potential vorticity (GPV) is derived. From the discussion of tendency equation of GPV, in some very thin transitional areas, GPV is found nonconserved because of the introduction of the condensation and freezing probability function, even in frictionless and moist adiabatic air motion.

Photomicrographic Investigation of Spontaneous Freezing Temperatures of Supercooled Water Droplets

NASA Technical Reports Server (NTRS)

Dorsch, R. G.; Hacker, P. T.

1950-01-01

A photomicrographic technique for investigating eupercooled. water droplets has been devised and. used. to determine the spontaneous freezing temperatures of eupercooled. water droplets of the size ordinarily found. in the atmosphere. The freezing temperatures of 4527 droplets ranging from 8.75 to 1000 microns in diameter supported on a platinum surface and 571 droplets supported on copper were obtained. The average spontaneous freezing temperature decreased with decrease in the size of the droplets. The effect of size on the spontaneous freezing temperature was particularly marked below 60 microns. Frequency-distribution curves of the spontaneous freezing temperatures observed for droplets of a given size were obtained. Although no droplet froze at a temperature above 20 0 F, all droplets melted at 32 F. Results obtained with a copper support did not differ essentially from those obtained with a platinum surface.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mamontov, Eugene; O'Neil, Hugh

In this paper, we have studied microscopic dynamics of a protein in carbon disulfide, a non-glass forming solvent, down to its freezing temperature of ca. 160 K. We have utilized quasielastic neutron scattering. A comparison of lysozyme hydrated with water and dissolved in carbon disulfide reveals a stark difference in the temperature dependence of the protein's microscopic relaxation dynamics induced by the solvent. In the case of hydration water, the common protein glass-forming solvent, the protein relaxation slows down in response to a large increase in the water viscosity on cooling down, exhibiting a well-known protein dynamical transition. The dynamicalmore » transition disappears in non-glass forming carbon disulfide, whose viscosity remains a weak function of temperature all the way down to freezing at just below 160 K. The microscopic relaxation dynamics of lysozyme dissolved in carbon disulfide is sustained down to the freezing temperature of its solvent at a rate similar to that measured at ambient temperature. Finally, our results demonstrate that protein dynamical transition is not merely solvent-assisted, but rather solvent-induced, or, more precisely, is a reflection of the temperature dependence of the solvent's glass-forming dynamics.« less

Are superhydrophobic surfaces best for icephobicity?

PubMed

Jung, Stefan; Dorrestijn, Marko; Raps, Dominik; Das, Arindam; Megaridis, Constantine M; Poulikakos, Dimos

2011-03-15

Ice formation can have catastrophic consequences for human activity on the ground and in the air. Here we investigate water freezing delays on untreated and coated surfaces ranging from hydrophilic to superhydrophobic and use these delays to evaluate icephobicity. Supercooled water microdroplets are inkjet-deposited and coalesce until spontaneous freezing of the accumulated mass occurs. Surfaces with nanometer-scale roughness and higher wettability display unexpectedly long freezing delays, at least 1 order of magnitude longer than typical superhydrophobic surfaces with larger hierarchical roughness and low wettability. Directly related to the main focus on heterogeneous nucleation and freezing delay of supercooled water droplets, the observed ensuing crystallization process consisted of two distinct phases: one very rapid recalescent partial solidification phase and a subsequent slower phase. Observations of the droplet collision process employed for the continuous liquid mass accumulation up to the point of ice formation reveal a previously unseen atmospheric-pressure, subfreezing-temperature regime for liquid-on-liquid bounce. On the basis of the entropy reduction of water near a solid surface, we formulate a modification to the classical heterogeneous nucleation theory, which predicts the observed freezing delay trends. Our results bring to question recent emphasis on super water-repellent surface formulations for ice formation retardation and suggest that anti-icing design must optimize the competing influences of both wettability and roughness.

Influence of vertical and lateral heat transfer on permafrost thaw, peatland landscape transition, and groundwater flow

USGS Publications Warehouse

Kurylyk, Barret L.; Masaki, Masaki; Quinton, William L.; McKenzie, Jeffrey M.; Voss, Clifford I.

2016-01-01

Recent climate change has reduced the spatial extent and thickness of permafrost in many discontinuous permafrost regions. Rapid permafrost thaw is producing distinct landscape changes in the Taiga Plains of the Northwest Territories, Canada. As permafrost bodies underlying forested peat plateaus shrink, the landscape slowly transitions into unforested wetlands. The expansion of wetlands has enhanced the hydrologic connectivity of many watersheds via new surface and near-surface flow paths, and increased streamflow has been observed. Furthermore, the decrease in forested peat plateaus results in a net loss of boreal forest and associated ecosystems. This study investigates fundamental processes that contribute to permafrost thaw by comparing observed and simulated thaw development and landscape transition of a peat plateau-wetland complex in the Northwest Territories, Canada from 1970 to 2012. Measured climate data are first used to drive surface energy balance simulations for the wetland and peat plateau. Near-surface soil temperatures simulated in the surface energy balance model are then applied as the upper boundary condition to a three-dimensional model of subsurface water flow and coupled energy transport with freeze-thaw. Simulation results demonstrate that lateral heat transfer, which is not considered in many permafrost models, can influence permafrost thaw rates. Furthermore, the simulations indicate that landscape evolution arising from permafrost thaw acts as a positive feedback mechanism that increases the energy absorbed at the land surface and produces additional permafrost thaw. The modeling results also demonstrate that flow rates in local groundwater flow systems may be enhanced by the degradation of isolated permafrost bodies.

Simulation of Changes in the Near-Surface Soil Freeze/Thaw Cycle Using CLM4.5 With Four Atmospheric Forcing Data Sets

NASA Astrophysics Data System (ADS)

Guo, Donglin; Wang, Aihui; Li, Duo; Hua, Wei

2018-03-01

Change in the near-surface soil freeze/thaw cycle is critical for assessments of hydrological activity, ecosystems, and climate change. Previous studies investigated the near-surface soil freeze/thaw cycle change mostly based on in situ observations and satellite monitoring. Here numerical simulation method is tested to estimate the long-term change in the near-surface soil freeze/thaw cycle in response to recent climate warming for its application to predictions. Four simulations are performed at 0.5° × 0.5° resolution from 1979 to 2009 using the Community Land Model version 4.5, each driven by one of the four atmospheric forcing data sets (i.e., one default Climate Research Unit-National Centers for Environmental Prediction [CRUNCEP] and three newly developed Modern Era Retrospective-Analysis for Research and Applications, Climate Forecast System Reanalysis, and European Centre for Medium-Range Weather Forecasts Reanalysis Interim). The observations from 299 weather stations in both Russia and China are employed to validate the simulated results. The results show that all simulations reasonably reproduce the observed variations in the ground temperature, the freeze start and end dates, and the freeze duration (the correlation coefficients range from 0.47 to 0.99, and the Nash-Sutcliffe efficiencies range from 0.19 to 0.98). Part of the simulations also exactly simulate the trends of the ground temperature, the freeze start and end dates, and the freeze duration. Of the four simulations, the results from the simulation using the CRUNCEP data set show the best overall agreement with the in situ observations, indicating that the CRUNCEP data set could be preferentially considered as the basic atmospheric forcing data set for future prediction. The simulated area-averaged annual freeze duration shortened by 8.03 days on average from 1979 to 2009, with an uncertainty (one standard deviation) of 0.67 days caused by the different atmospheric forcing data sets. These results address the performance of numerical model in simulating the long-term changes in the near-surface soil freeze/thaw cycle and the role of different atmospheric forcing data sets in the simulation, which are useful for the prediction of future freeze/thaw dynamics.

Effects of buffer composition and processing conditions on aggregation of bovine IgG during freeze-drying.

PubMed

Sarciaux, J M; Mansour, S; Hageman, M J; Nail, S L

1999-12-01

The objective of this study was to identify critical formulation and processing variables affecting aggregation of bovine IgG during freeze-drying when no lyoprotective solute is used. Parameters examined were phosphate buffer concentration and counterion (Na versus K phosphate), added salts, cooling rate, IgG concentration, residual moisture level, and presence of a surfactant. No soluble aggregates were detected in any formulation after either freezing/thawing or freeze-drying. No insoluble aggregates were detected in any formulation after freezing, but insoluble aggregate levels were always detectable after freeze-drying. The data are consistent with a mechanism of aggregate formation involving denaturation of IgG at the ice/freeze-concentrate interface which is reversible upon freeze-thawing, but becomes irreversible after freeze-drying and reconstitution. Rapid cooling (by quenching in liquid nitrogen) results in more and larger aggregates than slow cooling on the shelf of the freeze-dryer. This observation is consistent with surface area measurements and environmental electron microscopic data showing a higher surface area of freeze-dried solids after fast cooling. Annealing of rapidly cooled solutions results in significantly less aggregation in reconstituted freeze-dried solids than in nonannealed controls, with a corresponding decrease in specific surface area of the freeze-dried, annealed system. Increasing the concentration of IgG significantly improves the stability of IgG against freeze-drying-induced aggregation, which may be explained by a smaller percentage of the protein residing at the ice/freeze-concentrate interface as IgG concentration is increased. A sodium phosphate buffer system consistently results in more turbid reconstituted solids than a potassium phosphate buffer system at the same concentration, but this effect is not attributable to a pH shift during freezing. Added salts such as NaCl or KCl contribute markedly to insoluble aggregate formation. Both sodium and potassium chloride contribute more to turbidity of the reconstituted solid than either sodium or potassium phosphate buffers at similar ionic strength, with sodium chloride resulting in a substantially higher level of aggregates than potassium chloride. At a given cooling rate, the specific surface area of dried solids is approximately a factor of 2 higher for the formulation containing sodium chloride than the formulation containing potassium chloride. Turbidity is also influenced by the extent of secondary drying, which underscores the importance of minimizing secondary drying of this system. Including a surfactant such as polysorbate 80, either in the formulation or in the water used for reconstitution, decreased, but did not eliminate, insoluble aggregates. There was no correlation between pharmaceutically acceptability of the freeze-dried cake and insoluble aggregate levels in the reconstituted product.

Fall Freeze-up of Sea Ice in the Beaufort-Chukchi Seas Using ERS-1 SAR and Buoy Data

NASA Technical Reports Server (NTRS)

Holt, B.; Winebrenner, B.; D., Nelson E.

1993-01-01

The lowering of air temperatures below freezing in the fall indicates the end of summer melt and the onset of steady sea ice growth. The thickness and condition of ice that remains at the end of summer has ramifications for the thickness that that ice will attain at the end of the following winter. This period also designates a shifting of key fluxes from upper ocean freshening from ice melt to increased salinity from brine extraction during ice growth. This transitional period has been examined in the Beaufort and Chukchi Seas using ERS-1 SAR imagery and air temperatures from drifting buoys during 1991 and 1992. The SAR imagery is used to examine the condition and types of ice present in this period. Much of the surface melt water has drained off at this time. Air temperatures from drifting buoys coincident in time and within 100 km radius of the SAR imagery have been obtained...

Hierarchical Freezing in a Lattice Model

NASA Astrophysics Data System (ADS)

Byington, Travis W.; Socolar, Joshua E. S.

2012-01-01

A certain two-dimensional lattice model with nearest and next-nearest neighbor interactions is known to have a limit-periodic ground state. We show that during a slow quench from the high temperature, disordered phase, the ground state emerges through an infinite sequence of phase transitions. We define appropriate order parameters and show that the transitions are related by renormalizations of the temperature scale. As the temperature is decreased, sublattices with increasingly large lattice constants become ordered. A rapid quench results in a glasslike state due to kinetic barriers created by simultaneous freezing on sublattices with different lattice constants.

Thin, Conductive Permafrost Surrounding Lake Fryxell Indicates Salts From Past Lakes, McMurdo Dry Valleys, Antarctica

NASA Astrophysics Data System (ADS)

Foley, N.; Tulaczyk, S. M.; Gooseff, M. N.; Myers, K. F.; Doran, P. T.; Auken, E.; Dugan, H. A.; Mikucki, J.; Virginia, R. A.

2017-12-01

In the McMurdo Dry Valleys (MDV), permafrost should be thick and liquid water rare. However, despite the well below zero mean annual temperature in this cryospheric desert, liquid water can be found in lakes, summer melt streams, subglacial outflow, and - recent work has shown - underneath anomalously thin permafrost. In part, this niche hydrosphere is maintained by the presence of salts, which depress the freezing point of water to perhaps as cold as -10° Celsius. We detected widespread salty water across the MDV in lakes and at depth using a helicopter-borne Time Domain Electromagnetic (TDEM) sensor. By using the presence of brines to mark the transition from frozen permafrost (near the surface) to unfrozen ground (at depth), we have created a map of permafrost thickness in Lower Taylor Valley (LTV), a large MDV with a complex history of glaciation and occupation by lakes. Our results show that permafrost is thinner ( 200m) than would be expected based on geothermal gradient measurements (up to 1000m), a result of the freezing point depression caused by salt and potentially enhanced by an unfinished transient freezing process. Near Lake Fryxell, a large, brackish lake in the center of LTV, permafrost is very thin (about 30-40m) and notably more electrically conductive than more distal permafrost. This thin ring of conductive permafrost surrounding the lake basin most likely reflects the high presence of salts in the subsurface, preventing complete freezing. These salts may be a remnant of the salty bottom waters of a historic larger lake (LGM glacially dammed Lake Washburn) or the remnant of salty basal water from a past advance of Taylor Glacier, which now sits many km up-valley but is known to contain brines which currently flow onto the surface and directly into the subsurface aquifer.

Structural and Functional Insights into the Cryoprotection of Membranes by the Intrinsically Disordered Dehydrins*

PubMed Central

Clarke, Matthew W.; Boddington, Kelly F.; Warnica, Josephine M.; Atkinson, John; McKenna, Sarah; Madge, Jeffrey; Barker, Christine H.; Graether, Steffen P.

2015-01-01

Dehydration can be due to desiccation caused by a lack of environmental water or to freezing caused by a lack of liquid water. Plants have evolved a large family of proteins called LEA (late embryogenesis abundant) proteins, which include the intrinsically disordered dehydrin (dehydration protein) family, to combat these abiotic stresses. Although transcription and translation studies have shown a correlation between dehydration stress and the presence of dehydrins, the biochemical mechanisms have remained somewhat elusive. We examine here the effect and structure of a small model dehydrin (Vitis riparia K2) on the protection of membranes from freeze-thaw stress. This protein is able to bind to liposomes containing phosphatidic acid and protect the liposomes from fusing after freeze-thaw treatment. The presence of K2 did not measurably affect liposome surface accessibility or lipid mobility but did lower its membrane transition temperature by 3 °C. Using sodium dodecyl sulfate as a membrane model, we examined the NMR structure of K2 in the presence and absence of the micelle. Biochemical and NMR experiments show that the conserved, lysine-rich segments are involved in the binding of the dehydrin to a membrane, whereas the poorly conserved φ segments play no role in binding or protection. PMID:26370084

Nonspecific esterase reaction in hyperplastic urinary bladder epithelium induced by administration of N-butyl-N-(4-hydroxybutyl)nitrosamine, freezing and formalin instillation in rats.

PubMed Central

Akagi, A.; Otsuka, H.

1988-01-01

Chronological changes in nonspecific esterase (NSE) activity in hyperplasia of the bladder mucosa in Wistar rats induced by the administration of 0.05% N-butyl-N-(4-hydroxybutyl)nitrosamine (BBN) in their drinking water for up to 20 weeks and in reversible regenerative hyperplasia by freeze ulceration and 20% formalin instillation in the bladder were compared. In regenerative hyperplasia foci with strong NSE activity could not be proved throughout the experimental period, while the foci were detected in hyperplastic epithelium induced by BBN treatment for more than 3 weeks. The focus of NSE high activity persisted for 56 weeks after withdrawal of the carcinogen and the focus or area with the same NSE reaction appeared in papilloma and transitional cell carcinoma seen in weeks 7 to 20 of BBN treatment. The appearance of focal strong activity of NSE seemed to be a promising marker for the precursor lesions of bladder tumors. Short uniform, pleomorphic microvilli were observed on the cell surface of preneoplastic and carcinomatous lesions by BBN as well as on that of regenerative hyperplasia after freeze ulceration and formalin instillation. Images Fig. 5 Fig. 6 Fig. 7 Fig. 8 Fig. 9 Fig. 10 Fig. 11 Fig. 12 Fig. 13 PMID:3390388

Influence of entanglements on glass transition temperature of polystyrene

NASA Astrophysics Data System (ADS)

Ougizawa, Toshiaki; Kinugasa, Yoshinori

2013-03-01

Chain entanglement is essential behavior of polymeric molecules and it seems to affect many physical properties such as not only viscosity of melt state but also glass transition temperature (Tg). But we have not attained the quantitative estimation because the entanglement density is considered as an intrinsic value of the polymer at melt state depending on the chemical structure. Freeze-drying method is known as one of the few ways to make different entanglement density sample from dilute solution. In this study, the influence of entanglements on Tg of polystyrene obtained by the freeze-dried method was estimated quantitatively. The freeze-dried samples showed Tg depression with decreasing the concentration of precursor solution due to the lower entanglement density and their depressed Tg would be saturated when the almost no intermolecular entanglement was formed. The molecular weight dependence of the maximum value of Tg depression was discussed.

The interdependence of lake ice and climate in central North America

NASA Technical Reports Server (NTRS)

Jelacic, A. J. (Principal Investigator)

1972-01-01

There are no author-identified significant results in this report. This investigation is to identify any correlations between the freeze/ thaw cycles of lakes and regional weather variations. ERTS-1 imagery of central Canada and north central United States is examined on a seasonal basis. The ice conditions of certain major study lakes are noted and recorded on magnetic tape, from which the movement of a freeze/thaw transition zone may be deduced. Weather maps and tables are used to establish any obvious correlations. The process of selecting major study lakes is discussed, and a complete lake directory is presented. Various routines of the software support library are described, accompanied by output samples. Procedures used for ERTS imagery processing are presented along with the data analysis plan. Application of these procedures to selected ERTS imagery has demonstrated their utility. Preliminary results show that the freeze/thaw transition zone can be monitored from ERTS.

Functionalised Silk Fibres

DTIC Science & Technology

2012-07-30

rubber moulds (14 x 5 x 6 mm; RL060, ProSciTech, QLD), frozen at -20ºC overnight, and placed in a freeze - dryer (FD355DMP, FTS Systems) for 24 hours...surface area, low volume materials: electrospun fibres and freeze -dried sponges (Figure 9). Each new material type is described in detail below...surface area materials generated from recombinant honeybee silk proteins. (A) Electrospun fibres, scale bar is 200 nm. (B) Freeze dried sponges

Chemical potential dependence of particle ratios within a unified thermal approach

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bashir, I., E-mail: inamhep@gmail.com; Nanda, H.; Uddin, S.

2016-06-15

A unified statistical thermal freeze-out model (USTFM) is used to study the chemical potential dependence of identified particle ratios at mid-rapidity in heavy-ion collisions. We successfully reproduce the experimental data ranging from SPS energies to LHC energies, suggesting the statistical nature of the particle production in these collisions and hence the validity of our approach. The behavior of the freeze-out temperature is studied with respect to chemical potential. The freeze-out temperature is found to be universal at the RHIC and LHC and is close to the QCD predicted phase transition temperature, suggesting that the chemical freeze-out occurs soon after themore » hadronization takes place.« less

From Glass Formation to Icosahedral Ordering by Curving Three-Dimensional Space.

PubMed

Turci, Francesco; Tarjus, Gilles; Royall, C Patrick

2017-05-26

Geometric frustration describes the inability of a local molecular arrangement, such as icosahedra found in metallic glasses and in model atomic glass formers, to tile space. Local icosahedral order, however, is strongly frustrated in Euclidean space, which obscures any causal relationship with the observed dynamical slowdown. Here we relieve frustration in a model glass-forming liquid by curving three-dimensional space onto the surface of a 4-dimensional hypersphere. For sufficient curvature, frustration vanishes and the liquid "freezes" in a fully icosahedral structure via a sharp "transition." Frustration increases upon reducing the curvature, and the transition to the icosahedral state smoothens while glassy dynamics emerge. Decreasing the curvature leads to decoupling between dynamical and structural length scales and the decrease of kinetic fragility. This sheds light on the observed glass-forming behavior in Euclidean space.

Freeze-thawing behaviour of highly concentrated aqueous alkali chloride-glucose systems.

PubMed

Kajiwara, K; Motegi, A; Murase, N

2001-01-01

The freeze-thawing behaviour of highly concentrated aqueous alkali chloride-glucose systems was investigated by differential scanning calorimetry (DSC). In the aqueous NaCl-glucose solution system, single or double glass transitions followed by the corresponding devitrification exotherms were observed during rewarming. In the aqueous KCl-glucose solution system, on the other hand, a single glass transition followed by an exotherm was observed during rewarming. The presence of double glass transitions observed for a certain composition of the aqueous NaCl-glucose solution was taken as an evidence for the liquid-liquid immiscibility at low temperatures. Two kinds of crystallisation accompanied by exotherms during rewarming were identified by X-ray diffraction as ice and ice/NaCl x 2H(2)O, or ice/KCl eutectic component.

Temperature and flow measurements on near-freezing aviation fuels in a wing-tank model

NASA Technical Reports Server (NTRS)

Friedman, R.; Stockemer, F. J.

1980-01-01

Freezing behavior, pumpability, and temperature profiles for aviation turbine fuels were measured in a 190-liter tank chilled to simulate internal temperature gradients encountered in commercial airplane wing tanks. When the bulk of the fuel was above the specification freezing point, pumpout of the fuel removed all fuel except a layer adhering to the bottom chilled surfaces, and the unpumpable fraction depended on the fuel temperature near these surfaces. When the bulk of the fuel was at or below the freezing point, pumpout ceased when solids blocked the pump inlet, and the unpumpable fraction depended on the overall average temperature.

Effects of Artificial Supercooling Followed by Slow Freezing on the Microstructure and Qualities of Pork Loin

PubMed Central

2016-01-01

This study investigated the effects of artificial supercooling followed by still air freezing (SSF) on the qualities of pork loin. The qualities of pork frozen by SSF were compared with the fresh control (CT, stored at 4℃ for 24 h), slow freezing (SAF, still air freezing) and rapid freezing (EIF, ethanol immersion freezing) treatments. Compared with no supercooling phenomena of SAF and EIF, the extent of supercooling obtained by SSF treatment was 1.4℃. Despite that SSF was conducted with the same method with SAF, application of artificial supercooling accelerated the phase transition (traverse from -0.6℃ to -5℃) from 3.07 h (SAF) to 2.23 h (SSF). The observation of a microstructure indicated that the SSF prevented tissue damage caused by ice crystallization and maintained the structural integrity. The estimated quality parameters reflected that SSF exhibited superior meat quality compared with slow freezing (SAF). SSF showed better water-holding capacity (lower thawing loss, cooking loss and expressible moisture) and tenderness than SAF, and these quality parameters of SSF were not significantly different with ultra-fast freezing treatment (EIF). Consequently, the results demonstrated that the generation of supercooling followed by conventional freezing potentially had the advantage of minimizing the quality deterioration caused by the slow freezing of meat. PMID:27857541

Hydrogel, aerogel and film of cellulose nanofibrils functionalized with silver nanoparticles.

PubMed

Dong, Hong; Snyder, James F; Tran, Dat T; Leadore, Julia L

2013-06-20

In this work, we describe hydrogels, aerogels and films of nanofibrillated cellulose (NFC) functionalized with metal nanoparticles using silver as an example. The TEMPO process used to produce NFC generates negatively charged surface carboxylate groups that provide high binding capability to transition metal species such as Ag(+). The gelation of NFC triggered by transition monovalent metal ions was revealed for the first time. The interaction was utilized to bind Ag(+) on the NFC surface and simultaneously induce formation of NFC-Ag(+) hydrogels, where Ag(+) was slowly reduced to Ag nanoparticles by hydroxyl groups on NFC without additional reducing agent. The NFC-Ag(+) hydrogel was initiated by strong association of carboxylate groups on NFC with Ag(+) and sufficient NFC surface charge reduction. The stiff hydrogel has a storage modulus leveled off at a plateau value of ~6800Pa. Porous aerogels and flat thin films comprising a continuous matrix of NFC were decorated with Ag nanoparticles through freeze-drying or solution-casting of NFC-Ag(+) dispersions with low contents of Ag(+), respectively, followed by UV reduction. The presence of Ag species on NFC reduced coalescence of nanofibrils in the film formation as revealed from AFM phase images. Copyright © 2013 Elsevier Ltd. All rights reserved.

Electrical Capacitance Tomography Measurement of the Migration of Ice Frontal Surface in Freezing Soil

NASA Astrophysics Data System (ADS)

Liu, J.; Suo, X. M.; Zhou, S. S.; Meng, S. Q.; Chen, S. S.; Mu, H. P.

2016-12-01

The tracking of the migration of ice frontal surface is crucial for the understanding of the underlying physical mechanisms in freezing soil. Owing to the distinct advantages, including non-invasive sensing, high safety, low cost and high data acquisition speed, the electrical capacitance tomography (ECT) is considered to be a promising visualization measurement method. In this paper, the ECT method is used to visualize the migration of ice frontal surface in freezing soil. With the main motivation of the improvement of imaging quality, a loss function with multiple regularizers that incorporate the prior formation related to the imaging objects is proposed to cast the ECT image reconstruction task into an optimization problem. An iteration scheme that integrates the superiority of the split Bregman iteration (SBI) method is developed for searching for the optimal solution of the proposed loss function. An unclosed electrodes sensor is designed for satisfying the requirements of practical measurements. An experimental system of one dimensional freezing in frozen soil is constructed, and the ice frontal surface migration in the freezing process of the wet soil sample containing five percent of moisture is measured. The visualization measurement results validate the feasibility and effectiveness of the ECT visualization method

Mangrove expansion and contraction at a poleward range limit: Climate extremes and land-ocean temperature gradients

USGS Publications Warehouse

Osland, Michael J.; Day, Richard H.; Hall, Courtney T.; Brumfield, Marisa D; Dugas, Jason; Jones, William R.

2017-01-01

Within the context of climate change, there is a pressing need to better understand the ecological implications of changes in the frequency and intensity of climate extremes. Along subtropical coasts, less frequent and warmer freeze events are expected to permit freeze-sensitive mangrove forests to expand poleward and displace freeze-tolerant salt marshes. Here, our aim was to better understand the drivers of poleward mangrove migration by quantifying spatiotemporal patterns in mangrove range expansion and contraction across land-ocean temperature gradients. Our work was conducted in a freeze-sensitive mangrove-marsh transition zone that spans a land-ocean temperature gradient in one of the world's most wetland-rich regions (Mississippi River Deltaic Plain; Louisiana, USA). We used historical air temperature data (1893-2014), alternative future climate scenarios, and coastal wetland coverage data (1978-2011) to investigate spatiotemporal fluctuations and climate-wetland linkages. Our analyses indicate that changes in mangrove coverage have been controlled primarily by extreme freeze events (i.e., air temperatures below a threshold zone of -6.3 to -7.6 °C). We expect that in the past 121 years, mangrove range expansion and contraction has occurred across land-ocean temperature gradients. Mangrove resistance, resilience, and dominance were all highest in areas closer to the ocean where temperature extremes were buffered by large expanses of water and saturated soil. Under climate change, these areas will likely serve as local hotspots for mangrove dispersal, growth, range expansion, and displacement of salt marsh. Collectively, our results show that the frequency and intensity of freeze events across land-ocean temperature gradients greatly influences spatiotemporal patterns of range expansion and contraction of freeze-sensitive mangroves. We expect that, along subtropical coasts, similar processes govern the distribution and abundance of other freeze-sensitive organisms. In broad terms, our findings can be used to better understand and anticipate the ecological effects of changing winter climate extremes, especially within the transition zone between tropical and temperate climates.

Protein brownian rotation at the glass transition temperature of a freeze-concentrated buffer probed by superparamagnetic nanoparticles.

PubMed

Eloi, J-C; Okuda, M; Jones, S E Ward; Schwarzacher, W

2013-06-18

For applications from food science to the freeze-thawing of proteins it is important to understand the often complex freezing behavior of solutions of biomolecules. Here we use a magnetic method to monitor the Brownian rotation of a quasi-spherical cage-shaped protein, apoferritin, approaching the glass transition Tg in a freeze-concentrated buffer (Tris-HCl). The protein incorporates a synthetic magnetic nanoparticle (Co-doped Fe3O4 (magnetite)). We use the magnetic signal from the nanoparticles to monitor the protein orientation. As T decreases toward Tg of the buffer solution the protein's rotational relaxation time increases exponentially, taking values in the range from a few seconds up to thousands of seconds, i.e., orders of magnitude greater than usually accessed, e.g., by NMR. The longest relaxation times measured correspond to estimated viscosities >2 MPa s. As well as being a means to study low-temperature, high-viscosity environments, our method provides evidence that, for the cooling protocol used, the following applies: 1), the concentration of the freeze-concentrated buffer at Tg is independent of its initial concentration; 2), little protein adsorption takes place at the interface between ice and buffer; and 3), the protein is free to rotate even at temperatures as low as 207 K. Copyright © 2013 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Effect of ageing of K-feldspar on its ice nucleating efficiency in immersion, deposition and contact freezing modes

NASA Astrophysics Data System (ADS)

Peckhaus, Andreas; Bachmann, Felix; Hoffmann, Nadine; Koch, Michael; Kiselev, Alexei; Leisner, Thomas

2015-04-01

Recently K-feldspar was identified as one of the most active atmospheric ice nucleating particles (INP) of mineral origin [1]. Seeking the explanation to this phenomena we have conducted extensive experimental investigation of the ice nucleating efficiency of K-feldspar in three heterogeneous freezing modes. The immersion freezing of K-feldspar was investigated with the cold stage using arrays of nanoliter-size droplets containing aqueous suspension of polydisperse feldspar particles. For contact freezing, the charged droplets of supercooled water were suspended in the laminar flow of the DMA-selected feldspar-containing particles, allowing for determination of freezing probability on a single particle-droplet contact [2]. The nucleation and growth of ice via vapor deposition on the crystalline surfaces of macroscopic feldspar particles have been investigated in the Environmental Scanning Electron Microscope (ESEM) under humidified nitrogen atmosphere. The ice nucleation experiments were supplemented with measurements of effective surface area of feldspar particles and ion chromatography (IC) analysis of the leached framework cations (K+, Na+, Ca2+, Mg2+). In this contribution we focus on the role of surface chemistry influencing the IN efficiency of K-feldspar, in particular the connection between the degree of surface hydroxylation and its ability to induce local structural ordering in the interfacial layer in water molecules (as suggested by recent modeling efforts). We mimic the natural process of feldspar ageing by suspending it in water or weak aqueous solution of carbonic acid for different time periods, from minutes to months, and present its freezing efficiency as a function of time. Our immersion freezing experiments show that ageing have a nonlinear effect on the freezing behavior of feldspar within the investigated temperature range (-40°C to -10°C). On the other hand, deposition nucleation of ice observed in the ESEM reveals clear different pattern between freshly cleaved and aged mineral surfaces. This effect is especially pronounced for surfaces having different crystallographic orientations (001 and 010), with 001 being clearly preferential for ice nucleation. The factor two change of the BET effective area of the naturally aged feldspar particles is also indicative for the change in the surface morphology. Based on the IC analysis of framework cations removal from the surface of feldspar, we discuss the possible implications of this process for the interpretation of observed freezing behavior of feldspars. [1] Atkinson, J.D., Murray, B.J., Woodhouse, M.T., Whale, T.F., Baustian, K.J., Carslaw, K.S., Dobbie, S., O'Sullivan, D., and Malkin, T.L.: The importance of feldspar for ice nucleation by mineral dust in mixed-phase clouds. Nature, 498, 355-358, 2013 [2] Hoffmann, N., Kiselev, A., Rzesanke, D., Duft, D., and Leisner, T.: Experimental quantification of contact freezing in an electrodynamic balance. Atmos. Meas. Tech., 6, 2373-2382, 2013.

Fundamental technical elements of freeze-fracture/freeze-etch in biological electron microscopy.

PubMed

Carson, Johnny L

2014-09-11

Freeze-fracture/freeze-etch describes a process whereby specimens, typically biological or nanomaterial in nature, are frozen, fractured, and replicated to generate a carbon/platinum "cast" intended for examination by transmission electron microscopy. Specimens are subjected to ultrarapid freezing rates, often in the presence of cryoprotective agents to limit ice crystal formation, with subsequent fracturing of the specimen at liquid nitrogen cooled temperatures under high vacuum. The resultant fractured surface is replicated and stabilized by evaporation of carbon and platinum from an angle that confers surface three-dimensional detail to the cast. This technique has proved particularly enlightening for the investigation of cell membranes and their specializations and has contributed considerably to the understanding of cellular form to related cell function. In this report, we survey the instrument requirements and technical protocol for performing freeze-fracture, the associated nomenclature and characteristics of fracture planes, variations on the conventional procedure, and criteria for interpretation of freeze-fracture images. This technique has been widely used for ultrastructural investigation in many areas of cell biology and holds promise as an emerging imaging technique for molecular, nanotechnology, and materials science studies.

Validation of Remote Sensing Retrieval Products using Data from a Wireless Sensor-Based Online Monitoring in Antarctica

PubMed Central

Li, Xiuhong; Cheng, Xiao; Yang, Rongjin; Liu, Qiang; Qiu, Yubao; Zhang, Jialin; Cai, Erli; Zhao, Long

2016-01-01

Of the modern technologies in polar-region monitoring, the remote sensing technology that can instantaneously form large-scale images has become much more important in helping acquire parameters such as the freezing and melting of ice as well as the surface temperature, which can be used in the research of global climate change, Antarctic ice sheet responses, and cap formation and evolution. However, the acquirement of those parameters is impacted remarkably by the climate and satellite transit time which makes it almost impossible to have timely and continuous observation data. In this research, a wireless sensor-based online monitoring platform (WSOOP) for the extreme polar environment is applied to obtain a long-term series of data which is site-specific and continuous in time. Those data are compared and validated with the data from a weather station at Zhongshan Station Antarctica and the result shows an obvious correlation. Then those data are used to validate the remote sensing products of the freezing and melting of ice and the surface temperature and the result also indicated a similar correlation. The experiment in Antarctica has proven that WSOOP is an effective system to validate remotely sensed data in the polar region. PMID:27869668

Validation of Remote Sensing Retrieval Products using Data from a Wireless Sensor-Based Online Monitoring in Antarctica.

PubMed

Li, Xiuhong; Cheng, Xiao; Yang, Rongjin; Liu, Qiang; Qiu, Yubao; Zhang, Jialin; Cai, Erli; Zhao, Long

2016-11-17

Of the modern technologies in polar-region monitoring, the remote sensing technology that can instantaneously form large-scale images has become much more important in helping acquire parameters such as the freezing and melting of ice as well as the surface temperature, which can be used in the research of global climate change, Antarctic ice sheet responses, and cap formation and evolution. However, the acquirement of those parameters is impacted remarkably by the climate and satellite transit time which makes it almost impossible to have timely and continuous observation data. In this research, a wireless sensor-based online monitoring platform (WSOOP) for the extreme polar environment is applied to obtain a long-term series of data which is site-specific and continuous in time. Those data are compared and validated with the data from a weather station at Zhongshan Station Antarctica and the result shows an obvious correlation. Then those data are used to validate the remote sensing products of the freezing and melting of ice and the surface temperature and the result also indicated a similar correlation. The experiment in Antarctica has proven that WSOOP is an effective system to validate remotely sensed data in the polar region.

Microscopic relaxations in a protein sustained down to 160 K in a non-glass forming organic solvent

DOE PAGES

Mamontov, Eugene; O'Neil, Hugh

2016-05-03

In this paper, we have studied microscopic dynamics of a protein in carbon disulfide, a non-glass forming solvent, down to its freezing temperature of ca. 160 K. We have utilized quasielastic neutron scattering. A comparison of lysozyme hydrated with water and dissolved in carbon disulfide reveals a stark difference in the temperature dependence of the protein's microscopic relaxation dynamics induced by the solvent. In the case of hydration water, the common protein glass-forming solvent, the protein relaxation slows down in response to a large increase in the water viscosity on cooling down, exhibiting a well-known protein dynamical transition. The dynamicalmore » transition disappears in non-glass forming carbon disulfide, whose viscosity remains a weak function of temperature all the way down to freezing at just below 160 K. The microscopic relaxation dynamics of lysozyme dissolved in carbon disulfide is sustained down to the freezing temperature of its solvent at a rate similar to that measured at ambient temperature. Finally, our results demonstrate that protein dynamical transition is not merely solvent-assisted, but rather solvent-induced, or, more precisely, is a reflection of the temperature dependence of the solvent's glass-forming dynamics.« less

Effects of high pressure freezing (HPF) on denaturation of natural actomyosin extracted from prawn (Metapenaeus ensis).

PubMed

Cheng, Lina; Sun, Da-Wen; Zhu, Zhiwei; Zhang, Zhihang

2017-08-15

Effects of protein denaturation caused by high pressure freezing, involving Pressure-Factors (pressure, time) and Freezing-Factors (temperature, phase transition, recrystallization, ice crystal types), are complicated. In the current study, the conformation and functional changes of natural actomyosin (NAM) under pressure assisted freezing (PAF, 100,150,300,400,500MPa P -20°C/25min ), pressure shift freezing (PSF, 200MPa P -20°C/25min ), and immersion freezing ( 0.1MPa P -20°C/5min ) after pressure was released to 0.1MPa, as compared to normal immersion freezing process (IF, 0.1MPa P -20°C/30min ). Results indicated that PSF ( 200MPa P -20°C/30min ) could reduce the denaturation of frozen NAM and a pressure of 300MPa was the critical point to induce such a denaturation. During the periods of B→D in PSF or B→C→D in PAF, the generation and growth of ice crystals played an important role on changing the secondary and tertiary structure of the treated NAM. Copyright © 2017 Elsevier Ltd. All rights reserved.

Local structural ordering in surface-confined liquid crystals

NASA Astrophysics Data System (ADS)

Śliwa, I.; Jeżewski, W.; Zakharov, A. V.

2017-06-01

The effect of the interplay between attractive nonlocal surface interactions and attractive pair long-range intermolecular couplings on molecular structures of liquid crystals confined in thin cells with flat solid surfaces has been studied. Extending the McMillan mean field theory to include finite systems, it has been shown that confining surfaces can induce complex orientational and translational ordering of molecules. Typically, local smectic A, nematic, and isotropic phases have been shown to coexist in certain temperature ranges, provided that confining cells are sufficiently thick, albeit finite. Due to the nonlocality of surface interactions, the spatial arrangement of these local phases can display, in general, an unexpected complexity along the surface normal direction. In particular, molecules located in the vicinity of surfaces can still be organized in smectic layers, even though nematic and/or isotropic order can simultaneously appear in the interior of cells. The resulting surface freezing of smectic layers has been confirmed to occur even for rather weak surface interactions. The surface interactions cannot, however, prevent smectic layers from melting relatively close to system boundaries, even when molecules are still arranged in layers within the central region of the system. The internal interfaces, separating individual liquid-crystal phases, are demonstrated here to form fronts of local finite-size transitions that move across cells under temperature changes. Although the complex molecular ordering in surface confined liquid-crystal systems can essentially be controlled by temperature variations, specific thermal properties of these systems, especially the nature of the local transitions, are argued to be strongly conditioned to the degree of molecular packing.

Proton NMR study of extra Virgin Olive Oil with temperature: Freezing and melting kinetics

NASA Astrophysics Data System (ADS)

Mallamace, Domenico; Longo, Sveva; Corsaro, Carmelo

2018-06-01

The thermal properties of an extra Virgin Olive Oil (eVOO) depend on its composition and indeed characterize its quality. Many studies have shown that the freezing and melting behaviors of eVOOs can serve for geographical or chemical discrimination. We use Nuclear Magnetic Resonance spectroscopy to study the evolution of the fatty acids bands as a function of temperature during freezing and melting processes. In such a way we can follow separately the variations in the thermal properties of the different molecular groups during these thermodynamic phase transitions. The data indicate that the methyl group which is at the end of every fatty chain displays the major changes during both freezing and melting processes.

Dynamical freeze-out criterion in a hydrodynamical description of Au + Au collisions at √{sNN}=200 GeV and Pb + Pb collisions at √{sNN}=2760 GeV

NASA Astrophysics Data System (ADS)

Ahmad, Saeed; Holopainen, Hannu; Huovinen, Pasi

2017-05-01

In hydrodynamical modeling of ultrarelativistic heavy-ion collisions, the freeze-out is typically assumed to take place at a surface of constant temperature or energy density. A more physical approach is to assume that freeze-out takes place at a surface of constant Knudsen number. We evaluate the Knudsen number as a ratio of the expansion rate of the system to the pion-scattering rate and apply the constant Knudsen number freeze-out criterion to the ideal hydrodynamical description of heavy-ion collisions at the Relativistic Heavy Ion Collider at BNL (√{sNN}=200 GeV) and the Large Hadron Collider (√{sNN}=2760 GeV) energies. We see that once the numerical values of freeze-out temperature and freeze-out Knudsen number are chosen to produce similar pT distributions, the elliptic and triangular anisotropies are similar too, in both event-by-event and averaged initial state calculations.

Effective freezing rate for semen cryopreservation in endangered Mediterranean brown trout (Salmo trutta macrostigma) inhabiting the Biferno river (South Italy).

PubMed

Iaffaldano, Nicolaia; Di Iorio, Michele; Manchisi, Angelo; Esposito, Stefano; Gibertoni, Pier Paolo

2016-10-01

This study was designed to determine: (i) the in vitro effects of different freezing rates on post-thaw semen quality of Mediterranean brown trout (Salmo trutta macrostigma) from the Biferno river; and (ii) the in vivo fertilization and hatching percentage of freezing rate giving rise to the best post-thaw semen quality. Pooled semen samples were diluted 1:3 (v:v) in a freezing extender composed of 300 mM glucose, 10% egg yolk and 10% dimethyl sulfoxide (DMSO). The extended semen was packaged in 0.25 ml plastic straws and frozen at different heights above the liquid nitrogen surface (1, 5 or 10 cm) for 10 min to give three different freezing rates. Semen samples were thawed at 30°C for 10 s. The variables assessed after thawing were sperm motility, duration of motility and viability. Our results clearly indicate a significant effect of freezing rate on post-thaw semen quality. Semen frozen 5 cm above the liquid nitrogen surface showed the best quality after freezing/thawing. Based on these in vitro data, 2 groups of 200 eggs were fertilized with fresh semen or semen frozen 5 cm above the liquid nitrogen surface. Fertilization and hatching rates recorded for eggs fertilized with frozen semen were significantly lower (25.4% and 22.5%, respectively) than the ones obtained using fresh semen (87.8% and 75.5%, respectively). An effective freezing protocol will allow for the creation of a sperm cryobank to recover the original population of Mediterranean brown trout in the Biferno river.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Khrapak, Sergey A.; Joint Institute for High Temperatures, 125412 Moscow; Chaudhuri, Manis

We put forward an approximate method to locate the fluid-solid (freezing) phase transition in systems of classical particles interacting via a wide range of Lennard-Jones-type potentials. This method is based on the constancy of the properly normalized second derivative of the interaction potential (freezing indicator) along the freezing curve. As demonstrated recently it yields remarkably good agreement with previous numerical simulation studies of the conventional 12-6 Lennard-Jones (LJ) fluid [S.A.Khrapak, M.Chaudhuri, G.E.Morfill, Phys. Rev. B 134, 052101 (2010)]. In this paper, we test this approach using a wide range of the LJ-type potentials, including LJ n-6 and exp-6 models, andmore » find that it remains sufficiently accurate and reliable in reproducing the corresponding freezing curves, down to the triple-point temperatures. One of the possible application of the method--estimation of the freezing conditions in complex (dusty) plasmas with ''tunable'' interactions--is briefly discussed.« less

In situ study on atomic mechanism of melting and freezing of single bismuth nanoparticles

PubMed Central

Li, Yingxuan; Zang, Ling; Jacobs, Daniel L.; Zhao, Jie; Yue, Xiu; Wang, Chuanyi

2017-01-01

Experimental study of the atomic mechanism in melting and freezing processes remains a formidable challenge. We report herein on a unique material system that allows for in situ growth of bismuth nanoparticles from the precursor compound SrBi2Ta2O9 under an electron beam within a high-resolution transmission electron microscope (HRTEM). Simultaneously, the melting and freezing processes within the nanoparticles are triggered and imaged in real time by the HRTEM. The images show atomic-scale evidence for point defect induced melting, and a freezing mechanism mediated by crystallization of an intermediate ordered liquid. During the melting and freezing, the formation of nucleation precursors, nucleation and growth, and the relaxation of the system, are directly observed. Based on these observations, an interaction–relaxation model is developed towards understanding the microscopic mechanism of the phase transitions, highlighting the importance of cooperative multiscale processes. PMID:28194017

In situ study on atomic mechanism of melting and freezing of single bismuth nanoparticles

NASA Astrophysics Data System (ADS)

Li, Yingxuan; Zang, Ling; Jacobs, Daniel L.; Zhao, Jie; Yue, Xiu; Wang, Chuanyi

2017-02-01

Experimental study of the atomic mechanism in melting and freezing processes remains a formidable challenge. We report herein on a unique material system that allows for in situ growth of bismuth nanoparticles from the precursor compound SrBi2Ta2O9 under an electron beam within a high-resolution transmission electron microscope (HRTEM). Simultaneously, the melting and freezing processes within the nanoparticles are triggered and imaged in real time by the HRTEM. The images show atomic-scale evidence for point defect induced melting, and a freezing mechanism mediated by crystallization of an intermediate ordered liquid. During the melting and freezing, the formation of nucleation precursors, nucleation and growth, and the relaxation of the system, are directly observed. Based on these observations, an interaction-relaxation model is developed towards understanding the microscopic mechanism of the phase transitions, highlighting the importance of cooperative multiscale processes.

In situ study on atomic mechanism of melting and freezing of single bismuth nanoparticles.

PubMed

Li, Yingxuan; Zang, Ling; Jacobs, Daniel L; Zhao, Jie; Yue, Xiu; Wang, Chuanyi

2017-02-13

Experimental study of the atomic mechanism in melting and freezing processes remains a formidable challenge. We report herein on a unique material system that allows for in situ growth of bismuth nanoparticles from the precursor compound SrBi 2 Ta 2 O 9 under an electron beam within a high-resolution transmission electron microscope (HRTEM). Simultaneously, the melting and freezing processes within the nanoparticles are triggered and imaged in real time by the HRTEM. The images show atomic-scale evidence for point defect induced melting, and a freezing mechanism mediated by crystallization of an intermediate ordered liquid. During the melting and freezing, the formation of nucleation precursors, nucleation and growth, and the relaxation of the system, are directly observed. Based on these observations, an interaction-relaxation model is developed towards understanding the microscopic mechanism of the phase transitions, highlighting the importance of cooperative multiscale processes.

The effect of low temperature on Antarctic endolithic green algae

NASA Technical Reports Server (NTRS)

Meyer, M. A.; Morris, G. J.; Friedmann, E. I.

1988-01-01

Laboratory experiments show that undercooling to about -5 degrees C occurs in colonized Beacon sandstones of the Ross Desert, Antarctica. High-frequency temperature oscillations between 5 degrees C and -5 degrees C or -10 degrees C (which occur in nature on the rock surface) did not damage Hemichloris antarctica. In a cryomicroscope, H. antarctica appeared to be undamaged after slow or rapid cooling to -50 degrees C. 14CO2 incorporation after freezing to -20 degrees C was unaffected in H. antarctica or in Trebouxia sp. but slightly depressed in Stichococcus sp. (isolated from a less extreme Antarctic habitat). These results suggest that the freezing regime in the Antarctic desert is not injurious to endolithic algae. It is likely that the freezing-point depression inside the rock makes available liquid water for metabolic activity at subzero temperatures. Freezing may occur more frequently on the rock surface and contribute to the abiotic nature of the surface.

Optimization of a cryoprotective medium to increase the viability of freeze-dried Streptococcus thermophilus by response surface methodology

USDA-ARS?s Scientific Manuscript database

Streptococcus thermophilus normally exhibits different survival rates in different bacteria medium during freeze-drying. In this study, response surface methodology (RSM) was applied on the design of experiments for optimizing the cryoprotective medium. Results showed that the most significant facto...

Development of a freeze-tolerant solar water heater using crosslinked polyethylene as a material of construction. Final report, June 18, 1976--October 1, 1977

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bradley, J.M.

The feasibility of building a freeze-tolerant absorber for a solar water heater out of carbon-black-reinforced crosslinked polyethylene has been explored. Ten-foot tube specimens made from various crosslinked polyethylene formulations were filled with water at various pressures, and then placed into a deep freeze, then thawed and frozen again for 100 freeze-thaw cycles, or until the tube specimen failed. Tube diameters were measured before and after each freezing to determine how much distention the freezing caused, and how much permanent distention was caused by the strains of repeated freezings. Five tube specimens containing water at as high as 80 psi survivedmore » 100 freeze-thaw cycles. Also, a flat plate collector was fabricated using as absorber surface a single 400 ft tube of carbon-black-reinforced crosslinked polyethylene in the form of a flat spiral coil and this collector was tested for performance at the Los Alamos Scientific Laboratory. The performance test indicates that the absorbancy of such a flat spiral coil to solar radiation is similar to typical black surfaces used on solar absorbers. Thus, it does seem very feasible that domestic water can be directly heated in a solar collector having an absorber made from crosslinked polyethylene, and that this collector can safely withstand at least 100 freeze-thaw cycles.« less

Freezing Bubbles

NASA Astrophysics Data System (ADS)

Kingett, Christian; Ahmadi, Farzad; Nath, Saurabh; Boreyko, Jonathan

2017-11-01

The two-stage freezing process of a liquid droplet on a substrate is well known; however, how bubbles freeze has not yet been studied. We first deposited bubbles on a silicon substrate that was chilled at temperatures ranging from -10 °C to -40 °C, while the air was at room temperature. We observed that the freeze front moved very slowly up the bubble, and in some cases, even came to a complete halt at a critical height. This slow freezing front propagation can be explained by the low thermal conductivity of the thin soap film, and can be observed more clearly when the bubble size or the surface temperature is increased. This delayed freezing allows the frozen portion of the bubble to cool the air within the bubble while the top part is still liquid, which induces a vapor pressure mismatch that either collapses the top or causes the top to pop. In cases where the freeze front reaches the top of the bubble, a portion of the top may melt and slowly refreeze; this can happen more than just once for a single bubble. We also investigated freezing bubbles inside of a freezer where the air was held at -20 °C. In this case, the bubbles freeze quickly and the ice grows radially from nucleation sites instead of perpendicular to the surface, which provides a clear contrast with the conduction limited room temperature bubbles.

Adsorption inhibition as a mechanism of freezing resistance in polar fishes.

PubMed Central

Raymond, J A; DeVries, A L

1977-01-01

Polar fishes are known to have serum proteins and glycoproteins that protect them from freezing, by a noncolligative process. Measurements of antifreeze concentrations in ice and scanning electron micrographs of freeze-dried antifreeze solutions indicate that the antifreezes are incorporated in ice during freezing. The antifreezes also have a pronounced effect on the crystal habit of ice grown in their presence. Each of four antifreezes investigated caused ice to grow in long needles whose axes were parallel to the ice c axis. Together these results indicate the antifreezes adsorb to ice surfaces and inhibit their growth. A model in which adsorbed antifreezes raise the curvature of growth steps on the ice surface is proposed to account for the observed depression of the temperature at which freezing occurs and agrees well with experimental observations. The model is similar to one previously proposed for other cases of crystal growth inhibition. Images PMID:267952

Structure, phonon properties, and order-disorder transition in the metal formate framework of [NH4][Mg(HCOO)3].

PubMed

Mączka, Mirosław; Pietraszko, Adam; Macalik, Bogusław; Hermanowicz, Krzysztof

2014-01-21

We report the synthesis, crystal structure, thermal, dielectric, IR, and Raman studies of [NH4][Mg(HCOO)3] formate. Single-crystal X-ray diffraction shows that it crystallizes in the hexagonal space group P6322, with orientationally disordered NH4(+) ions located in the cages of the network. Upon cooling, [NH4][Mg(HCOO)3] undergoes a phase transition at around 255 K to the ferroelectric P63 structure. Raman and IR spectra show a strong increase in intensity of the N-H stretching bands as well as narrowing of the bands related to the NH4(+) ions upon cooling. These changes indicate that the phase transition is due to orientational ordering of the NH4(+) ions. Analysis of the Raman data show, however, that the rotational and translational motions of NH4(+) do not freeze completely at the phase transition but exhibit further slowing down below 255 K, and the motional freezing becomes nearly complete below 140 K.

Glass transition of aqueous solutions involving annealing-induced ice recrystallization resolves liquid-liquid transition puzzle of water

PubMed Central

Zhao, Li-Shan; Cao, Ze-Xian; Wang, Qiang

2015-01-01

Liquid-liquid transition of water is an important concept in condensed-matter physics. Recently, it was claimed to have been confirmed in aqueous solutions based on annealing-induced upshift of glass-liquid transition temperature, . Here we report a universal water-content, , dependence of for aqueous solutions. Solutions with vitrify/devitrify at a constant temperature, , referring to freeze-concentrated phase with left behind ice crystallization. Those solutions with totally vitrify at under conventional cooling/heating process though, of the samples annealed at temperatures   to effectively evoke ice recrystallization is stabilized at . Experiments on aqueous glycerol and 1,2,4-butanetriol solutions in literature were repeated, and the same samples subject to other annealing treatments equally reproduce the result. The upshift of by annealing is attributable to freeze-concentrated phase of solutions instead of ‘liquid II phase of water’. Our work also provides a reliable method to determine hydration formula and to scrutinize solute-solvent interaction in solution. PMID:26503911

Through-vial impedance spectroscopy of the mechanisms of annealing in the freeze-drying of maltodextrin: the impact of annealing hold time and temperature on the primary drying rate.

PubMed

Smith, Geoff; Arshad, Muhammad Sohail; Polygalov, Eugene; Ermolina, Irina

2014-06-01

The study aims to investigate the impact of annealing hold time and temperature on the primary drying rate/duration of a 10% (w/v) solution of maltodextrin with an emphasis on how the mechanisms of annealing might be understood from the in-vial measurements of the ice crystal growth and the glass transition. The electrical impedance of the solution within a modified glass vial was recorded between 10 and 10(6) Hz during freeze-drying cycles with varying annealing hold times (1-5 h) and temperatures. Primary drying times decreased by 7%, 27% and 34% (1.1, 4.3 and 5.5 h) with the inclusion of an annealing step at temperatures of -15°C, -10°C and -5°C, respectively. The glass transition was recorded at approximately -16°C during the re-heating and re-cooling steps, which is close to the glass transition (Tg ') reported for 10% (w/v) maltodextrin and therefore indicates that a maximum freeze concentration (∼86%, w/w, from the Gordon-Taylor equation) was achieved during first freezing, with no further ice being formed on annealing. This observation, coupled to the decrease in electrical resistance that was observed during the annealing hold time, suggests that the reduction in the drying time was because of improved connectivity of ice crystals because of Ostwald ripening rather than devitrification. © 2014 Wiley Periodicals, Inc. and the American Pharmacists Association.

Formation of stable submicron peptide or protein particles by thin film freezing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Johnston, Keith P.; Engstrom, Joshua; Williams, III, Robert O.

The present invention includes compositions and methods for preparing micron-sized or submicron-sized particles by dissolving a water soluble effective ingredient in one or more solvents; spraying or dripping droplets solvent such that the effective ingredient is exposed to a vapor-liquid interface of less than 50, 100, 150, 200, 250, 200, 400 or 500 cm.sup.-1 area/volume to, e.g., increase protein stability; and contacting the droplet with a freezing surface that has a temperature differential of at least 30.degree. C. between the droplet and the surface, wherein the surface freezes the droplet into a thin film with a thickness of less thanmore » 500 micrometers and a surface area to volume between 25 to 500 cm.sup.-1.« less

Isolation of a Soluble Component of Plasmodium berghei Which Induces Immunity in Rats

PubMed Central

Grothaus, G. D.; Kreier, J. P.

1980-01-01

Soluble material was obtained from sonically freed plasmodiae by three procedures. Two procedures, cryo-impacting and freeze-thawing, were evaluated for their ability to disrupt the parasites and release soluble material. The soluble materials obtained by these procedures were compared to materials washed from the surfaces of sonically freed parasites. Between 35 and 40% of the total parasite protein was solubilized by freeze-thawing or cryo-impacting. One cycle of freeze-thawing released nearly as much protein as could be released by this method, and additional cycles of freeze-thawing had little additional effect. Cryo-impacting solubilized only a small amount of protein in addition to that which was released by the cycle of freeze-thawing inherent in the procedure. Reductions in the packed cell volume of the material remaining after freeze-thawing or cryo-impacting indicate that the insoluble fragments are broken into smaller pieces as treatment is extended. Electron microscopy of 30-s cryo-impacted and three-times freeze-thawed parasites revealed membrane fragments similar in appearance. Patterns obtained by polyacrylamide gel electrophoresis of the soluble material from freeze-thawed and cryo-impacted parasites were also similar, and approximately 13 protein bands were demonstrated. The material washed from the surfaces of the free parasites, on the other hand, resolved into only two to four major bands on the gel columns. In immunization studies, the soluble and insoluble fractions obtained by freeze-thawing or cryo-impacting and the material washed from the surfaces of the parasites all stimulated a protective immune response. On the basis of the amount of protein required to stimulate roughly comparable immunity, the soluble fraction obtained by freeze-thawing or cryo-impacting free parasites was about twice as potent an immunogen as was the insoluble fraction. The material obtained by gentle washing of the freed parasites was approximately 20 times as potent an immunogen as were the freed parasites and about 7 times as potent as the soluble material obtained by freeze-thawing or cryo-impacting. Images Fig. 1 Fig. 2 PMID:6991439

Local structural mechanism for frozen-in dynamics in metallic glasses

NASA Astrophysics Data System (ADS)

Liu, X. J.; Wang, S. D.; Wang, H.; Wu, Y.; Liu, C. T.; Li, M.; Lu, Z. P.

2018-04-01

The nature of the glass transition is a fundamental and long-standing intriguing issue in the condensed-matter physics and materials science community. In particular, the structural response by which a liquid is arrested dynamically to form a glass or amorphous solid upon approaching its freezing temperature [the glass transition temperature (Tg)] remains unclear. Various structural scenarios in terms of the percolation theory have been proposed recently to understand such a phenomenon; however, there is still no consensus on what the general percolation entity is and how the entity responds to the sudden slowdown dynamics during the glass transition. In this paper, we demonstrate that one-dimensional local linear ordering (LLO) is a universal structural motif associated with the glass transition for various metallic glasses. The quantitative evolution of LLO with temperature indicates that a percolating LLO network forms to serve as the backbone of the rigid glass solid when the temperature approaches the freezing point, resulting in the frozen-in dynamics accompanying the glass transition. The percolation transition occurs by pinning different LLO networks together, which only needs the introduction of a small number of "joint" atoms between them, and therefore the energy expenditure is very low.

Hydrogen Crystallization in Low-Density Aerogels

DOE PAGES

Kucheyev, S. O.; Van Cleve, E.; Johnston, L. T.; ...

2015-03-17

Crystallization of liquids confined in disordered low-density nanoporous scaffolds is poorly understood. Here in this work, we use relaxation calorimetry to study the liquid–solid phase transition of H 2 in a series of silica and carbon (nanotube- and graphene-based) aerogels with porosities ≳94%. Results show that freezing temperatures of H 2 inside all the aerogels studied are depressed but do not follow predictions of the Gibbs–Thomson theory based on average pore diameters measured by conventional gas sorption techniques. Instead, we find that, for each material family investigated, the depression of average freezing temperatures scales linearly with the ratio of themore » internal surface area (measured by gas sorption) and the total pore volume derived from the density of aerogel monoliths. The slope of such linear dependences is, however, different for silica and carbon aerogels, which we attribute to microporosity of carbons and the presence of macropores in silica aerogels. In conclusion, our results have important implications for the analysis of pore size distributions of low-density nanoporous materials and for controlling crystallization of fuel layers in targets for thermonuclear fusion energy applications.« less

Hydrogen crystallization in low-density aerogels.

PubMed

Kucheyev, S O; Van Cleve, E; Johnston, L T; Gammon, S A; Worsley, M A

2015-04-07

Crystallization of liquids confined in disordered low-density nanoporous scaffolds is poorly understood. Here, we use relaxation calorimetry to study the liquid-solid phase transition of H2 in a series of silica and carbon (nanotube- and graphene-based) aerogels with porosities ≳94%. Results show that freezing temperatures of H2 inside all the aerogels studied are depressed but do not follow predictions of the Gibbs-Thomson theory based on average pore diameters measured by conventional gas sorption techniques. Instead, we find that, for each material family investigated, the depression of average freezing temperatures scales linearly with the ratio of the internal surface area (measured by gas sorption) and the total pore volume derived from the density of aerogel monoliths. The slope of such linear dependences is, however, different for silica and carbon aerogels, which we attribute to microporosity of carbons and the presence of macropores in silica aerogels. Our results have important implications for the analysis of pore size distributions of low-density nanoporous materials and for controlling crystallization of fuel layers in targets for thermonuclear fusion energy applications.

Effects of annealing on the physical properties of therapeutic proteins during freeze drying process.

PubMed

Lim, Jun Yeul; Lim, Dae Gon; Kim, Ki Hyun; Park, Sang-Koo; Jeong, Seong Hoon

2018-02-01

Effects of annealing steps during the freeze drying process on etanercept, model protein, were evaluated using various analytical methods. The annealing was introduced in three different ways depending on time and temperature. Residual water contents of dried cakes varied from 2.91% to 6.39% and decreased when the annealing step was adopted, suggesting that they are directly affected by the freeze drying methods Moreover, the samples were more homogenous when annealing was adopted. Transition temperatures of the excipients (sucrose, mannitol, and glycine) were dependent on the freeze drying steps. Size exclusion chromatography showed that monomer contents were high when annealing was adopted and also they decreased less after thermal storage at 60°C. Dynamic light scattering results exhibited that annealing can be helpful in inhibiting aggregation and that thermal storage of freeze-dried samples preferably induced fragmentation over aggregation. Shift of circular dichroism spectrum and of the contents of etanercept secondary structure was observed with different freeze drying steps and thermal storage conditions. All analytical results suggest that the physicochemical properties of etanercept formulation can differ in response to different freeze drying steps and that annealing is beneficial for maintaining stability of protein and reducing the time of freeze drying process. Copyright © 2017 Elsevier B.V. All rights reserved.

Effect of cooling rate on the survival of cryopreserved rooster sperm: Comparison of different distances in the vapor above the surface of the liquid nitrogen.

PubMed

Madeddu, M; Mosca, F; Abdel Sayed, A; Zaniboni, L; Mangiagalli, M G; Colombo, E; Cerolini, S

2016-08-01

The aim of the present trial was to study the effect of different freezing rates on the survival of cryopreserved rooster semen packaged in straws. Slow and fast freezing rates were obtained keeping straws at different distances in the vapor above the surface of the nitrogen during freezing. Adult Lohmann roosters (n=27) were used. Two experiments were conducted. In Experiment 1, semen was packaged in straws and frozen comparing the distances of 1, 3 and 5cm in nitrogen vapor above the surface of the liquid nitrogen. In Experiment 2, the distances of 3, 7 and 10cm above the surfaces of the liquid nitrogen were compared. Sperm viability, motility and progressive motility and the kinetic variables were assessed in fresh and cryopreserved semen samples. The recovery rates after freezing/thawing were also calculated. In Experiment 1, there were no significant differences among treatments for all semen quality variables. In Experiment 2, the percentage of viable (46%) and motile (22%) sperm in cryopreserved semen was greater when semen was placed 3cm compared with 7 and 10cm in the vapor above the surface of the liquid nitrogen. The recovery rate of progressive motile sperm after thawing was also greater when semen was stored 3cm in the vapor above the surface of the liquid nitrogen. More rapid freezing rates are required to improve the survival of rooster sperm after cryopreservation and a range of distances from 1 to 5cm in nitrogen vapor above the surface of the liquid nitrogen is recommended for optimal sperm viability. Copyright © 2016 Elsevier B.V. All rights reserved.

Spontaneous self-dislodging of freezing water droplets and the role of wettability

PubMed Central

Schutzius, Thomas M.; Eghlidi, Hadi; Poulikakos, Dimos

2017-01-01

Spontaneous removal of liquid, solidifying liquid and solid forms of matter from surfaces, is of significant importance in nature and technology, where it finds applications ranging from self-cleaning to icephobicity and to condensation systems. However, it is a great challenge to understand fundamentally the complex interaction of rapidly solidifying, typically supercooled, droplets with surfaces, and to harvest benefit from it for the design of intrinsically icephobic materials. Here we report and explain an ice removal mechanism that manifests itself simultaneously with freezing, driving gradual self-dislodging of droplets cooled via evaporation and sublimation (low environmental pressure) or convection (atmospheric pressure) from substrates. The key to successful self-dislodging is that the freezing at the droplet free surface and the droplet contact area with the substrate do not occur simultaneously: The frozen phase boundary moves inward from the droplet free surface toward the droplet–substrate interface, which remains liquid throughout most of the process and freezes last. We observe experimentally, and validate theoretically, that the inward motion of the phase boundary near the substrate drives a gradual reduction in droplet–substrate contact. Concurrently, the droplet lifts from the substrate due to its incompressibility, density differences, and the asymmetric freezing dynamics with inward solidification causing not fully frozen mass to be displaced toward the unsolidified droplet–substrate interface. Depending on surface topography and wetting conditions, we find that this can lead to full dislodging of the ice droplet from a variety of engineered substrates, rendering the latter ice-free. PMID:28973877

The relevance of the amorphous state to pharmaceutical dosage forms: glassy drugs and freeze dried systems.

PubMed

Craig, D Q; Royall, P G; Kett, V L; Hopton, M L

1999-03-15

Many pharmaceuticals, either by accident or design, may exist in a total or partially amorphous state. Consequently, it is essential to have an understanding of the physico-chemical principles underpinning the behaviour of such systems. In this discussion, the nature of the glassy state will be described, with particular emphasis on the molecular processes associated with glass transitional behaviour and the use of thermal methods for characterising the glass transition temperature, Tg. The practicalities of such measurements, the significance of the accompanying relaxation endotherm and plasticization effects are considered. The advantages and difficulties associated with the use of amorphous drugs will be outlined, with discussion given regarding the problems associated with physical and chemical stability. Finally, the principles of freeze drying will be described, including discussion of the relevance of glass transitional behaviour to product stability. Copyright

Effect of Multiple Freezing/Thawing Cycles on the Structural and Functional Properties of Waxy Rice Starch

PubMed Central

Tao, Han; Yan, Juan; Zhao, Jianwei; Tian, Yaoqi; Jin, Zhengyu; Xu, Xueming

2015-01-01

The structural and functional properties of non-gelatinized waxy rice starch were investigated after 1, 3, 7, and 10 freezing/thawing cycles. Freezing caused an increasing damaged starch from 1.36% in native waxy rice starch to 5.77% in 10 freezing/thawing-treated starch (FTS), as evidenced by the cracking surface on starch granules. More dry matter concentration was leached, which was characterized by high amylopectin concentration (4.34 mg/mL). The leaching was accompanied by a decrease in relative crystallinity from 35.19% in native starch to 31.34% in 10 FTS. Freezing treatment also led to significant deviations in the functional characteristics, for instance decreased gelatinization temperature range, enthalpy, and pasting viscosities. The resistant starch content of 10FTS significantly decreased from 58.9% to 19%, whereas the slowly digested starch content greatly increased from 23.8% in native starch to 50.3%. The increase in susceptibility to enzyme hydrolysis may be attributed to porous granular surface, amylopectin leaching, and the decrease in the relative crystallinity caused by freezing water. PMID:26018506

Effect of multiple freezing/thawing cycles on the structural and functional properties of waxy rice starch.

PubMed

Tao, Han; Yan, Juan; Zhao, Jianwei; Tian, Yaoqi; Jin, Zhengyu; Xu, Xueming

2015-01-01

The structural and functional properties of non-gelatinized waxy rice starch were investigated after 1, 3, 7, and 10 freezing/thawing cycles. Freezing caused an increasing damaged starch from 1.36% in native waxy rice starch to 5.77% in 10 freezing/thawing-treated starch (FTS), as evidenced by the cracking surface on starch granules. More dry matter concentration was leached, which was characterized by high amylopectin concentration (4.34 mg/mL). The leaching was accompanied by a decrease in relative crystallinity from 35.19% in native starch to 31.34% in 10 FTS. Freezing treatment also led to significant deviations in the functional characteristics, for instance decreased gelatinization temperature range, enthalpy, and pasting viscosities. The resistant starch content of 10FTS significantly decreased from 58.9% to 19%, whereas the slowly digested starch content greatly increased from 23.8% in native starch to 50.3%. The increase in susceptibility to enzyme hydrolysis may be attributed to porous granular surface, amylopectin leaching, and the decrease in the relative crystallinity caused by freezing water.

Freeze-dried powdered yacon: effects of FOS on serum glucose, lipids and intestinal transit in the elderly.

PubMed

Scheid, M M A; Genaro, P S; Moreno, Y M F; Pastore, G M

2014-10-01

Freeze-dried powdered yacon (FDY) can be considered a prebiotic product due to its fructooligosaccharides (FOS) content. The effect of 9 weeks of daily intake of FDY containing 7.4 g of FOS on glucose, lipid metabolism and intestinal transit in a group of elderly people was investigated. Seventy-two elderly (mean age 67.11 ± 6.11) men and women were studied for 9 weeks in a double-blind, placebo-controlled experiment. They were randomly assigned to the supplement group (which received 7.4 g of FOS as FDY) or the control group. At the beginning and end of the study, anthropometric measurements, blood sampling, clinical analyses and dietary intake were assessed. A daily intake of FDY containing 7.4 g of FOS for 9 weeks was associated with a mean decrease in serum glucose (p = 0.013), but supplementation did not reduce serum lipids in the study group. The administered dose did not adversely affect intestinal transit. It did not cause bloating, flatulence or intestinal discomfort. Freeze-dried powdered yacon is a good source of FOS, and daily consumption can have a favourable effect on serum glucose in the elderly. It is also practical, easy and safe to use and store.

Detection of Collapse and Crystallization of Saccharide, Protein, and Mannitol Formulations by Optical Fibers in Lyophilization

PubMed Central

Horn, Jacqueline; Friess, Wolfgang

2018-01-01

The collapse temperature (Tc) and the glass transition temperature of freeze-concentrated solutions (Tg') as well as the crystallization behavior of excipients are important physicochemical characteristics which guide the cycle development in freeze-drying. The most frequently used methods to determine these values are differential scanning calorimetry (DSC) and freeze-drying microscopy (FDM). The objective of this study was to evaluate the optical fiber system (OFS) unit as alternative tool for the analysis of Tc, Tg' and crystallization events. The OFS unit was also tested as a potential online monitoring tool during freeze-drying. Freeze/thawing and freeze-drying experiments of sucrose, trehalose, stachyose, mannitol, and highly concentrated IgG1 and lysozyme solutions were carried out and monitored by the OFS. Comparative analyses were performed by DSC and FDM. OFS and FDM results correlated well. The crystallization behavior of mannitol could be monitored by the OFS during freeze/thawing as it can be done by DSC. Online monitoring of freeze-drying runs detected collapse of amorphous saccharide matrices. The OFS unit enabled the analysis of both Tc and crystallization processes, which is usually carried out by FDM and DSC. The OFS can hence be used as novel measuring device. Additionally, detection of these events during lyophilization facilitates online-monitoring. Thus the OFS is a new beneficial tool for the development and monitoring of freeze-drying processes. PMID:29435445

Detection of Collapse and Crystallization of Saccharide, Protein and Mannitol Formulations by Optical Fibers in Lyophilization

NASA Astrophysics Data System (ADS)

Horn, Jacqueline; Friess, Wolfgang

2018-01-01

The collapse temperature (Tc) and the glass transition temperature of freeze-concentrated solutions (Tg’) as well as the crystallization behavior of excipients are important physicochemical characteristics which guide the cycle development in freeze-drying. The most frequently used methods to determine these values are differential scanning calorimetry (DSC) and freeze-drying microscopy (FDM). The objective of this study was to evaluate the optical fiber system (OFS) unit as alternative tool for the analysis of Tc, Tg’ and crystallization events. The OFS unit was also tested as a potential online monitoring tool during freeze-drying. Freeze/thawing and freeze-drying experiments of sucrose, trehalose, stachyose, mannitol and highly concentrated IgG1 and lysozyme solutions were carried out and monitored by the OFS. Comparative analyses were performed by DSC and FDM. OFS and FDM results correlated well. The crystallization behavior of mannitol could be monitored by the OFS during freeze/thawing as it can be done by DSC. Online monitoring of freeze-drying runs detected collapse of amorphous saccharide matrices. The OFS unit enabled the analysis of both Tc and crystallization processes, which is usually carried out by FDM and DSC. The OFS can hence be used as novel measuring device. Additionally, detection of these events during lyophilization facilitate online-monitoring. Thus the OFS is a new beneficial tool for the development and monitoring of freeze-drying processes.

Ice Nucleation Efficiency of Hydroxylated Organic Surfaces Is Controlled by Their Structural Fluctuations and Mismatch to Ice.

PubMed

Qiu, Yuqing; Odendahl, Nathan; Hudait, Arpa; Mason, Ryan; Bertram, Allan K; Paesani, Francesco; DeMott, Paul J; Molinero, Valeria

2017-03-01

Heterogeneous nucleation of ice induced by organic materials is of fundamental importance for climate, biology, and industry. Among organic ice-nucleating surfaces, monolayers of long chain alcohols are particularly effective, while monolayers of fatty acids are significantly less so. As these monolayers expose to water hydroxyl groups with an order that resembles the one in the basal plane of ice, it was proposed that lattice matching between ice and the surface controls their ice-nucleating efficiency. Organic monolayers are soft materials and display significant fluctuations. It has been conjectured that these fluctuations assist in the nucleation of ice. Here we use molecular dynamic simulations and laboratory experiments to investigate the relationship between the structure and fluctuations of hydroxylated organic surfaces and the temperature at which they nucleate ice. We find that these surfaces order interfacial water to form domains with ice-like order that are the birthplace of ice. Both mismatch and fluctuations decrease the size of the preordered domains and monotonously decrease the ice freezing temperature. The simulations indicate that fluctuations depress the freezing efficiency of monolayers of alcohols or acids to half the value predicted from lattice mismatch alone. The model captures the experimental trend in freezing efficiencies as a function of chain length and predicts that alcohols have higher freezing efficiency than acids of the same chain length. These trends are mostly controlled by the modulation of the structural mismatch to ice. We use classical nucleation theory to show that the freezing efficiencies of the monolayers are directly related to their free energy of binding to ice. This study provides a general framework to relate the equilibrium thermodynamics of ice binding to a surface and the nonequilibrium ice freezing temperature and suggests that these could be predicted from the structure of interfacial water.

Soil Biogeochemistry in a Changing Climate: Effect of Snow Removal

NASA Astrophysics Data System (ADS)

Patel, K.; Tatariw, C.; Fernandez, I. J.; Macrae, J. D.; Ohno, T.

2016-12-01

Winter snowpack plays an important role in ecosystem functioning, thermally insulating the subnivean soil from freezing temperatures. Wintertime microbial mineralization of organic material results in accumulation of nutrients under the snowpack, which are available post-melt for plant root uptake. The northeastern United States has experienced declining snow accumulation, and climate models project this trend will continue in the future. Intermittent and reduced snow cover increases soil freezing and frost damage, which can have implications on spring nutrient availability and forest productivity. We conducted a 2-year snow removal experiment in the Dwight B. DeMeritt Forest at the University of Maine to study subnivean winter processes, and to examine the effect of a decreased snowpack on soil winter and spring biogeochemistry. Surface organic soils were collected during winter and spring of 2015 and 2016, years with sharply contrasting snow accumulation, to track temporal changes in nutrient dynamics as the system evolved from under the snowpack. Laboratory extractions and incubations were performed to quantify the inorganic available nitrogen, dissolved organic carbon (DOC), and potential net N-mineralization (PNNM) in field moist soils. Snow removal resulted in decreased winter soil temperatures (2-8°C colder than the reference plots). There was an increased incidence of rain-on-soil events in the winter, forming concrete frost. Freeze-thaw cycles in the treatment plots resulted in higher NH4-N and DOC concentrations, but lower PNNM, compared to the reference plots. Treatment effects on DOC and NH4-N concentrations were not seen in the spring, although the effects on PNNM persisted. Our findings demonstrated that freeze-thaw cycles play an important role in the timing and magnitude of soil nutrient availability during the vernal transition. Understanding these processes becomes increasingly important when defining forest ecosystem response to a changing climate.

Effects of drying-wetting and freezing-thawing cycle on leachability of metallic elements in mine soils

NASA Astrophysics Data System (ADS)

Bang, H.; Kim, J.; Hyun, S.

2016-12-01

Mine leachate derived from contaminated mine sites with metallic elements can pose serious risks on human society and environment. Only labile fraction of metallic elements in mine soils is subject to leaching and movement by rainfall. Lability of metallic element in soil is a function of bond strengths between metal and soil surfaces, which is influenced by environmental condition (e.g., rainfall intensity, duration, temperature, etc.) The purpose of this study was to elucidate the effects of various climate conditions on the leaching patterns and lability of metallic elements in mine soils. To do this, two mine soils were sampled from two abandoned mine sites located in Korea. Leaching test were conducted using batch decant-refill method. Various climatic conditions were employed in leaching test such as (1) oven drying (40oC) - wetting cycles, (2) air drying (20oC) - wetting cycle, and (3) freezing (-40oC) - thawing cycles. Duration of drying and freezing were varied from 4 days to 2 weeks. Concentration of metallic elements, pH, Eh and concentration of dissolved iron and sulfate in leachate from each leaching process was measured. To identify the changes of labile fraction in mine soils after each of drying or freezing period, sequential extraction procedure (five fraction) was used to compare labile fraction (i.e., F1 + F2) of metallic elements. The concentration of metallic elements in mine leachate was increased after drying and freezing procedure. The amounts of released metallic element from mine soils was changed depending on their drying or freezing period. In addition, labile fraction of metallic elements in soil was also changed after drying and freezing. The changes in labile fraction after drying and freezing might be due to the increased soil surface area by pore water volume expansion. Further study is therefore needed to evaluate the impact of altered physical properties of soils such as hydration of soil surface area and shrinking by drying and freezing cycles.

Mangrove expansion and contraction at a poleward range limit: climate extremes and land-ocean temperature gradients.

PubMed

Osland, Michael J; Day, Richard H; Hall, Courtney T; Brumfield, Marisa D; Dugas, Jason L; Jones, William R

2017-01-01

Within the context of climate change, there is a pressing need to better understand the ecological implications of changes in the frequency and intensity of climate extremes. Along subtropical coasts, less frequent and warmer freeze events are expected to permit freeze-sensitive mangrove forests to expand poleward and displace freeze-tolerant salt marshes. Here, our aim was to better understand the drivers of poleward mangrove migration by quantifying spatiotemporal patterns in mangrove range expansion and contraction across land-ocean temperature gradients. Our work was conducted in a freeze-sensitive mangrove-marsh transition zone that spans a land-ocean temperature gradient in one of the world's most wetland-rich regions (Mississippi River Deltaic Plain; Louisiana, USA). We used historical air temperature data (1893-2014), alternative future climate scenarios, and coastal wetland coverage data (1978-2011) to investigate spatiotemporal fluctuations and climate-wetland linkages. Our analyses indicate that changes in mangrove coverage have been controlled primarily by extreme freeze events (i.e., air temperatures below a threshold zone of -6.3 to -7.6°C). We expect that in the past 121 yr, mangrove range expansion and contraction has occurred across land-ocean temperature gradients. Mangrove resistance, resilience, and dominance were all highest in areas closer to the ocean where temperature extremes were buffered by large expanses of water and saturated soil. Under climate change, these areas will likely serve as local hotspots for mangrove dispersal, growth, range expansion, and displacement of salt marsh. Collectively, our results show that the frequency and intensity of freeze events across land-ocean temperature gradients greatly influences spatiotemporal patterns of range expansion and contraction of freeze-sensitive mangroves. We expect that, along subtropical coasts, similar processes govern the distribution and abundance of other freeze-sensitive organisms. In broad terms, our findings can be used to better understand and anticipate the ecological effects of changing winter climate extremes, especially within the transition zone between tropical and temperate climates. © 2016 by the Ecological Society of America.

Experimental evidence for modifying the current physical model for ice accretion on aircraft surfaces

NASA Technical Reports Server (NTRS)

Olsen, W.; Walker, E.

1986-01-01

Closeup movies, still photographs, and other experimental data suggest that the current physical model for ice accretion needs significant modification. At aircraft airspeeds there was no flow of liquid over the surface of the ice after a short initial flow, even at barely subfreezing temperatures. Instead, there were very large stationary drops on the ice surface that lose water from their bottoms by freezing and replenish their liquid by catching the microscopic cloud droplets. This observation disagrees with the existing physical model, which assumes there is a thin liquid film continuously flowing over the ice surface. With no such flow, the freezing-fraction concept of the model fails when a mass balance is performed on the surface water. Rime ice does, as the model predicts, form when the air temperature is low enough to cause the cloud droplets to freeze almost immediately on impact. However, the characteristic shapes of horn-glaze ice or rime ice are primarily caused by the ice shape affecting the airflow locally and consequently the droplet catch and the resulting ice shape. Ice roughness greatly increases the heat transfer coefficient, stops the movement of drops along the surface, and may also affect the airflow initially and thereby the droplet catch. At high subreezing temperatures the initial flow and shedding of surface drops have a large effect on the ice shape. At the incipient freezing limit, no ice forms.

The surface area of soil organic matter

USGS Publications Warehouse

Chiou, C.T.; Lee, J.-F.; Boyd, S.A.

1990-01-01

The previously reported surface area for soil organic matter (SOM) of 560-800 m2/g as determined by the ethylene glycol (EG) retention method was reexamined by the standard BET method based on nitrogen adsorption at liquid nitrogen temperature. Test samples consisted of two high organic content soils, a freeze-dried soil humic acid, and an oven-dried soil humic acid. The measured BET areas for these samples were less than 1 m2/g, except for the freeze-dried humic acid. The results suggest that surface adsorption of nonionic organic compounds by SOM is practically insignificant in comparison to uptake by partition. The discrepancy between the surface areas of SOM obtained by BET and EG methods was explained in terms of the 'free surface area' and the 'apparent surface area' associated with these measurements.The previously reported surface area for soil organic matter (SOM) of 560-800 m2/g as determined by the ethylene glycol (EG) retention method was reexamined by the standard BET method based on nitrogen adsorption at liquid nitrogen temperature. Test samples consisted of two high organic content soils, a freeze-dried soil humic acid, and an oven-dried soil humic acid. The measured BET areas for these samples were less than 1 m2/g, except for the freeze-dried humic acid. The results suggest that surface adsorption of nonionic organic compounds by SOM is practically insignificant in comparison to uptake by partition. The discrepancy between the surface areas of SOM obtained by BET and EG methods was explained in terms of the 'free surface area' and the 'apparent surface area' associated with these measurements.

Freeze-Drying of Plant Tissue Containing HBV Surface Antigen for the Oral Vaccine against Hepatitis B

PubMed Central

Milczarek, Magdalena; Pajtasz-Piasecka, Elżbieta; Wietrzyk, Joanna

2014-01-01

The aim of this study was to develop a freeze-drying protocol facilitating successful processing of plant material containing the small surface antigen of hepatitis B virus (S-HBsAg) while preserving its VLP structure and immunogenicity. Freeze-drying of the antigen in lettuce leaf tissue, without any isolation or purification step, was investigated. Each process step was consecutively evaluated and the best parameters were applied. Several drying profiles and excipients were tested. The profile of 20°C for 20 h for primary and 22°C for 2 h for secondary drying as well as sucrose expressed efficient stabilisation of S-HBsAg during freeze-drying. Freezing rate and postprocess residual moisture were also analysed as important factors affecting S-HBsAg preservation. The process was reproducible and provided a product with VLP content up to 200 µg/g DW. Assays for VLPs and total antigen together with animal immunisation trials confirmed preservation of antigenicity and immunogenicity of S-HBsAg in freeze-dried powder. Long-term stability tests revealed that the stored freeze-dried product was stable at 4°C for one year, but degraded at elevated temperatures. As a result, a basis for an efficient freeze-drying process has been established and a suitable semiproduct for oral plant-derived vaccine against HBV was obtained. PMID:25371900

Computational investigation of surface freezing in a molecular model of water.

PubMed

Haji-Akbari, Amir; Debenedetti, Pablo G

2017-03-28

Water freezes in a wide variety of low-temperature environments, from meteors and atmospheric clouds to soil and biological cells. In nature, ice usually nucleates at or near interfaces, because homogenous nucleation in the bulk can only be observed at deep supercoolings. Although the effect of proximal surfaces on freezing has been extensively studied, major gaps in understanding remain regarding freezing near vapor-liquid interfaces, with earlier experimental studies being mostly inconclusive. The question of how a vapor-liquid interface affects freezing in its vicinity is therefore still a major open question in ice physics. Here, we address this question computationally by using the forward-flux sampling algorithm to compute the nucleation rate in a freestanding nanofilm of supercooled water. We use the TIP4P/ice force field, one of the best existing molecular models of water, and observe that the nucleation rate in the film increases by seven orders of magnitude with respect to bulk at the same temperature. By analyzing the nucleation pathway, we conclude that freezing in the film initiates not at the surface, but within an interior region where the formation of double-diamond cages (DDCs) is favored in comparison with the bulk. This, in turn, facilitates freezing by favoring the formation of nuclei rich in cubic ice, which, as demonstrated by us earlier, are more likely to grow and overcome the nucleation barrier. The films considered here are ultrathin because their interior regions are not truly bulk-like, due to their subtle structural differences with the bulk.

Computational investigation of surface freezing in a molecular model of water

PubMed Central

Haji-Akbari, Amir; Debenedetti, Pablo G.

2017-01-01

Water freezes in a wide variety of low-temperature environments, from meteors and atmospheric clouds to soil and biological cells. In nature, ice usually nucleates at or near interfaces, because homogenous nucleation in the bulk can only be observed at deep supercoolings. Although the effect of proximal surfaces on freezing has been extensively studied, major gaps in understanding remain regarding freezing near vapor–liquid interfaces, with earlier experimental studies being mostly inconclusive. The question of how a vapor–liquid interface affects freezing in its vicinity is therefore still a major open question in ice physics. Here, we address this question computationally by using the forward-flux sampling algorithm to compute the nucleation rate in a freestanding nanofilm of supercooled water. We use the TIP4P/ice force field, one of the best existing molecular models of water, and observe that the nucleation rate in the film increases by seven orders of magnitude with respect to bulk at the same temperature. By analyzing the nucleation pathway, we conclude that freezing in the film initiates not at the surface, but within an interior region where the formation of double-diamond cages (DDCs) is favored in comparison with the bulk. This, in turn, facilitates freezing by favoring the formation of nuclei rich in cubic ice, which, as demonstrated by us earlier, are more likely to grow and overcome the nucleation barrier. The films considered here are ultrathin because their interior regions are not truly bulk-like, due to their subtle structural differences with the bulk. PMID:28292905

Neutron scattering study of the freezing of water near a cupric oxide surface

NASA Astrophysics Data System (ADS)

Torres, J.; Buck, Z. N.; Zhang, F. Z.; Chen, T.; Winholtz, R. A.; Kaiser, H.; Ma, H. B.; Taub, H.; Tyagi, M.

Oscillating heat pipes (OHP) offer promising two-phase heat transfer for a variety of applications, including cooling of electronic devices.2 Recently, it has been shown that a hydrophilic CuO coating on either the evaporator or condenser sections of a flat-plate OHP can significantly enhance its thermal performance.3 This finding has motivated us to assess the strength of the CuO/H2O interaction by investigating the freezing behavior of H2O in proximity to a CuO surface. Using the High-Flux Backscattering Spectrometer at NIST, we have measured the intensity of neutrons scattered elastically from a well-hydrated sample of CuO-coated Cu foils that mimic the oxide surfaces in a flat-plate OHP. We observe abrupt freezing of bulk-like H2O above the CuO surface at 270 K followed by continuous freezing of the interfacial H2O down to 265 K. This freezing behavior is qualitatively similar to that found for water near a zwitterionic single-supported bilayer lipid membrane.3 Further studies are planned to compare the diffusion coefficients of the interfacial water for the coated and uncoated OHPs.22F.Z. Zhang et al., submitted to J. Heat Transfer. 3M. Bai et al., Europhys. Lett. 98, 48006 (2012); Miskowiec et al., Europhys. Lett. 107, 28008 (2014). Supported by NSF Grant Nos. DMR-0944772 and DGE-1069091.

Heterogeneous nucleation of ice on carbon surfaces.

PubMed

Lupi, Laura; Hudait, Arpa; Molinero, Valeria

2014-02-26

Atmospheric aerosols can promote the heterogeneous nucleation of ice, impacting the radiative properties of clouds and Earth's climate. The experimental investigation of heterogeneous freezing of water droplets by carbonaceous particles reveals widespread ice freezing temperatures. It is not known which structural and chemical characteristics of soot account for the variability in ice nucleation efficiency. Here we use molecular dynamics simulations to investigate the nucleation of ice from liquid water in contact with graphitic surfaces. We find that atomically flat carbon surfaces promote heterogeneous nucleation of ice, while molecularly rough surfaces with the same hydrophobicity do not. Graphitic surfaces and other surfaces that promote ice nucleation induce layering in the interfacial water, suggesting that the order imposed by the surface on liquid water may play an important role in the heterogeneous nucleation mechanism. We investigate a large set of graphitic surfaces of various dimensions and radii of curvature and find that variations in nanostructures alone could account for the spread in the freezing temperatures of ice on soot in experiments. We conclude that a characterization of the nanostructure of soot is needed to predict its ice nucleation efficiency.

The fast-ice growth and freezing of the bottom in the Braganzavagen Gulf (Van Mijenfjorden, Svalbard)

NASA Astrophysics Data System (ADS)

Bogorodsky, Petr; Marchenko, Aleksey; Pnyushkov, Andrey; Filchuk, Kirill; Morozov, Yevgenii; Ryzhov, Ivan

2017-04-01

The results of oceanographic and sea ice studies in the shallow Braganzavågen Gulf (Van Mijenfjorden, Svalbard) in March 2016 are presented. These studies are a continuation of observational efforts initiated by UNIS (Svalbard, Norway) in 2014. 2016 field campaign includes instrumental measurements of snow and ice properties in the fjord (e.g., ice thicknesses, temperatures, and salinities), as well as high-resolution CTD measurements within the under-ice water column. Collected observations were accompanied by freezing simulations of adjacent water and bottom ground layers performed with a one-dimensional thermodynamic model (Bogorodskii and Pnyushkov, 2015). The model uses two methods to reproduce phase transition areas - a "classic" (frontal) method for the fast ice, and transition in the continuous media (mushy zone) for the bottom sediments. Meteorological observations during the winter 2015-16 at Sveagruva (northwest coast) were used in these simulations as the atmospheric forcing. Numerical experiments were carried out for the initial salinity of 35 psu and 2 m water depth. The simulations start with the beginning of water freezing determined by a steady air temperature transition through the freezing point. The start of freezing was also verified by comparison with sea ice charts available for the Van Mijenfjorden for the period of simulations. Model simulations showed that the growth of sea ice in shallow (<1 m) areas of the basin significantly increases water salinity in the under-ice layer. For instance, at a 0.5 m depth the salinity in the under ice water layer exceeds 160 psu, which corresponds to the freezing temperature below -9C. In fact, the water salinity does not reach high values because of the horizontal mixing. However, available hydrological observations showed relatively small (0.2-0.5 m) amplitudes of tides - the major contributor to the horizontal exchange in this area. These small amplitudes likely suggest small advective salt fluxes induced by tides, and thus their little effect on the rate of ice formation at seasonal time scales. As expected, substantial water cooling in the under-ice layer leads to freezing of the bottom ground, mostly evident in areas with small depths. For example, during the cold season this freezing may be as large as 1 m at a fjord part with typical depths of 0.5 m. In general, the model shows a relativity good agreement with direct observations of fast ice properties. However, due to uncertainty in the thermodynamic properties of the ground, the quantitative description of the heat transfer processes in this layer is still incomplete and required additional clarification in the specially targeted field experiments.

A water activity based model of heterogeneous ice nucleation kinetics for freezing of water and aqueous solution droplets

DOE Office of Scientific and Technical Information (OSTI.GOV)

Knopf, Daniel A.; Alpert, Peter A.

Immersion freezing of water and aqueous solutions by particles acting as ice nuclei (IN) is a common process of heterogeneous ice nucleation which occurs in many environments, especially in the atmosphere where it results in the glaciation of clouds. Here we experimentally show, using a variety of IN types suspended in various aqueous solutions, that immersion freezing temperatures and kinetics can be described solely by temperature, T, and solution water activity, aw, which is the ratio of the vapour pressure of the solution and the saturation water vapour pressure under the same conditions and, in equilibrium, equivalent to relative humiditymore » (RH). This allows the freezing point and corresponding heterogeneous ice nucleation rate coefficient, Jhet, to be uniquely expressed by T and aw, a result we term the aw based immersion freezing model (ABIFM). This method is independent of the nature of the solute and accounts for several varying parameters, including cooling rate and IN surface area, while providing a holistic description of immersion freezing and allowing prediction of freezing temperatures, Jhet, frozen fractions, ice particle production rates and numbers. Our findings are based on experimental freezing data collected for various IN surface areas, A, and cooling rates, r, of droplets variously containing marine biogenic material, two soil humic acids, four mineral dusts, and one organic monolayer acting as IN. For all investigated IN types we demonstrate that droplet freezing temperatures increase as A increases. Similarly, droplet freezing temperatures increase as the cooling rate decreases. The log 10(J het) values for the various IN types derived exclusively by T and aw, provide a complete description of the heterogeneous ice nucleation kinetics. Thus, the ABIFM can be applied over the entire range of T, RH, total particulate surface area, and cloud activation timescales typical of atmospheric conditions. Finally, we demonstrate that ABIFM can be used to derive frozen fractions of droplets and ice particle production for atmospheric models of cirrus and mixed phase cloud conditions.« less

A water activity based model of heterogeneous ice nucleation kinetics for freezing of water and aqueous solution droplets.

PubMed

Knopf, Daniel A; Alpert, Peter A

2013-01-01

Immersion freezing of water and aqueous solutions by particles acting as ice nuclei (IN) is a common process of heterogeneous ice nucleation which occurs in many environments, especially in the atmosphere where it results in the glaciation of clouds. Here we experimentally show, using a variety of IN types suspended in various aqueous solutions, that immersion freezing temperatures and kinetics can be described solely by temperature, T, and solution water activity, a(w), which is the ratio of the vapour pressure of the solution and the saturation water vapour pressure under the same conditions and, in equilibrium, equivalent to relative humidity (RH). This allows the freezing point and corresponding heterogeneous ice nucleation rate coefficient, J(het), to be uniquely expressed by T and a(w), a result we term the a(w) based immersion freezing model (ABIFM). This method is independent of the nature of the solute and accounts for several varying parameters, including cooling rate and IN surface area, while providing a holistic description of immersion freezing and allowing prediction of freezing temperatures, J(het), frozen fractions, ice particle production rates and numbers. Our findings are based on experimental freezing data collected for various IN surface areas, A, and cooling rates, r, of droplets variously containing marine biogenic material, two soil humic acids, four mineral dusts, and one organic monolayer acting as IN. For all investigated IN types we demonstrate that droplet freezing temperatures increase as A increases. Similarly, droplet freezing temperatures increase as the cooling rate decreases. The log10(J(het)) values for the various IN types derived exclusively by Tand a(w), provide a complete description of the heterogeneous ice nucleation kinetics. Thus, the ABIFM can be applied over the entire range of T, RH, total particulate surface area, and cloud activation timescales typical of atmospheric conditions. Lastly, we demonstrate that ABIFM can be used to derive frozen fractions of droplets and ice particle production for atmospheric models of cirrus and mixed phase cloud conditions.

A water activity based model of heterogeneous ice nucleation kinetics for freezing of water and aqueous solution droplets

DOE PAGES

Knopf, Daniel A.; Alpert, Peter A.

2013-04-24

Immersion freezing of water and aqueous solutions by particles acting as ice nuclei (IN) is a common process of heterogeneous ice nucleation which occurs in many environments, especially in the atmosphere where it results in the glaciation of clouds. Here we experimentally show, using a variety of IN types suspended in various aqueous solutions, that immersion freezing temperatures and kinetics can be described solely by temperature, T, and solution water activity, aw, which is the ratio of the vapour pressure of the solution and the saturation water vapour pressure under the same conditions and, in equilibrium, equivalent to relative humiditymore » (RH). This allows the freezing point and corresponding heterogeneous ice nucleation rate coefficient, Jhet, to be uniquely expressed by T and aw, a result we term the aw based immersion freezing model (ABIFM). This method is independent of the nature of the solute and accounts for several varying parameters, including cooling rate and IN surface area, while providing a holistic description of immersion freezing and allowing prediction of freezing temperatures, Jhet, frozen fractions, ice particle production rates and numbers. Our findings are based on experimental freezing data collected for various IN surface areas, A, and cooling rates, r, of droplets variously containing marine biogenic material, two soil humic acids, four mineral dusts, and one organic monolayer acting as IN. For all investigated IN types we demonstrate that droplet freezing temperatures increase as A increases. Similarly, droplet freezing temperatures increase as the cooling rate decreases. The log 10(J het) values for the various IN types derived exclusively by T and aw, provide a complete description of the heterogeneous ice nucleation kinetics. Thus, the ABIFM can be applied over the entire range of T, RH, total particulate surface area, and cloud activation timescales typical of atmospheric conditions. Finally, we demonstrate that ABIFM can be used to derive frozen fractions of droplets and ice particle production for atmospheric models of cirrus and mixed phase cloud conditions.« less

Weight loss and isotopic shifts for water drops frozen on a liquid nitrogen surface.

PubMed

Eguchi, Keiko; Abe, Osamu; Hiyama, Tetsuya

2008-10-01

A liquid nitrogen freezing method was used to collect raindrops for the determination of isotope-size distribution. Water drops that fall onto a surface of liquid nitrogen stay suspended for 10 to 20 s, until their temperature reaches the Leidenfrost point (126 K). As their temperature falls to the freezing point, they release their heat by thermal conduction. At the freezing point, latent heat of fusion is released, along with a significant loss of water. After freezing completely, the ice droplets stay suspended, cooling by thermal conduction until they reach the Leidenfrost point. They then lose buoyancy and start sinking. Consistent isotopic changes of 1.5 +/- 0.4 and 0.33 +/- 0.05 per thousand for hydrogen and oxygen, respectively, were found for droplets with radii between 1.0 and 1.5 mm. Isotope fractionation appeared to occur at the same time as water loss, as the droplets were freezing, in what was probably a kinetic effect.

Thermodynamic functions, freezing transition, and phase diagram of dense carbon-oxygen mixtures in white dwarfs

DOE Office of Scientific and Technical Information (OSTI.GOV)

Iyetomi, H.; Ogata, S.; Ichimaru, S.

1989-07-01

Equations of state for dense carbon-oxygen (C-O) binary-ionic mixtures (BIM's) appropriate to the interiors of white dwarfs are investigated through Monte Carlo simulations, by solution of relevant integral equations andvariational calculations in the density-functional formalism. It is thereby shown that the internal energies of the C-O BIM solids and fluids both obey precisely the linear mixing formulas. We then present an accurate calculation of the phase diagram associated with freezing transitions in such BIM materials, resulting in a novel prediction of an azeotropic diagram. Discontinuities of the mass density across the azeotropic phase boundaries areevaluated numerically for application to amore » study of white-dwarf evolution.« less

Normal velocity freeze-out of the Richtmyer-Meshkov instability when a rarefaction is reflected

NASA Astrophysics Data System (ADS)

Wouchuk, J. G.; Sano, T.

2015-02-01

The Richtmyer-Meshkov instability (RMI) develops when a shock front hits a rippled contact surface separating two different fluids. After the incident shock refraction, a transmitted shock is always formed and another shock or a rarefaction is reflected back. The pressure-entropy-vorticity fields generated by the rippled wave fronts are responsible for the generation of hydrodynamic perturbations in both fluids. In linear theory, the contact surface ripple reaches an asymptotic normal velocity which is dependent on the incident shock Mach number, fluids density ratio, and compressibilities. It was speculated in the past about the possibility of getting a zero value for the asymptotic normal velocity, a phenomenon that was called "freeze-out" [G. Fraley, Phys. Fluids 29, 376 (1986), 10.1063/1.865722; K. Mikaelian, Phys. Fluids 6, 356 (1994), 10.1063/1.868091, A. L. Velikovich et al., Phys. Plasmas 8, 592 (2001), 10.1063/1.1335829]. In a previous paper, freeze-out was studied for the case when a shock is reflected at the contact surface [J. G. Wouchuk and K. Nishihara, Phys. Rev. E 70, 026305 (2004), 10.1103/PhysRevE.70.026305]. In this work the freeze-out of the RMI is studied for the case in which a rarefaction is reflected back. Two different regimes are found: nearly equal preshock densities at the interface at any shock intensity, and very large density difference for strong shocks. The contour curves that relate shock Mach number and preshock density ratio are obtained in both regimes for fluids with equal and different compressibilities. An analysis of the temporal evolution of different cases of freeze-out is shown. It is seen that the freeze-out is the result of the interaction between the unstable interface and the rippled wave fronts. As a general and qualitative criterion to look for freeze-out situations, it is seen that a necessary condition for freeze-out is the same orientation for the tangential velocities generated at each side of the contact surface at t =0 + . A comparison with the results of previous works is also shown.

Has the conversion of natural wetlands to agricultural land increased the incidence and severity of damaging freezes in south Florida?

USGS Publications Warehouse

Marshall, C.H.; Pielke, R.A.; Steyaert, L.T.

2004-01-01

On several occasions, winter freezes have wrought severe destruction on Florida agriculture. A series of devastating freezes around the turn of the twentieth century, and again during the 1980s, were related to anomalies in the large-scale flow of the ocean–atmosphere system. During the twentieth century, substantial areas of wetlands in south Florida were drained and converted to agricultural land for winter fresh vegetable and sugarcane production. During this time, much of the citrus industry also was relocated to those areas to escape the risk of freeze farther to the north. The purpose of this paper is to present a modeling study designed to investigate whether the conversion of the wetlands to agriculture itself could have resulted in or exacerbated the severity of recent freezes in those agricultural areas of south Florida.For three recent freeze events, a pair of simulations was undertaken with the Regional Atmospheric Modeling System. One member of each pair employed land surface properties that represent pre-1900s (near natural) land cover, whereas the other member of each pair employed data that represent near-current land-use patterns as derived from analysis of Landsat data valid for 1992/93. These two different land cover datasets capture well the conversion of wetlands to agriculture in south Florida during the twentieth century. Use of current land surface properties resulted in colder simulated minimum temperatures and temperatures that remained below freezing for a longer period at locations of key agricultural production centers in south Florida that were once natural wetlands. Examination of time series of the surface energy budget from one of the cases reveals that when natural land cover is used, a persistent moisture flux from the underlying wetlands during the nighttime hours served to prevent the development of below-freezing temperatures at those same locations. When the model results were subjected to an important sensitivity factor, the depth of standing water in the wetlands, the outcome remained consistent. These results provide another example of the potential for humans to perturb the climate system in ways that can have severe socioeconomic consequences by altering the land surface alone.

Microscopic relaxations in a protein sustained down to 160K in a non-glass forming organic solvent.

PubMed

Mamontov, E; O'Neill, H

2017-01-01

We have studied microscopic dynamics of a protein in carbon disulfide, a non-glass forming solvent, down to its freezing temperature of ca. 160K. We have utilized quasielastic neutron scattering. A comparison of lysozyme hydrated with water and dissolved in carbon disulfide reveals a stark difference in the temperature dependence of the protein's microscopic relaxation dynamics induced by the solvent. In the case of hydration water, the common protein glass-forming solvent, the protein relaxation slows down in response to a large increase in the water viscosity on cooling down, exhibiting a well-known protein dynamical transition. The dynamical transition disappears in non-glass forming carbon disulfide, whose viscosity remains a weak function of temperature all the way down to freezing at just below 160K. The microscopic relaxation dynamics of lysozyme dissolved in carbon disulfide is sustained down to the freezing temperature of its solvent at a rate similar to that measured at ambient temperature. Our results demonstrate that protein dynamical transition is not merely solvent-assisted, but rather solvent-induced, or, more precisely, is a reflection of the temperature dependence of the solvent's glass-forming dynamics. We hypothesize that, if the long debated idea regarding the direct link between the microscopic relaxations and the biological activity in proteins is correct, then not only the microscopic relaxations, but also the activity, could be sustained in proteins all the way down to the freezing temperature of a non-glass forming solvent with a weak temperature dependence of its viscosity. This article is part of a Special Issue entitled "Science for Life" Guest Editor: Dr. Austen Angell, Dr. Salvatore Magazù and Dr. Federica Migliardo. Copyright © 2016 Elsevier B.V. All rights reserved.

Description of Mixed-Phase Clouds in Weather Forecast and Climate Models

DTIC Science & Technology

2014-09-30

deficits, leading to freeze-up of both sea ice and the ocean surface. The surface albedo and processes impacting the energy content of the upper ocean...appear key to producing a temporal difference be- tween the freeze-up of the sea - ice surface and adjacent open water. While synoptic conditions, atmos...Leck, 2013: Cloud and boundary layer interactions over the Arctic sea - ice in late summer, Atmos. Chem. Phys. Discuss., 13, 13191-13244, doi

Identification of a dynamic temperature threshold for soil moisture freeze/thaw (F/T) state classification using soil real dielectric constant derivatives.

NASA Astrophysics Data System (ADS)

Pardo, R.; Berg, A. A.; Warland, J. S.

2017-12-01

The use of microwave remote sensing for surface ground ice detection has been well documented using both active and passive systems. Typical validation of these remotely sensed F/T state products relies on in-situ air or soil temperature measurements and a threshold of 0°C to identify frozen soil. However, in soil pores, the effects of capillary and adsorptive forces combine with the presence of dissolved salts to depress the freezing point. This is further confounded by the fact that water over this temperature range releases/absorbs latent heat of freezing/fusion. Indeed, recent results from SLAPEx2015, a campaign conducted to evaluate the ability to detect F/T state and examine the controls on F/T detection at multiple resolutions, suggest that using a soil temperature of 0°C as a threshold for freezing may not be appropriate. Coaxial impedance sensors, like Steven's HydraProbeII (HP), are the most widely used soil sensor in water supply forecast and climatological networks. These soil moisture probes have recently been used to validate remote sensing F/T products. This kind of validation is still relatively uncommon and dependent on categorical techniques based on seasonal reference states of frozen and non-frozen soil conditions. An experiment was conducted to identify the correlation between the phase state of the soil moisture and the probe measurements. Eight soil cores were subjected to F/T transitions in an environmental chamber. For each core, at a depth of 2.5 cm, the temperature and real dielectric constant (rdc) were measured every five minutes using HPs while two heat pulse probes captured the apparent heat capacity 24 minutes apart. Preliminary results show the phase transition of water is bounded by inflection points in the soil temperature, attributed to latent heat. The rdc, however, appears to be highly sensitive to changes in the water preceding the phase change. This opens the possibility of estimating a dynamic temperature threshold for soil F/T by identifying the soil temperatures at the times during which these inflection points in the soil rdc occur. This technique provides a more accurate threshold for F/T product than the static reference temperature currently established.

Fundamental Boiling and RP-1 Freezing Experiments

NASA Technical Reports Server (NTRS)

Goode, Brian; Turner, Larry D. (Technical Monitor)

2001-01-01

This paper describes results from experiments performed to help understand certain aspects of the MC-1 engine prestart thermal conditioning procedure. The procedure was constrained by the fact that the engine must chill long enough to get quality LOX at the LOX pump inlet but must be short enough to prevent freezing of RP-1 in the fuel pump. A chill test of an MC-1 LOX impeller was performed in LN2 to obtain data on film boiling, transition boiling and impeller temperature histories. The transition boiling data was important to the chill time so a subsequent experiment was performed chilling simple steel plates in LOX to obtain similar data for LOX. To address the fuel freezing concern, two experiments were performed. First, fuel was frozen in a tray and its physical characteristics were observed and temperatures of the fuel were measured. The result was physical characteristics as a function of temperature. Second was an attempt to measure the frozen thickness of RP-1 on a cold wall submerged in warm RP-1 and to develop a method for calculating that thickness for other conditions.

Design of freeze-drying processes for pharmaceuticals: practical advice.

PubMed

Tang, Xiaolin; Pikal, Michael J

2004-02-01

Design of freeze-drying processes is often approached with a "trial and error" experimental plan or, worse yet, the protocol used in the first laboratory run is adopted without further attempts at optimization. Consequently, commercial freeze-drying processes are often neither robust nor efficient. It is our thesis that design of an "optimized" freeze-drying process is not particularly difficult for most products, as long as some simple rules based on well-accepted scientific principles are followed. It is the purpose of this review to discuss the scientific foundations of the freeze-drying process design and then to consolidate these principles into a set of guidelines for rational process design and optimization. General advice is given concerning common stability issues with proteins, but unusual and difficult stability issues are beyond the scope of this review. Control of ice nucleation and crystallization during the freezing step is discussed, and the impact of freezing on the rest of the process and final product quality is reviewed. Representative freezing protocols are presented. The significance of the collapse temperature and the thermal transition, denoted Tg', are discussed, and procedures for the selection of the "target product temperature" for primary drying are presented. Furthermore, guidelines are given for selection of the optimal shelf temperature and chamber pressure settings required to achieve the target product temperature without thermal and/or mass transfer overload of the freeze dryer. Finally, guidelines and "rules" for optimization of secondary drying and representative secondary drying protocols are presented.

Model for heat and mass transfer in freeze-drying of pellets.

PubMed

Trelea, Ioan Cristian; Passot, Stéphanie; Marin, Michèle; Fonseca, Fernanda

2009-07-01

Lyophilizing frozen pellets, and especially spray freeze-drying, have been receiving growing interest. To design efficient and safe freeze-drying cycles, local temperature and moisture content in the product bed have to be known, but both are difficult to measure in the industry. Mathematical modeling of heat and mass transfer helps to determine local freeze-drying conditions and predict effects of operation policy, and equipment and recipe changes on drying time and product quality. Representative pellets situated at different positions in the product slab were considered. One-dimensional transfer in the slab and radial transfer in the pellets were assumed. Coupled heat and vapor transfer equations between the temperature-controlled shelf, the product bulk, the sublimation front inside the pellets, and the chamber were established and solved numerically. The model was validated based on bulk temperature measurement performed at two different locations in the product slab and on partial vapor pressure measurement in the freeze-drying chamber. Fair agreement between measured and calculated values was found. In contrast, a previously developed model for compact product layer was found inadequate in describing freeze-drying of pellets. The developed model represents a good starting basis for studying freeze-drying of pellets. It has to be further improved and validated for a variety of product types and freeze-drying conditions (shelf temperature, total chamber pressure, pellet size, slab thickness, etc.). It could be used to develop freeze-drying cycles based on product quality criteria such as local moisture content and glass transition temperature.

Controlling condensation and frost growth with chemical micropatterns.

PubMed

Boreyko, Jonathan B; Hansen, Ryan R; Murphy, Kevin R; Nath, Saurabh; Retterer, Scott T; Collier, C Patrick

2016-01-22

In-plane frost growth on chilled hydrophobic surfaces is an inter-droplet phenomenon, where frozen droplets harvest water from neighboring supercooled liquid droplets to grow ice bridges that propagate across the surface in a chain reaction. To date, no surface has been able to passively prevent the in-plane growth of ice bridges across the population of supercooled condensate. Here, we demonstrate that when the separation between adjacent nucleation sites for supercooled condensate is properly controlled with chemical micropatterns prior to freezing, inter-droplet ice bridging can be slowed and even halted entirely. Since the edge-to-edge separation between adjacent supercooled droplets decreases with growth time, deliberately triggering an early freezing event to minimize the size of nascent condensation was also necessary. These findings reveal that inter-droplet frost growth can be passively suppressed by designing surfaces to spatially control nucleation sites and by temporally controlling the onset of freezing events.

Controlling condensation and frost growth with chemical micropatterns

DOE PAGES

Boreyko, Jonathan B.; Hansen, Ryan R.; Murphy, Kevin R.; ...

2016-01-22

Frost growth on chilled hydrophobic surfaces is an inter-droplet phenomenon, where frozen droplets harvest water from supercooled liquid droplets to grow ice bridges that propagate across the surface in a chain reaction. To date, no surface has been able to passively prevent the in-plane growth of frost across the population of supercooled condensate. Here, we demonstrate that when the nucleation sites for supercooled condensate are properly controlled with chemical micropatterns, the speed of frost growth can be slowed and even halted entirely. This stoppage of frost growth is attributed to the large interdroplet separation between condensate upon the onset ofmore » freezing, which was controlled by the pitch of the chemical patterns and by deliberately triggering an early freezing event. Lastly, these findings reveal that frost growth can be passively suppressed by designing surfaces to spatially control nucleation sites and/or temporally control the onset of freezing events.« less

Controlling condensation and frost growth with chemical micropatterns

PubMed Central

Boreyko, Jonathan B.; Hansen, Ryan R.; Murphy, Kevin R.; Nath, Saurabh; Retterer, Scott T.; Collier, C. Patrick

2016-01-01

In-plane frost growth on chilled hydrophobic surfaces is an inter-droplet phenomenon, where frozen droplets harvest water from neighboring supercooled liquid droplets to grow ice bridges that propagate across the surface in a chain reaction. To date, no surface has been able to passively prevent the in-plane growth of ice bridges across the population of supercooled condensate. Here, we demonstrate that when the separation between adjacent nucleation sites for supercooled condensate is properly controlled with chemical micropatterns prior to freezing, inter-droplet ice bridging can be slowed and even halted entirely. Since the edge-to-edge separation between adjacent supercooled droplets decreases with growth time, deliberately triggering an early freezing event to minimize the size of nascent condensation was also necessary. These findings reveal that inter-droplet frost growth can be passively suppressed by designing surfaces to spatially control nucleation sites and by temporally controlling the onset of freezing events. PMID:26796663

Fundamentals of freeze-drying.

PubMed

Nail, Steven L; Jiang, Shan; Chongprasert, Suchart; Knopp, Shawn A

2002-01-01

Given the increasing importance of reducing development time for new pharmaceutical products, formulation and process development scientists must continually look for ways to "work smarter, not harder." Within the product development arena, this means reducing the amount of trial and error empiricism in arriving at a formulation and identification of processing conditions which will result in a quality final dosage form. Characterization of the freezing behavior of the intended formulation is necessary for developing processing conditions which will result in the shortest drying time while maintaining all critical quality attributes of the freeze-dried product. Analysis of frozen systems was discussed in detail, particularly with respect to the glass transition as the physical event underlying collapse during freeze-drying, eutectic mixture formation, and crystallization events upon warming of frozen systems. Experiments to determine how freezing and freeze-drying behavior is affected by changes in the composition of the formulation are often useful in establishing the "robustness" of a formulation. It is not uncommon for seemingly subtle changes in composition of the formulation, such as a change in formulation pH, buffer salt, drug concentration, or an additional excipient, to result in striking differences in freezing and freeze-drying behavior. With regard to selecting a formulation, it is wise to keep the formulation as simple as possible. If a buffer is needed, a minimum concentration should be used. The same principle applies to added salts: If used at all, the concentration should be kept to a minimum. For many proteins a combination of an amorphous excipient, such as a disaccharide, and a crystallizing excipient, such as glycine, will result in a suitable combination of chemical stability and physical stability of the freeze-dried solid. Concepts of heat and mass transfer are valuable in rational design of processing conditions. Heat transfer by conduction--the dominant mechanism of heat transfer in freeze-drying--is inefficient at the pressures used in freeze-drying. Steps should be taken to improve the thermal contact between the product and the shelf of the freeze dryer, such as eliminating metal trays from the drying process. Quantitation of the heat transfer coefficient for the geometry used is a useful way of assessing the impact of changes in the system such as elimination of product trays and changes in the vial. Because heat transfer by conduction through the vapor increases with increasing pressure, the commonly held point of view that "the lower the pressure, the better" is not true with respect to process efficiency. The optimum pressure for a given product is a function of the temperature at which freeze-drying is carried out, and lower pressures are needed at low product temperatures. The controlling resistance to mass transfer is almost always the resistance of the partially dried solids above the submination interface. This resistance can be minimized by avoiding fill volumes of more than about half the volume of the container. The development scientist should also recognize that very high concentrations of solute may not be appropriate for optimum freeze-drying, particularly if the resistance of the dried product layer increases sharply with concentration. Although the last 10 years has seen the publication of a significant body of literature of great value in allowing development scientists and engineers to "work smarter," there is still much work needed in both the science and the technology of freeze-drying. Scientific development is needed for improving analytical methodology for characterization of frozen systems and freeze-dried solids. A better understanding of the relationship between molecular mobility and reactivity is needed to allow accurate prediction of product stability at the intended storage temperature based on accelerated stability at higher temperatures. This requires that the temperature dependence of glass transition-associated mobility, particularly at temperatures below the glass transition, be studied in greater depth. The relevance of the concept of strong and fragile glasses to frozen systems and freeze-dried solids has only begun to be explored. The list of pharmaceutically acceptable protective solutes is very short, and more imagination--and work--is needed in order to develop pharmaceutically acceptable alternative stabilizers. There is a need for technology development in process monitoring, particularly in developing a way to measure the status of the product during freezing and freeze-drying without placing temperature measurement probes in individual vials of product. The current practice of placing thermocouples in vials is uncertain with respect to reliability of the data, inconsistent with elimination of personnel in close proximity to open vials of product in an aseptic environment, and incompatible with technology for automatic material handling in freeze-drying. In addition, a method for controlling the degree of supercooling during freezing would allow better control of freezing rate and would, in many cases, result in more consistent product quality.

Effects of morphology parameters on anti-icing performance in superhydrophobic surfaces

NASA Astrophysics Data System (ADS)

Nguyen, Thanh-Binh; Park, Seungchul; Lim, Hyuneui

2018-03-01

In this paper, we report the contributions of actual ice-substrate contact area and nanopillar height to passive anti-icing performance in terms of adhesion force and freezing time. Well-textured nanopillars with various parameters were fabricated via colloidal lithography and a dry etching process. The nanostructured quartz surface was coated with low-energy material to confer water-repellent properties. These superhydrophobic surfaces were investigated to determine the parameters essential for reducing adhesion strength and delaying freezing time. A well-textured surface with nanopillars of very small top diameter, regardless of height, could reduce adhesion force and delay freezing time in a subsequent de-icing process. Small top diameters of nanopillars also ensured the metastable Cassie-Baxter state based on energy barrier calculations. The results demonstrated the important role of areal fraction in anti-icing efficiency, and the negligible contribution of texture height. This insight into icing phenomena should lead to design of improved ice-phobic surfaces in the future.

Antioxidant capacity of fresh and stored breast milk: is -80°C optimal temperature for freeze storage?

PubMed

Sari, Fatma Nur; Akdag, Arzu; Dizdar, Evrim Alyamac; Uras, Nurdan; Erdeve, Omer; Erel, Ozcan; Dilmen, Ugur

2012-06-01

To determine total antioxidant capacity and total oxidation status in fresh and freeze stored (at -80°C) breast milk during the stages of lactation. Samples of colostrum, transitional and mature milk were collected from 44 healthy women at 3, 8 and 30 days after birth. The total milk volume collected (6 ml) was divided in two aliquot parts: 3 ml for the fresh analysis which was done immediately after the extraction and 3 ml for storage under freezing conditions at -80°C for two months. The antioxidant status and oxidative stress of the fresh and stored breast milk were assessed via determination of total antioxidant capacity and total oxidation status. Antioxidant capacity of transitional and mature milk decreased (p = 0.0001, p = 0.028, respectively); however, antioxidant capacity of colostrum did not change by storage at -80°C (p > 0.05). Total antioxidant capacity of fresh and stored breast milk significantly decreased during the stages of lactation (p < 0.0001, p = 0.028, respectively). Total oxidation status showed no significant difference in fresh and stored breast milk during the stages of lactation (p > 0.05). Freeze storage of breast milk at -80°C for two months seems not to be the optimal condition to preserve the antioxidant capacity of breast milk.

Effect of Latent Heat Released by Freezing Droplets during Frost Wave Propagation.

PubMed

Chavan, Shreyas; Park, Deokgeun; Singla, Nitish; Sokalski, Peter; Boyina, Kalyan; Miljkovic, Nenad

2018-05-21

Frost spreads on nonwetting surfaces during condensation frosting via an interdroplet frost wave. When a supercooled condensate water droplet freezes on a hydrophobic or superhydrophobic surface, neighboring droplets still in the liquid phase begin to evaporate. Two possible mechanisms govern the evaporation of neighboring water droplets: (1) The difference in saturation pressure of the water vapor surrounding the liquid and frozen droplets induces a vapor pressure gradient, and (2) the latent heat released by freezing droplets locally heats the substrate, leading to evaporation of nearby droplets. The relative significance of these two mechanisms is still not understood. Here, we study the significance of the latent heat released into the substrate by freezing droplets, and its effect on adjacent droplet evaporation, by studying the dynamics of individual water droplet freezing on aluminum-, copper-, and glass-based hydrophobic and superhydrophobic surfaces. The latent heat flux released into the substrate was calculated from the measured droplet sizes and the respective freezing times ( t f ), defined as the time from initial ice nucleation within the droplet to complete droplet freezing. To probe the effect of latent heat release, we performed three-dimensional transient finite element simulations showing that the transfer of latent heat to neighboring droplets is insignificant and accounts for a negligible fraction of evaporation during microscale frost wave propagation. Furthermore, we studied the effect of substrate thermal conductivity on the transfer of latent heat transfer to neighboring droplets by investigating the velocity of ice bridge formation. The velocity of the ice bridge was independent of the substrate thermal conductivity, indicating that adjacent droplet evaporation during condensation frosting is governed solely by vapor pressure gradients. This study not only provides key insights into the individual droplet freezing process but also elucidates the negligible role of latent heat released into the substrate during frost wave propagation.

7 CFR 51.2 - Terms defined.

Code of Federal Regulations, 2011 CFR

2011-01-01

... resulting from improper handling after packing; progressive pathological, physiological, and virus diseases, including fungal and bacterial roots; and freezing damage which may occur in transit or storage; or any...

Homogenous Surface Nucleation of Solid Polar Stratospheric Cloud Particles

NASA Technical Reports Server (NTRS)

Tabazadeh, A.; Hamill, P.; Salcedo, D.; Gore, Warren J. (Technical Monitor)

2002-01-01

A general surface nucleation rate theory is presented for the homogeneous freezing of crystalline germs on the surfaces of aqueous particles. While nucleation rates in a standard classical homogeneous freezing rate theory scale with volume, the rates in a surface-based theory scale with surface area. The theory is used to convert volume-based information on laboratory freezing rates (in units of cu cm, seconds) of nitric acid trihydrate (NAT) and nitric acid dihydrate (NAD) aerosols into surface-based values (in units of sq cm, seconds). We show that a surface-based model is capable of reproducing measured nucleation rates of NAT and NAD aerosols from concentrated aqueous HNO3 solutions in the temperature range of 165 to 205 K. Laboratory measured nucleation rates are used to derive free energies for NAT and NAD germ formation in the stratosphere. NAD germ free energies range from about 23 to 26 kcal mole, allowing for fast and efficient homogeneous NAD particle production in the stratosphere. However, NAT germ formation energies are large (greater than 26 kcal mole) enough to prevent efficient NAT particle production in the stratosphere. We show that the atmospheric NAD particle production rates based on the surface rate theory are roughly 2 orders of magnitude larger than those obtained from a standard volume-based rate theory. Atmospheric volume and surface production of NAD particles will nearly cease in the stratosphere when denitrification in the air exceeds 40 and 78%, respectively. We show that a surface-based (volume-based) homogeneous freezing rate theory gives particle production rates, which are (not) consistent with both laboratory and atmospheric data on the nucleation of solid polar stratospheric cloud particles.

Self-healing Characteristics of Collagen Coatings with Respect to Surface Abrasion

PubMed Central

Kim, Chang-Lae; Kim, Dae-Eun

2016-01-01

A coating based on collagen with self-healing properties was developed for applications in mechanical components that are prone to abrasion due to contact with a counter surface. The inherent swelling behavior of collagen in water was exploited as the fundamental mechanism behind self-healing of a wear scar formed on the surface. The effects of freeze-drying process and water treatment of the collagen coatings on their mechanical and self-healing properties were analyzed. Water was also used as the medium to trigger the self-healing effect of the collagen coatings after the wear test. It was found that collagen coatings without freeze-drying did not demonstrate any self-healing effect whereas the coatings treated by freeze-drying process showed remarkable self-healing effect. Overall, collagen coatings that were freeze-dried and water treated showed the best friction and self-healing properties. Repeated self-healing ability of these coatings with respect to wear scar was also demonstrated. It was also confirmed that the self-healing property of the collagen coating was effective over a relatively wide range of temperature. PMID:27010967

Self-healing Characteristics of Collagen Coatings with Respect to Surface Abrasion

NASA Astrophysics Data System (ADS)

Kim, Chang-Lae; Kim, Dae-Eun

2016-03-01

A coating based on collagen with self-healing properties was developed for applications in mechanical components that are prone to abrasion due to contact with a counter surface. The inherent swelling behavior of collagen in water was exploited as the fundamental mechanism behind self-healing of a wear scar formed on the surface. The effects of freeze-drying process and water treatment of the collagen coatings on their mechanical and self-healing properties were analyzed. Water was also used as the medium to trigger the self-healing effect of the collagen coatings after the wear test. It was found that collagen coatings without freeze-drying did not demonstrate any self-healing effect whereas the coatings treated by freeze-drying process showed remarkable self-healing effect. Overall, collagen coatings that were freeze-dried and water treated showed the best friction and self-healing properties. Repeated self-healing ability of these coatings with respect to wear scar was also demonstrated. It was also confirmed that the self-healing property of the collagen coating was effective over a relatively wide range of temperature.

Particle-size dependence of immersion freezing: Investigation of INUIT test aerosol particles with freely suspended water drops.

NASA Astrophysics Data System (ADS)

Diehl, Karoline; Debertshäuser, Michael; Eppers, Oliver; Jantsch, Evelyn; Mitra, Subir K.

2014-05-01

One goal of the research group INUIT (Ice Nuclei research UnIT) is to investigate the efficiencies of several test ice nuclei under comparable conditions but with different experimental techniques. In the present studies, two methods are used: the Mainz vertical wind tunnel and an acoustic levitator placed inside a cold chamber. In both cases drops are freely levitated, either at their terminal velocity in the wind tunnel updraft or around the nodes of a standing ultrasonic wave in the acoustic levitator. Thus, heat transfer conditions are well approximated, and wall contact effects on freezing as well as electrical charges of the drops are avoided. Drop radii are 370 μm and 1 mm, respectively. In the wind tunnel, drops are investigated at constant temperatures within a certain time period and the onset of freezing is observed directly. In the acoustic levitator, the drop temperature decreases during the experiments and is measured by an in-situ calibrated Infrared thermometer. The onset of freezing is indicated by a rapid rise of the drop surface temperature because of the release of latent heat. Investigated test ice nuclei are Snomax® as a proxy of biological particles and illite NX as well as K-feldspar as represents of mineral dust. The particle concentrations are 1 × 10-12 to 3 × 10-6 g Snomax® per drop and 5 × 10-9 to 5 × 10-5 g mineral dust per drop. Freezing temperatures are between -2 and -18° C in case of Snomax® and between -14 and -26° C in case of mineral dust. The lower the particle masses per drop the lower are the freezing temperatures. For similar particle concentrations in the drops, the median freezing temperatures determined by the two techniques agree well within the measurement errors. With the knowledge of the specific particle surface area of the mineral dusts, the results are interpreted also in terms of particle surface area per drop. Results from the wind tunnel experiments which are performed at constant temperatures indicate that the freezing times are shorter the lower the temperatures are. For evaluation and comparisons of the data, two models of heterogeneous freezing are applied, the stochastic and the time-independent singular description. The nucleation rate coefficients J(T) as well as the surface densities of active sites ns(T) or the numbers of active sites nm(T) are determined from the experimental data. It is shown that both models are suited to describe the present heterogeneous freezing results for the range of investigated particle masses or surface areas per drop. The comparison of the results from the two experimental techniques evaluated with the time-independent singular model indicates an excellent agreement within the measurement errors.

Observations and modeling of northern mid-latitude recurring slope lineae (RSL) suggest recharge by a present-day martian briny aquifer

NASA Astrophysics Data System (ADS)

Stillman, David E.; Michaels, Timothy I.; Grimm, Robert E.; Hanley, Jennifer

2016-02-01

Recurring slope lineae (RSL) are narrow (0.5-5 m) dark features on Mars that incrementally lengthen down steep slopes, fade in colder seasons, and recur annually. These features have been identified from the northern to southern mid-latitudes. Here, we describe how observations of northern mid-latitude RSL in northern Chryse Planitia and southwestern Acidalia Planitia (CAP) suggest that brines start flowing before northern spring equinox and continue for more than half a Mars-year (490 ± 40 sols, spanning solar longitude 337° ± 11°-224° ± 20°). All CAP RSL are found on the steep slopes of craters and their source zones are at or below the elevation of the surrounding plains. Spacecraft-derived surface temperature observations cannot resolve individual RSL, so thermal modeling was used to determine that CAP RSL have a freezing temperature of 238-252 K, freeze and melt diurnally, and flow only occurs within the top ∼8 cm of the regolith. Furthermore, we calculate that a typical CAP RSL has a water budget of 1.5-5.6 m3/m of headwall. Therefore, such a large water budget makes annual recharge via atmospheric or subsurface diffusion sources unlikely. Alternatively, we hypothesize that the most plausible RSL source is a briny aquifer with a freezing temperature less than or equal to the mean annual CAP surface temperature (220-225 K). The annual cycle is as follows: in late autumn, the shallowest part of the brine feeding the source zone freezes, forming an ice dam. As spring approaches, temperatures rise and the dam is breached. Brine is discharged and the RSL initially lengthens rapidly (>1.86 m/sol), the lengthening rate then slows considerably, to ∼0.25 m/sol. Eventually, the losses equal the discharge rate and the RSL reaches its equilibrium phase. As brine flows in the RSL some of the water is lost to the atmosphere, therefore the freezing temperature of the brine within the RSL is higher (238-252 K) as the brine transitions to a super-eutectic salt concentration. In the late autumn, falling temperatures restore the ice dam and the H2O in the RSL slowly sublimates away. Overall, CAP RSL possess a significantly different seasonality and much longer duration than typical southern mid-latitude RSL, suggesting that RSL at different latitude bands have different source types. Lastly, CAP RSL are the best evidence that shallow groundwater may still exist on Mars.

Water/ice phase transition: The role of zirconium acetate, a compound with ice-shaping properties

NASA Astrophysics Data System (ADS)

Marcellini, Moreno; Fernandes, Francisco M.; Dedovets, Dmytro; Deville, Sylvain

2017-04-01

Few compounds feature ice-shaping properties. Zirconium acetate is one of the very few inorganic compounds reported so far to have ice-shaping properties similar to that of ice-shaping proteins, encountered in many organisms living at low temperature. When a zirconium acetate solution is frozen, oriented and perfectly hexagonal ice crystals can be formed and their growth follows the temperature gradient. To shed light on the water/ice phase transition while freezing zirconium acetate solution, we carried out differential scanning calorimetry measurements. From our results, we estimate how many water molecules do not freeze because of their interaction with Zr cations. We estimate the colligative properties of the Zr acetate on the apparent critical temperature. We further show that the phase transition is unaffected by the nature of the base which is used to adjust the pH. Our results provide thus new hints on the ice-shaping mechanism of zirconium acetate.

Water/ice phase transition: The role of zirconium acetate, a compound with ice-shaping properties.

PubMed

Marcellini, Moreno; Fernandes, Francisco M; Dedovets, Dmytro; Deville, Sylvain

2017-04-14

Few compounds feature ice-shaping properties. Zirconium acetate is one of the very few inorganic compounds reported so far to have ice-shaping properties similar to that of ice-shaping proteins, encountered in many organisms living at low temperature. When a zirconium acetate solution is frozen, oriented and perfectly hexagonal ice crystals can be formed and their growth follows the temperature gradient. To shed light on the water/ice phase transition while freezing zirconium acetate solution, we carried out differential scanning calorimetry measurements. From our results, we estimate how many water molecules do not freeze because of their interaction with Zr cations. We estimate the colligative properties of the Zr acetate on the apparent critical temperature. We further show that the phase transition is unaffected by the nature of the base which is used to adjust the pH. Our results provide thus new hints on the ice-shaping mechanism of zirconium acetate.

Does deposition freezing really exist? At least different as we thought

NASA Astrophysics Data System (ADS)

Abdelmonem, Ahmed

2017-04-01

The structural and chemical properties of the surface of an IN-particle (INP) play a major role in its IN ability. This role is not well explored in terms of water/INP-surface molecular-level interactions. Recent MD simulations on deposition freezing showed that water first deposits as liquid clusters and then crystallize isothermally from there [1]. We probe freezing of water on INPs of different structural and chemical properties under varying supersaturation conditions using non-linear optical spectroscopy, mainly second harmonic generation (SHG) and sum frequency generation (SFG) [2, 3]. This presentation will show very recent preliminary experimental results comparing deposition, condensation and immersion freezing (DF, CF and IF respectively) on an atmospheric relevant metal oxide surface (mica) using supercooled SHG measurements. It is found that the signal drops upon the formation of a thin film regardless of 1) the freezing path (DF or CF), 2) the formed phase (ice or liquid), indicating a similar molecular structuring. The observed structuring similarity between DF, CF and LC films is a kick-off experimental confirmation of those computational results. References 1. Lupi, L., N. Kastelowitz, and V. Molinero, Vapor deposition of water on graphitic surfaces: Formation of amorphous ice, bilayer ice, ice I, and liquid water. The Journal of Chemical Physics, 2014. 141(18): p. 18C508. 2. Abdelmonem, A., J. Lützenkirchen, and T. Leisner, Probing ice-nucleation processes on the molecular level using second harmonic generation spectroscopy. Atmospheric Measurement Techniques, 2015. 8(8): p. 3519-3526. 3. Abdelmonem, A., et al., Surface charge-induced orientation of interfacial water suppresses heterogeneous ice nucleation on α-alumina (0001). Angewandte Chemie (Submitted), 2017.

A continuum model for meltwater flow through compacting snow

NASA Astrophysics Data System (ADS)

Meyer, Colin R.; Hewitt, Ian J.

2017-12-01

Meltwater is produced on the surface of glaciers and ice sheets when the seasonal energy forcing warms the snow to its melting temperature. This meltwater percolates into the snow and subsequently runs off laterally in streams, is stored as liquid water, or refreezes, thus warming the subsurface through the release of latent heat. We present a continuum model for the percolation process that includes heat conduction, meltwater percolation and refreezing, as well as mechanical compaction. The model is forced by surface mass and energy balances, and the percolation process is described using Darcy's law, allowing for both partially and fully saturated pore space. Water is allowed to run off from the surface if the snow is fully saturated. The model outputs include the temperature, density, and water-content profiles and the surface runoff and water storage. We compare the propagation of freezing fronts that occur in the model to observations from the Greenland Ice Sheet. We show that the model applies to both accumulation and ablation areas and allows for a transition between the two as the surface energy forcing varies. The largest average firn temperatures occur at intermediate values of the surface forcing when perennial water storage is predicted.

Freeze chromatography method and apparatus

DOEpatents

Scott, C.D.

1987-04-16

A freeze chromatography method and apparatus are provided which enable separation of the solutes contained in a sample. The apparatus includes an annular column construction comprising cylindrical inner and outer surfaces defining an annular passage therebetween. One of the surfaces is heated and the other cooled while passing an eluent through the annular passageway so that the eluent in contact with the cooled surface freezes and forms a frozen eluent layer thereon. A mixture of solutes dissolved in eluent is passed through the annular passageway in contact with the frozen layer so that the sample solutes in the mixture will tend to migrate either toward or away the frozen layer. The rate at which the mixture flows through the annular passageway is controlled so that the distribution of the sample solutes approaches that at equilibrium and thus a separation between the sample solutes occurs. 3 figs.

Dynamical singularities of glassy systems in a quantum quench.

PubMed

Obuchi, Tomoyuki; Takahashi, Kazutaka

2012-11-01

We present a prototype of behavior of glassy systems driven by quantum dynamics in a quenching protocol by analyzing the random energy model in a transverse field. We calculate several types of dynamical quantum amplitude and find a freezing transition at some critical time. The behavior is understood by the partition-function zeros in the complex temperature plane. We discuss the properties of the freezing phase as a dynamical chaotic phase, which are contrasted to those of the spin-glass phase in the static system.

Site-Directed Nanotherapeutics to Abrogate RRMS and Promote Remyelination Repair

DTIC Science & Technology

2012-09-01

peptides. Freezing of the NP without cryoprotection leads to disassembling, freezing with a cryoprotectant to aggregation and/or surface modification...Furthermore to get all the necessary inductions to work in the labs delayed the onset of the practical work further. • Long lasting defect in freeze ... dryer prevented a more in depth investigations of long term storage of nanoparticles. • No peptide sequence to bind to myelin is available

Synergistic structures from magnetic freeze casting with surface magnetized alumina particles and platelets.

PubMed

Frank, Michael B; Hei Siu, Sze; Karandikar, Keyur; Liu, Chin-Hung; Naleway, Steven E; Porter, Michael M; Graeve, Olivia A; McKittrick, Joanna

2017-12-01

Magnetic freeze casting utilizes the freezing of water, a low magnetic field and surface magnetized materials to make multi-axis strengthened porous scaffolds. A much greater magnetic moment was measured for larger magnetized alumina platelets compared with smaller particles, which indicated that more platelet aggregation occurred within slurries. This led to more lamellar wall alignment along the magnetic field direction during magnetic freeze casting at 75 mT. Slurries with varying ratios of magnetized particles to platelets (0:1, 1:3, 1:1, 3:1, 7:1, 1:0) produced porous scaffolds with different structural features and degrees of lamellar wall alignment. The greatest mechanical enhancement in the magnetic field direction was identified in the synergistic condition with the highest particle to platelet ratio (7:1). Magnetic freeze casting with varying ratios of magnetized anisotropic and isotropic alumina provided insights about how heterogeneous morphologies aggregate within lamellar walls that impact mechanical properties. Fabrication of strengthened scaffolds with multi-axis aligned porosity was achieved without introducing different solid materials, freezing agents or additives. Resemblance of 7:1 particle to platelet scaffold microstructure to wood light-frame house construction is framed in the context of assembly inspiration being derived from both natural and synthetic sources. Copyright © 2017 Elsevier Ltd. All rights reserved.

Insights into seasonal active layer dynamics by monitoring relative velocity changes using ambient seismic noise

NASA Astrophysics Data System (ADS)

James, S. R.; Knox, H. A.; Cole, C. J.; Abbott, R. E.; Screaton, E.

2016-12-01

Seasonal freeze and thaw of the active layer above permafrost results in dramatic changes in seismic velocity. We used daily cross correlations of ambient seismic noise recorded at Poker Flat Research Range in central Alaska to create a nearly continuous 2-year record of relative velocity changes. This analysis required that we modify the Moving Window Cross-spectral Analysis technique used in the Python package MSNoise to reduce the occurrence of cycle skipping. Results show relative velocity variations follow a seasonal pattern, where velocities decrease in late spring through the summer months and increase through the fall and winter months. This timing is consistent with active layer freeze and thaw in this region. These results were compared to a suite of ground- and satellite-based measurements to identify relationships. A decrease in relative velocities in late spring closely follows the timing of snow melt recorded in nearby ground temperatures and snow-depth logs. This transition also aligns with a decrease in the Normalized Difference Snow Index (NDSI) derived from multi-temporal Landsat 8 satellite imagery collected over the study site. A gradual increase in relative velocity through the fall months occurs when temperatures below ground surface remain near zero. We suggest this is due to latent heat feedbacks that keep temperatures constant while active layer velocities increase from continued ice formation. This highlights the value in velocity variations for capturing details on the freezing process. In addition, spatial variations in the magnitude of velocity changes are consistent with thaw probe surveys. Exploring relationships with remote sensing may allow indirect measurements of thaw over larger areas and further surface wave analysis may allow for thickness evolution measurements. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

Curvature of the freeze-out line in heavy ion collisions

DOE PAGES

Bazavov, A.; Ding, H. -T.; Hegde, P.; ...

2016-01-28

Here, we calculate the mean and variance of net-baryon number and net-electric charge distributions from quantum chromodynamics (QCD) using a next-to-leading order Taylor expansion in terms of temperature and chemical potentials. Moreover, these expansions with experimental data from STAR and PHENIX are compared, we determine the freeze-out temperature in the limit of vanishing baryon chemical potential, and, for the first time, constrain the curvature of the freeze-out line through a direct comparison between experimental data on net-charge fluctuations and a QCD calculation. We obtain a bound on the curvature coefficient, κmore » $^f$$_2$$<0.011, that is compatible with lattice QCD results on the curvature of the QCD transition line.« less

Variable Temperature Nuclear Magnetic Resonance and Magnetic Resonance Imaging System as a Novel Technique for In Situ Monitoring of Food Phase Transition.

PubMed

Song, Yukun; Cheng, Shasha; Wang, Huihui; Zhu, Bei-Wei; Zhou, Dayong; Yang, Peiqiang; Tan, Mingqian

2018-01-24

A nuclear magnetic resonance (NMR) and magnetic resonance imaging (MRI) system with a 45 mm variable temperature (VT) sample probe (VT-NMR-MRI) was developed as an innovative technique for in situ monitoring of food phase transition. The system was designed to allow for dual deployment in either a freezing (-37 °C) or high temperature (150 °C) environment. The major breakthrough of the developed VT-NMR-MRI system is that it is able to measure the water states simultaneously in situ during food processing. The performance of the VT-NMR-MRI system was evaluated by measuring the phase transition for salmon flesh and hen egg samples. The NMR relaxometry results demonstrated that the freezing point of salmon flesh was -8.08 °C, and the salmon flesh denaturation temperature was 42.16 °C. The protein denaturation of egg was 70.61 °C, and the protein denaturation occurred at 24.12 min. Meanwhile, the use of MRI in phase transition of food was also investigated to gain internal structural information. All these results showed that the VT-NMR-MRI system provided an effective means for in situ monitoring of phase transition in food processing.

Jamming transitions induced by an attraction in pedestrian flow.

PubMed

Kwak, Jaeyoung; Jo, Hang-Hyun; Luttinen, Tapio; Kosonen, Iisakki

2017-08-01

We numerically study jamming transitions in pedestrian flow interacting with an attraction, mostly based on the social force model for pedestrians who can join the attraction. We formulate the joining probability as a function of social influence from others, reflecting that individual choice behavior is likely influenced by others. By controlling pedestrian influx and the social influence parameter, we identify various pedestrian flow patterns. For the bidirectional flow scenario, we observe a transition from the free flow phase to the freezing phase, in which oppositely walking pedestrians reach a complete stop and block each other. On the other hand, a different transition behavior appears in the unidirectional flow scenario, i.e., from the free flow phase to the localized jam phase and then to the extended jam phase. It is also observed that the extended jam phase can end up in freezing phenomena with a certain probability when pedestrian flux is high with strong social influence. This study highlights that attractive interactions between pedestrians and an attraction can trigger jamming transitions by increasing the number of conflicts among pedestrians near the attraction. In order to avoid excessive pedestrian jams, we suggest suppressing the number of conflicts under a certain level by moderating pedestrian influx especially when the social influence is strong.

Jamming transitions induced by an attraction in pedestrian flow

NASA Astrophysics Data System (ADS)

Kwak, Jaeyoung; Jo, Hang-Hyun; Luttinen, Tapio; Kosonen, Iisakki

2017-08-01

We numerically study jamming transitions in pedestrian flow interacting with an attraction, mostly based on the social force model for pedestrians who can join the attraction. We formulate the joining probability as a function of social influence from others, reflecting that individual choice behavior is likely influenced by others. By controlling pedestrian influx and the social influence parameter, we identify various pedestrian flow patterns. For the bidirectional flow scenario, we observe a transition from the free flow phase to the freezing phase, in which oppositely walking pedestrians reach a complete stop and block each other. On the other hand, a different transition behavior appears in the unidirectional flow scenario, i.e., from the free flow phase to the localized jam phase and then to the extended jam phase. It is also observed that the extended jam phase can end up in freezing phenomena with a certain probability when pedestrian flux is high with strong social influence. This study highlights that attractive interactions between pedestrians and an attraction can trigger jamming transitions by increasing the number of conflicts among pedestrians near the attraction. In order to avoid excessive pedestrian jams, we suggest suppressing the number of conflicts under a certain level by moderating pedestrian influx especially when the social influence is strong.

Freeze-Thaw Cycles and Soil Biogeochemistry: Implications for Greenhouse Gas emission

NASA Astrophysics Data System (ADS)

Rezanezhad, F.; Milojevic, T.; Oh, D. H.; Parsons, C. T.; Smeaton, C. M.; Van Cappellen, P.

2016-12-01

Freeze-thaw cycles represent a major natural climate forcing acting on soils at middle and high latitudes. Repeated freezing and thawing of soils changes their physical properties, geochemistry, and microbial community structure, which together govern the biogeochemical cycling of carbon and nutrients. In this presentation, we focus on how freeze-thaw cycles regulate carbon and nitrogen cycling and how these transformations influence greenhouse gas (GHG) fluxes. We present a novel approach, which combines the acquisition of physical and chemical data in a newly developed experimental soil column system. This system simulates realistic soil temperature profiles during freeze-thaw cycles. A high-resolution, Multi-Fiber Optode (MuFO) microsensor technique was used to detect oxygen (O2) continuously in the column at multiple depths. Surface and subsurface changes to gas and aqueous phase chemistry were measured to delineate the pathways and quantify soil respiration rates during freeze-thaw cycles. The results indicate that the time-dependent release of GHG from the soil surface is influenced by a combination of two key factors. Firstly, fluctuations in temperature and O2 availability affect soil biogeochemical activity and GHG production. Secondly, the recurrent development of a physical ice barrier prevents exchange of gaseous compounds between the soil and atmosphere during freezing conditions; removal of this barrier during thaw conditions increases GHG fluxes. During freezing, O2 levels in the unsaturated zone decreased due to restricted gas exchange with the atmosphere. As the soil thawed, O2 penetrated deeper into the soil enhancing the aerobic mineralization of organic carbon and nitrogen. Additionally, with the onset of thawing a pulse of gas flux occurred, which is attributed to the build-up of respiratory gases in the pore space during freezing. The latter implies enhanced anaerobic respiration as O2 supply ceases when the upper soil layer freezes.

Freezing of Dynamics of a Methyl Group in a Protein Hydrophobic Core at Cryogenic Temperatures by Deuteron NMR Spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vugmeyster, Liliya; Ostrovsky, Dmitry; Ford, Joseph J.

2010-03-31

Proteins undergo a number of changes when their temperature is dropped from the physiological range to much lower values. One of the most well-known dynamical changes undergone by proteins in a solid state is a so-called protein glass-transition, which is a dynamic transition occurring at about 200-230K leading to a loss of biological activity.1,2 X-ray diffraction, neutron scattering studies, and dielectric spectroscopy, as well as evidence from NMR relaxation measurements, indicate freezing of slow collective modes of motion below the glass transition temperature.3-8 Various arguments have been presented that connect the transition to solvent participation.1,4,8-10 In addition to the solvent-relatedmore » modes that are frozen below the glass-transition temperature, there are anharmonic motions at temperatures below 200K which are likely to be dominated by methyl group dynamics down to about 100K.2,5,7 Recent neutron-scattering and NMR studies emphasize the role of these modes in low temperature dynamics. 2,5,7,11,12 One of the latest works on the subject by Bajaj et al.11 has reported a structural transition associated with dynamic processes in a solvent-free polypeptide. Thus, protein dynamics at low temperatures are complex and more studies are required to discern their pattern.« less

Descent motions of the Huygens probe as measured by the Surface Science Package (SSP): Turbulent evidence for a cloud layer

NASA Astrophysics Data System (ADS)

Lorenz, Ralph D.; Zarnecki, John C.; Towner, Martin C.; Leese, Mark R.; Ball, Andrew J.; Hathi, Brijen; Hagermann, Axel; Ghafoor, Nadeem A. L.

2007-11-01

The Huygens probe underwent vigorous short-period motions during its parachute descent through the atmosphere of Saturn's moon Titan in January 2005, at least some of which were excited by the Titan environment. Several sensors in the Huygens Surface Science Package (SSP) detect these motions, indicating the transition to the smaller stabilizer parachute, the changing probe spin rate, aerodynamic buffeting, and pendulum motions. Notably, in an altitude range of about 20-30 km where methane drops will freeze, the frequency content and statistical kurtosis of the tilt data indicate excitation by turbulent air motions like those observed in freezing clouds on Earth, supporting the suggestion of Tokano et al. [Tokano, T., McKay, C.P., Neubauer, F.M., Atreya, S.K., Ferri, F., Fulchignoni, M., Niemann, H.B. (2006a). Methane drizzle on Titan. Nature 442, 432-435] that the probe passed through such a cloud layer. Motions are weak below 20 km, suggesting a quiescent lower atmosphere with turbulent fluctuations of nominally <0.15 m/s (to within a factor of ˜2) but more violent motions in the upper troposphere may have been excited by turbulent winds with amplitudes of 1-2 m/s. Descent in part of the stratosphere (150-120 km) was smooth despite strong ambient wind (˜100 m/s), but known anomalies in the probe spin prevent investigation of turbulence in the known wind-shear layer from 60 to 100 km.

Dissolution and characterization of biofunctional keratin particles extracted from chicken feathers

NASA Astrophysics Data System (ADS)

Sharma, Swati; Gupta, Arun; Chik, Syed Mohd Saufi Bin Tuan; Yeo Gek Kee, Chua; Poddar, Pradeep Kumar

2017-04-01

In the present study chicken feathers were hydrolyzed in alkaline environment. The pH value of feather hydrolyzed solution was adjusted according to the principle of isoelectric precipitation. Three kinds of precipitates of keratin polypeptide were collected at pH of 3.5, 5.5 and 7.5 respectively. The keratin solution were freeze dried and denoted as FKP1, FKP2, FKP3 respectively. All keratin particles possessed smooth, uniform and round surface by scanning electron microscope (SEM). FKP1, FKP2 and FKP3 had higher glass transition temperature examined by thermogravimetry (TG). Fourier transform infrared spectroscopy (FTIR) revealed that the extracted keratin retained the most of protein backbone, with the breakage of disulfide cross-links and hydrogen bonds.

Freezing curve-based monitoring to quickly evaluate the viability of biological materials subject to freezing or thermal injury.

PubMed

Liu, Jing; Zhou, Yi-Xin

2003-09-01

This paper is aimed at investigating the roles of freezing dynamics of a liquid droplet to characterize the properties of the material. In particular, freezing curve-based monitoring was proposed to quickly evaluate the viability of biological materials subject to freezing, re-warming, or other kinds of injury, which is an extremely important issue in practices such as cryobiology, hyperthermia, or freshness evaluation of bio-samples. An integrated micro analysis device was fabricated which is simple in structure and cheap to make. Preliminary freezing results demonstrated that minor changes in a biological material due to freezing or warming injury might result in a significant deviation of its freezing curve from that of the intact biomaterials. Several potential thermal indexes to quantify the material features were pointed out. Further, experiments were performed on some freezing and thawing processes of small amount of water on a cooling surface to test the effects of droplet sizes, measurement sites, cooling strength, and cooling geometry, etc., on the freezing responses of a water droplet. Their implementation in developing a new micro analysis system were suggested. This freezing curve-based monitoring method may open a new strategy for the evaluation of biomaterials subject to destruction in diverse fields.

The Soil Moisture Active Passive (SMAP) Radar: Measurements at High Latitudes and of Surface Freeze/Thaw State

NASA Technical Reports Server (NTRS)

Spencer, Michael; Dunbar, Scott; Chen, Curtis

2013-01-01

The Soil Moisture Active/Passive (SMAP) mission is scheduled for a late 2014 launch date. The mission will use both active radar and passive radiometer instruments at L-Band in order to achieve the science objectives of measuring soil moisture and land surface freeze-thaw state. To achieve requirements for a wide swath at sufficiently high resolution for both active and passive channels, an instrument architecture that uses a large rotating reflector is employed. In this paper, focus will be placed on the radar design. The radar will employ synthetic-aperture processing to achieve a "moderate" resolution dual-pol product over a 1000 km swath. Because the radar is operating continuously, very frequent temporal coverage will be achieved at high latitudes. This data will be used to produce a surface freeze/thaw state data product.

Spontaneous droplet trampolining on rigid superhydrophobic surfaces

NASA Astrophysics Data System (ADS)

Schutzius, Thomas M.; Jung, Stefan; Maitra, Tanmoy; Graeber, Gustav; Köhme, Moritz; Poulikakos, Dimos

2015-11-01

Spontaneous removal of condensed matter from surfaces is exploited in nature and in a broad range of technologies to achieve self-cleaning, anti-icing and condensation control. But despite much progress, our understanding of the phenomena leading to such behaviour remains incomplete, which makes it challenging to rationally design surfaces that benefit from its manifestation. Here we show that water droplets resting on superhydrophobic textured surfaces in a low-pressure environment can self-remove through sudden spontaneous levitation and subsequent trampoline-like bouncing behaviour, in which sequential collisions with the surface accelerate the droplets. These collisions have restitution coefficients (ratios of relative speeds after and before collision) greater than unity despite complete rigidity of the surface, and thus seemingly violate the second law of thermodynamics. However, these restitution coefficients result from an overpressure beneath the droplet produced by fast droplet vaporization while substrate adhesion and surface texture restrict vapour flow. We also show that the high vaporization rates experienced by the droplets and the associated cooling can result in freezing from a supercooled state that triggers a sudden increase in vaporization, which in turn boosts the levitation process. This effect can spontaneously remove surface icing by lifting away icy drops the moment they freeze. Although these observations are relevant only to systems in a low-pressure environment, they show how surface texturing can produce droplet-surface interactions that prohibit liquid and freezing water-droplet retention on surfaces.

Investigations Concerning Cavitation and Frost Fatigue in Clonal 84K Poplar Using High-Resolution Cavitron Measurements1[OPEN

PubMed Central

Feng, Feng; Ding, Fei; Tyree, Melvin T.

2015-01-01

Both drought and freezing-thawing of stems induce a loss of hydraulic conductivity (percentage loss of conductivity [PLC]) in woody plants. Drought-induced PLC is often accompanied by physical damage to pit membranes, causing a shift in vulnerability curves (cavitation fatigue). Hence, if cavitated stems are flushed to remove embolisms, the next vulnerability curve is different (shifted to lower tensions). The 84K poplar (Populus alba × Populus glandulosa) clone has small vessels that should be immune from frost-induced PLC, but results demonstrated that freezing-thawing in combination with tension synergistically increased PLC. Frost fatigue has already been defined, which is similar to cavitation fatigue but induced by freezing. Frost fatigue caused a transition from a single to a dual Weibull curve, but drought-fatigued stems had single Weibull curves shifted to lower tensions. Studying the combined impact of tension plus freezing on fatigue provided evidence that the mechanism of frost fatigue may be the extra water tension induced by freezing or thawing while spinning stems in a centrifuge rather than direct ice damage. A hypothesis is advanced that tension is enhanced as ice crystals grow or melt during the freeze or thaw event, respectively, causing a nearly identical fatigue event to that induced by drought. PMID:25786827

A theoretical extension of the soil freezing curve paradigm

NASA Astrophysics Data System (ADS)

Amiri, Erfan A.; Craig, James R.; Kurylyk, Barret L.

2018-01-01

Numerical models of permafrost evolution in porous media typically rely upon a smooth continuous relation between pore ice saturation and sub-freezing temperature, rather than the abrupt phase change that occurs in pure media. Soil scientists have known for decades that this function, known as the soil freezing curve (SFC), is related to the soil water characteristic curve (SWCC) for unfrozen soils due to the analogous capillary and sorptive effects experienced during both soil freezing and drying. Herein we demonstrate that other factors beyond the SFC-SWCC relationship can influence the potential range over which pore water phase change occurs. In particular, we provide a theoretical extension for the functional form of the SFC based upon the presence of spatial heterogeneity in both soil thermal conductivity and the freezing point depression of water. We infer the functional form of the SFC from many abrupt-interface 1-D numerical simulations of heterogeneous systems with prescribed statistical distributions of water and soil properties. The proposed SFC paradigm extension has the appealing features that it (1) is determinable from measurable soil and water properties, (2) collapses into an abrupt phase transition for homogeneous media, (3) describes a wide range of heterogeneity within a single functional expression, and (4) replicates the observed hysteretic behavior of freeze-thaw cycles in soils.

Hydroxyl Radical Formation in Solutions of Fe(III) and Hydrogen Peroxide - Impact of Freezing and Thawing Process

NASA Astrophysics Data System (ADS)

Arakaki, T.; Kinjo, M.; Shiroma, K.; Shibata, M.; Miyake, T.; Hirakawa, T.; Sakugawa, H.

2003-12-01

Hydroxyl radical formation was studied by detecting concentration of formate in solutions of hydrated formaldehyde, HOOH, and Fe(III) or Cu(II). Oxidation of hydrated formaldehyde by OH radical is known to form formate. Formate formation increased by about 4 times when the solution underwent freezing and thawing. Although the reaction mechanisms are not clearly understood, we believe that the concentration effect of freezing enhanced the catalytic reactions between HOOH and Fe(III) or Cu(II) and the reduction of transition metals, i.e., Fe(III) to Fe(II) and Cu(II) to Cu(I). The concentration effect also enhanced reactions between Fe(II) and HOOH or Cu(I) and HOOH, which generated OH radical (freeze-Fenton reaction). Study of the effects of pH showed that formate formation was the highest at pH = 4.0, indicating that the speciation of Fe(III) affected the formation of formate. Concentration-dependent experiments demonstrated that Fe is probably the limiting agent under typical atmospheric conditions. Our results suggested that the freezing process could be an important source of hydroxyl radical in high cloud, winter fog, rime ice and freezing acidic rain, and more importantly, a potentially additional oxidation mechanism in the atmosphere.

Density functional theory of freezing of a system of highly elongated ellipsoidal oligomer solutions

NASA Astrophysics Data System (ADS)

Dwivedi, Shikha; Mishra, Pankaj

2017-05-01

We have used the density functional theory of freezing to study the liquid crystalline phase behavior of a system of highly elongated ellipsoidal conjugated oligomers dispersed in three different solvents namely chloroform, toluene and their equimolar mixture. The molecules are assumed to interact via solvent-implicit coarse-grained Gay-Berne potential. Pair correlation functions needed as input in the density functional theory have been calculated using the Percus-Yevick (PY) integral equation theory. Considering the isotropic and nematic phases, we have calculated the isotropic-nematic phase transition parameters and presented the temperature-density and pressure-temperature phase diagrams. Different solvent conditions are found not only to affect the transition parameters but also determine the capability of oligomers to form nematic phase in various thermodynamic conditions. In principle, our results are verifiable through computer simulations.

Observation of surface layering in a nonmetallic liquid

NASA Astrophysics Data System (ADS)

Mo, Haiding; Evmenenko, Guennadi; Kewalramani, Sumit; Kim, Kyungil; Dutta, Pulak; Ehrlich, Steven

2006-03-01

Non-monotonic density profiles (layers) have previously been observed at the free surfaces of many metallic liquids, but not in isotropic dielectric liquids. Whether the presence of an electron gas is necessary for surface layering has been the subject of debate. Until recently, MD simulations have suggested that layering at free liquid interface may be a generic phenomenon and is not limited to the metallic liquids^1. The theories predict that if normal liquids can be cooled down to temperatures low enough, layering structure should be observed experimentally. However, this is difficult for most molecular liquids because these liquids freeze well above the temperature necessary for observing the layering structure. By studying the surface structure of liquid TEHOS (tetrakis(2-ethylhexoxy)silane), which combines relatively low freezing point and high boiling point compared to that of most molecular liquids, we have observed the evidence of layering at the free interface of liquid TEHOS using x-ray reflectivity. When cooled to T/Tc 0.25 (well above the bulk freezing point, Tc is the critical temperature of TEHOS), the surface roughness drops sharply and density oscillations appear near the surface. Lateral ordering of the surface layers is liquid-like, just as at liquid metal surfaces. 1. E. Chac'on and P. Tarazona, Phys. Rev. Lett. 91 166103-1 (2003)

Effect of drying methods of microencapsulated Lactobacillus acidophilus and Lactococcus lactis ssp. cremoris on secondary protein structure and glass transition temperature as studied by Fourier transform infrared and differential scanning calorimetry.

PubMed

Dianawati, Dianawati; Mishra, Vijay; Shah, Nagendra P

2013-03-01

Protective mechanisms of casein-based microcapsules containing mannitol on Lactobacillus acidophilus and Lactococcus lactis ssp. cremoris, changes in their secondary protein structures, and glass transition of the microcapsules were studied after spray- or freeze-drying and after 10 wk of storage in aluminum foil pouches containing different desiccants (NaOH, LiCl, or silica gel) at 25°C. An in situ Fourier transform infrared analysis was carried out to recognize any changes in fatty acids (FA) of bacterial cell envelopes, interaction between polar site of cell envelopes and microcapsules, and alteration of their secondary protein structures. Differential scanning calorimetry was used to determine glass transition of microcapsules based on glass transition temperature (T(g)) values. Hierarchical cluster analysis based on functional groups of cell envelopes and secondary protein structures was also carried out to classify the microencapsulated bacteria due to the effects of spray- or freeze-drying and storage for 10 wk. The results showed that drying process did not affect FA and secondary protein structures of bacteria; however, those structures were affected during storage depending upon the type of desiccant used. Interaction between exterior of bacterial cell envelopes and microencapsulant occurred after spray- or freeze-drying; however, these structures were maintained after storage in foil pouch containing sodium hydroxide. Method of drying and type of desiccants influenced the level of similarities of microencapsulated bacteria. Desiccants and method of drying affected glass transition, yet no T(g) ≤25°C was detected. This study demonstrated that the changes in FA and secondary structures of the microencapsulated bacteria still occurred during storage at T(g) above room temperature, indicating that the glassy state did not completely prevent chemical activities. Copyright © 2013 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Utschig, L. M.; Dalosto, S. D.; Thurnauer, M. C.

Metal ion binding to a surface site on photosynthetic reaction centers (RCs) modulates light-induced electron and proton transfer events in the RC. Whereas many studies have elucidated aspects of metal ion modulation events in Rhodobacter sphaeroides RCs, much less is understood about the surface site in Blastochloris viridis (Blc. viridis) RCs. Interestingly, electron paramagnetic resonance studies revealed two spectroscopically distinct Cu{sup 2+} surface site environments in Blc. viridis RCs. Herein, Cu{sup 2+} has been used to spectroscopically probe the structure of these Cu{sup 2+} site(s) in response to freezing conditions, temperature, and charge separation. One Cu{sup 2+} environment in Blc.more » viridis RCs, termed CuA, exhibits temperature-dependent conformational flexibility. Different conformation states of the CuA{sup 2+} site are trapped when the RC is frozen in the dark either by fast-freeze or slow-freeze procedure. The second Cu{sup 2+} environment, termed CuB, is structurally invariant to different freezing conditions and shows resolved hyperfine coupling to three nitrogen atoms. Cu{sup 2+} is most likely binding at the same location on the RC, but in different coordination environments which may reflect two distinct conformational states of the isolated Blc. viridis RC protein.« less

Direct mapping of the temperature and velocity gradients in discs. Imaging the vertical CO snow line around IM Lupi

NASA Astrophysics Data System (ADS)

Pinte, C.; Ménard, F.; Duchêne, G.; Hill, T.; Dent, W. R. F.; Woitke, P.; Maret, S.; van der Plas, G.; Hales, A.; Kamp, I.; Thi, W. F.; de Gregorio-Monsalvo, I.; Rab, C.; Quanz, S. P.; Avenhaus, H.; Carmona, A.; Casassus, S.

2018-01-01

Accurate measurements of the physical structure of protoplanetary discs are critical inputs for planet formation models. These constraints are traditionally established via complex modelling of continuum and line observations. Instead, we present an empirical framework to locate the CO isotopologue emitting surfaces from high spectral and spatial resolution ALMA observations. We apply this framework to the disc surrounding IM Lupi, where we report the first direct, i.e. model independent, measurements of the radial and vertical gradients of temperature and velocity in a protoplanetary disc. The measured disc structure is consistent with an irradiated self-similar disc structure, where the temperature increases and the velocity decreases towards the disc surface. We also directly map the vertical CO snow line, which is located at about one gas scale height at radii between 150 and 300 au, with a CO freeze-out temperature of 21 ± 2 K. In the outer disc (>300 au), where the gas surface density transitions from a power law to an exponential taper, the velocity rotation field becomes significantly sub-Keplerian, in agreement with the expected steeper pressure gradient. The sub-Keplerian velocities should result in a very efficient inward migration of large dust grains, explaining the lack of millimetre continuum emission outside of 300 au. The sub-Keplerian motions may also be the signature of the base of an externally irradiated photo-evaporative wind. In the same outer region, the measured CO temperature above the snow line decreases to ≈15 K because of the reduced gas density, which can result in a lower CO freeze-out temperature, photo-desorption, or deviations from local thermodynamic equilibrium.

Cryopreserving turkey semen in straws and nitrogen vapour using DMSO or DMA: effects of cryoprotectant concentration, freezing rate and thawing rate on post-thaw semen quality.

PubMed

Iaffaldano, N; Di Iorio, M; Miranda, M; Zaniboni, L; Manchisi, A; Cerolini, S

2016-04-01

1. This study was designed to identify a suitable protocol for freezing turkey semen in straws exposed to nitrogen vapour by examining the effects of dimethylacetamide (DMA) or dimethylsulfoxide (DMSO) as cryoprotectant (CPA), CPA concentration, freezing rate and thawing rate on in vitro post-thaw semen quality. 2. Pooled semen samples were diluted 1:1 (v:v) with a freezing extender composed of Tselutin diluent containing DMA or DMSO to give final concentrations of 8% or 18% DMA and 4% or 10% DMSO. The semen was packaged in 0.25 ml plastic straws and frozen at different heights above the liquid nitrogen (LN2) surface (1, 5 and 10 cm) for 10 min. Semen samples were thawed at 4°C for 5 min or at 50°C for 10 s. After thawing, sperm motility, viability and osmotic tolerance were determined. 3. Cryosurvival of turkey sperm was affected by DMSO concentration. Freezing rate affected the motility of sperm cryopreserved using both CPAs, while thawing rates showed an effect on the motility of sperm cryopreserved using DMA and on the viability of sperm cryopreserved using DMSO. Significant interactions between freezing rate × thawing rate on sperm viability in the DMA protocol were found. 4. The most effective freezing protocol was the use of 18% DMA or 10% DMSO with freezing 10 cm above the LN2 surface and a thawing temperature of 50°C. An efficient protocol for turkey semen would improve prospects for sperm cryobanks and the commercial use of frozen turkey semen.

Water at protein surfaces studied with femtosecond nonlinear spectroscopy

NASA Astrophysics Data System (ADS)

Bakker, Huib J.

We report on an investigation of the structure and dynamics of water molecules near protein surfaces with femtosecond nonlinear spectroscopic techniques. We measured the reorientation dynamics of water molecules near the surface of several globular protein surfaces, using polarization-resolved femtosecond infrared spectroscopy. We found that water molecules near the protein surface have a much slower reorientation than water molecules in bulk liquid water. The number of slow water molecules scales scales with the size of the hydrophobic surface of the protein. When we denature the proteins by adding an increasing amount of urea to the protein solution, we observe that the water-exposed surface increases by 50% before the secondary structure of the proteins changes. This finding indicates that protein unfolding starts with the protein structure becoming less tight, thereby allowing water to enter. With surface vibrational sum frequency generation (VSFG) spectroscopy, we studied the structure of water at the surface of antifreeze protein III. The measured VSFG spectra showed the presence of ice-like water layers at the ice-binding site of the protein in aqueous solution, at temperatures well above the freezing point. This ordered ice-like hydration layers at the protein surface likely plays an important role in the specific recognition and binding of anti-freeze protein III to nascent ice crystallites, and thus in its anti-freeze mechanism. This research is supported by the ''Nederlandse organisatie voor Wetenschappelijk Onderzoek (NWO).

Processes Leading to Beaded Channels Formation in Central Yakutia

NASA Astrophysics Data System (ADS)

Tarbeeva, A. M.; Lebedeva, L.; Efremov, V. S.; Krylenko, I. V.; Surkov, V. V.

2017-12-01

Beaded channels, consisting of deepened and widened pools and connecting narrow runs, are common fluvial forms in permafrost regions. Recent studies have shown that beaded channels are very important for connecting alluvial rivers with headwater lakes allowing fish passage and foraging habitats, as well as regulating river runoff. Beaded channels are known as typical thermokarst landforms; however, there is no evidence of their origin and formative processes. Geomorphological analyzes of beaded channels have been completed in several permafrost regions including field observations of Shestakovka River in Central Yakutia. The study aims to recognize the modern exogenic processes and formative mechanisms of beaded river channels. We show that beaded channel of Shestakovka River form in the perennially frozen sand with low ice content, leading us to hypothesize that thermokarst is not the main process of formation. Due to the significant volume of water, the pools don't freeze over entirely during winters, even under harsh climatic conditions. As a result, lenses of pressurized water remain under surface ice underlain by perennially thawed sediments. The presence of thawed sediments under the pools and frozen sediments under the runs leads to uneven thermoerosion of the riverbed during floods, providing the beaded form of the channel. In addition, freezing of pools during winter leads to pressure increasing under ice cover and formation of ice mounds, which crack several times during winter leading to disturbance of riverbanks. Many 1st to 3rd order streams have a specific transitional meandering-to-beaded form resembling the shape of unconfined meandering rivers, but consisting of pools and runs. However, such channels exhibit no evidences of present-day erosion of concave banks and sediment accumulation at the convex banks as typically being observed in normally meandering rivers. Such forms of channels indicates that their formation occurred by the greater channel-forming flow discharges in the past. Transition to the beaded channel planform took place only later, presumably as a result of climate changes. Reduction of water runoff and freezing over of taliks leaded to activation of cryogenic processes (thermokarst, uneven thermoerosion, disturbance of riverbanks during the cracking of ice mounds).

The Soil Moisture Active and Passive Mission (SMAP): Science and Applications

NASA Technical Reports Server (NTRS)

Entekhabi, Dara; O'Neill, Peggy; Njoku, Eni

2009-01-01

The Soil Moisture Active and Passive mission (SMAP) will provide global maps of soil moisture content and surface freeze/thaw state. Global measurements of these variables are critical for terrestrial water and carbon cycle applications. The SMAP observatory consists of two multipolarization L-band sensors, a radar and radiometer, that share a deployable-mesh reflector antenna. The combined observations from the two sensors will allow accurate estimation of soil moisture at hydrometeorological (10 km) and hydroclimatological (40 km) spatial scales. The rotating antenna configuration provides conical scans of the Earth surface at a constant look angle. The wide-swath (1000 km) measurements will allow global mapping of soil moisture and its freeze/thaw state with 2-3 days revisit. Freeze/thaw in boreal latitudes will be mapped using the radar at 3 km resolution with 1-2 days revisit. The synergy of active and passive observations enables measurements of soil moisture and freeze/thaw state with unprecedented resolution, sensitivity, area coverage and revisit.

Forecasting and modelling ice layer formation on the snowpack due to freezing precipitations in the Pyrenees

NASA Astrophysics Data System (ADS)

Quéno, Louis; Vionnet, Vincent; Cabot, Frédéric; Vrécourt, Dominique; Dombrowski-Etchevers, Ingrid

2017-04-01

In the Pyrenees, freezing precipitations in altitude occur at least once per winter, leading to the formation of a pure ice layer on the surface of the snowpack. It may lead to accidents and fatalities among mountaineers and skiers, with sometimes a higher human toll than avalanches. Such events are not predicted by the current operational systems for snow and avalanche hazard forecasting. A crowd-sourced database of surface ice layer occurrences is first built up, using reports from Internet mountaineering and ski-touring communities, to mitigate the lack of observations from conventional observation networks. A simple diagnostic of freezing precipitation is then developed, based on the cloud water content and screen temperature forecast by the Numerical Weather Prediction model AROME, operating at 2.5-km resolution. The performance of this diagnostic is assessed for the event of 5-6 January 2012, with a good representation of altitudinal and spatial distributions of the ice layer. An evaluation of the diagnostic for major events over five winters gives good skills of detection compared to the occurrences reported in the observation database. A new modelling of ice formation on the surface of the snowpack due to impinging supercooled water is added to the detailed snowpack model Crocus. It is combined to the atmospheric diagnostic of freezing precipitations and resulting snowpack simulations over a winter season capture well the formation of the main ice layers. Their influence on the snowpack stratigraphy is also realistically simulated. These simple methods enable to forecast the occurrence of surface ice layer formations with good confidence and to simulate their evolution within the snowpack, even if an accurate estimation of freezing precipitation amounts remains the main challenge.

Surface Structure of Yeast Protoplasts

PubMed Central

Streiblová, Eva

1968-01-01

The fine structure of the yeast cell wall during protoplast formation was studied by means of phase-contrast microscopy and the freeze-etching technique. The freeze-etching results indicated that at least in some cases the entire wall substance was not removed from the surface of the protoplasts. After a treatment of 30 min to 3 hr with 2% snail enzymes, an innermost thin wall layer as well as remnants of the fibrillar middle layer sometimes could be demonstrated. Images PMID:4867751

Freeze Tape Casting of Functionally Graded Porous Ceramics

NASA Technical Reports Server (NTRS)

Sofie, Stephen W.

2007-01-01

Freeze tape casting is a means of making preforms of ceramic sheets that, upon subsequent completion of fabrication processing, can have anisotropic and/or functionally graded properties that notably include aligned and graded porosity. Freeze tape casting was developed to enable optimization of the microstructures of porous ceramic components for use as solid oxide electrodes in fuel cells: Through alignment and grading of pores, one can tailor surface areas and diffusion channels for flows of gas and liquid species involved in fuel-cell reactions. Freeze tape casting offers similar benefits for fabrication of optimally porous ceramics for use as catalysts, gas sensors, and filters.

Investigating methods to estimate melting event parameters over Arctic sea- ice using SSM/I, OKEAN, and RADARSAT Data

NASA Astrophysics Data System (ADS)

Belchansky, G.; Eremeev, V.; Mordvintsev, I.; Platonov, N.; Douglas, D.

The melting events (early melt, melt onset, melt ponding, freeze-up onset) over Arctic sea-ice area are critical for climate and global change studies. They are combined with accuracy of surface energy balances estimates (due to contrasts in the short wave albedo of snow and ice, open water or melt ponds) and drives a number of important processes (onset of snow melt, thawing of boreal forest, etc). M icrowave measurements identify seasonal transition zones due to large differences in emissivity during melt onset, melt ponding and freeze-up periods. This report presents near coincident observation of backscatter cross section (0 ) and brightness temperature (Tb) from Russian OKEAN 01 satellite series, backscatter cross section (0) from RADARSAT-1, brightness temperatures (Tbs) from SSM/I sensors, and near-surface temperature derived from the International Arctic Buoy Program data (IABP) (Belchansky and Douglas, 2000, 2002). To determine the melt duration (time of freeze-up onset minus time of melt onset) passive and active microwave methods were developed. These methods used differences between SSM /I 19.3GHz,H and SSM/I 37.0 GHz, H channels (SSM/I Tb), OKEAN 0 (9.52GHz, VV) and Tb (37.47 GHz, H) channels, RADARSAT-1 0 (5.3GHz, HH), and a threshold technique. An evolution of the SSM/I Tb, OKEAN-01 0 and Tb, RADARSAT ScanSAR 0, MEAN ( 0), SD(0) and SD(0 ) / MEAN(0 ) as function of time was investigated along FY and MY dominant type ice areas during January 1996 through December 1998. The SSM/I, OKEAN and RADARSAT melt onset and freeze up onset algorithms were constructed. The SSM/I algorithm was based- on analysis of the SSM/I Tb. The OKEAN and RADARSAT ScanSAR algorithms were based, respectively, on analysis of OKEAN 0 and Tb of MY and FY sea ice at each MY and FY ice region (200 km by 200 km) determined in OKEAN imagery prior to melting period and changes in RADARSAT SD(0 ) / MEAN(0) of sea-ice during different stages of melting processes at each ice site (75 km by 75 km) determined prior to spring period in ScanSAR imagery. The averaged 12-h near surface temperatures derived from the IABP wer e used to analyze changes in the SSM/I Tb, OKEAN 0 and OKEAN Tb, RADARSAT SD(0) / MEAN(0), and to estimate respective thresholds associated with the melt onset and freeze-up onset. To highlight the sources of differences among various sensors results were compared to understand how the average the melt onset, melt duration and freeze-up onset estimates varied between different instruments and algorithms. A discrepancy in estimates resulted due to the nature of active and passive microwave measurements, frequency and polarization, number of channels, temperature and emissivity effects, and algorithm types. Higher spatial resolution of OKEAN-01 and RADARSAT-1 SAR was an important characteristic for obtaining better estimates of melting parameters. The SSM/ data provide a spatial resolution with global coverageI suitable for circulation models. Therefore OKEAN-01 and RADARSAT measurements can complement SSM/I data. These studies contribute to the growing body of documentation about the levels of disparity obtained when Arctic seasonal transition parameters are calculated using various types of satellite sensors and algorithms. ACKNOWLEDGEMENTS This work was carried out with the support from the International Arctic Research Center and Cooperative Institute for Arctic Research (IARC/CIFAR), University of Alaska Fairbanks. We would like to acknowledge the Alaska SAR Facility (Fairbanks), the National Snow and Ice Data Center (University of Colorado), and the Global Hydrology Resource Center, respectively, for providing RADARSAT images, the DMSP SSM/I Daily Polar Gridded Tb and Sea Ice Concentrations, the single-pass SSM/I brightness temperature data. REFERENCES Belchansky, G. I. and Douglas, D. C. (2000). Classification methods for monitoring Arctic sea-ice using OKEAN passive / active two-channel microwave data. J. Remote Sensing of Environment, Elsevier Science, New York. 73 (3): 307 -322. Belchansky, G. I. and Douglas, D. C. (2002). Seasonal comparisons of sea ice concentration estimates derived from SSM /I, OKEAN, and RADARSAT data. J. Remote Sensing of Environment, Elsevier Science, New York, 81 (1): 67-81.

Effect of freeze-thaw cycles on greenhouse gas fluxes from peat soils

NASA Astrophysics Data System (ADS)

Oh, H. D.; Rezanezhad, F.; Markelov, I.; McCarter, C. P. R.; Van Cappellen, P.

2017-12-01

The ongoing displacement of climate zones by global warming is increasing the frequency and intensity of freeze-thaw cycles in middle and high latitude regions, many of which are dominated by organic soils such as peat. Repeated freezing and thawing of soils changes their physical properties, geochemistry, and microbial community structure, which together govern the biogeochemical cycling of carbon and nutrients. In this presentation, we focus on how freeze-thaw cycles influence greenhouse gas fluxes from peat using a newly developed experimental soil column system that simulates realistic soil temperature profiles during freeze-thaw cycles. We measured the surface and subsurface changes to gas and aqueous phase chemistry to delineate the diffusion pathways and quantify soil greenhouse gas fluxes during freeze-thaw cycles using sulfur hexafluoride (SF6) as a conservative tracer. Three peat columns were assembled inside a temperature controlled chamber with different soil structures. All three columns were packed with 40 cm of undisturbed, slightly decomposed peat, where the soil of two columns had an additional 10 cm layer on top (one with loose Sphagnum moss and one with an impermeable plug). The results indicate that the release of SF6 and CO2 gas from the soil surface was influenced by the recurrent development of a physical ice barrier, which prevented gas exchange between the soil and atmosphere during freezing conditions. With the onset of thawing a pulse of SF6 and CO2 occurred, resulting in a flux of 3.24 and 2095.52 µmol/m2h, respectively, due to the build-up of gases in the liquid-phase pore space during freezing. Additionally, we developed a model to determine the specific diffusion coefficients for each peat column. These data allow us to better predict how increased frequency and intensity of freeze-thaw cycles will affect greenhouse gas emissions in northern peat soils.

Reversible shear-induced crystallization above equilibrium freezing temperature in a lyotropic surfactant system

PubMed Central

Rathee, Vikram; Krishnaswamy, Rema; Pal, Antara; Raghunathan, V. A.; Impéror-Clerc, Marianne; Pansu, Brigitte; Sood, A. K.

2013-01-01

We demonstrate a unique shear-induced crystallization phenomenon above the equilibrium freezing temperature in weakly swollen isotropic and lamellar mesophases with bilayers formed in a cationic-anionic mixed surfactant system. Synchrotron rheological X-ray diffraction study reveals the crystallization transition to be reversible under shear (i.e., on stopping the shear, the nonequilibrium crystalline phase melts back to the equilibrium mesophase). This is different from the shear-driven crystallization below , which is irreversible. Rheological optical observations show that the growth of the crystalline phase occurs through a preordering of the phase to an phase induced by shear flow, before the nucleation of the phase. Shear diagram of the phase constructed in the parameter space of shear rate vs. temperature exhibits and transitions above the equilibrium crystallization temperature , in addition to the irreversible shear-driven nucleation of in the phase below . In addition to revealing a unique class of nonequilibrium phase transition, the present study urges a unique approach toward understanding shear-induced phenomena in concentrated mesophases of mixed amphiphilic systems. PMID:23986497

A comparative study of K-rich and Na/Ca-rich feldspar ice-nucleating particles in a nanoliter droplet freezing assay

NASA Astrophysics Data System (ADS)

Peckhaus, Andreas; Kiselev, Alexei; Hiron, Thibault; Ebert, Martin; Leisner, Thomas

2016-09-01

A recently designed droplet freezing assay was used to study the freezing of up to 1500 identical 0.2 nL water droplets containing suspensions of one Na/Ca-rich feldspar and three K-rich and one Na/Ca-rich feldspar particles. Three types of experiments have been conducted: cooling ramp, isothermal freezing at a constant temperature, and freeze-thaw cycles. The observed freezing behavior has been interpreted with the help of a model based on the classical nucleation theory (soccer ball model (SBM); Niedermeier et al., 2015). By applying the model to the different freezing experiments conducted with the same ice-nucleating material, the unique sets of model parameters for specific feldspar suspensions could be derived. The SBM was shown to adequately describe the observed cooling rate dependence, the ice-nucleating active sites (INAS) surface density ns(T) in a wide temperature range, and the shift of the freezing curves towards lower temperature with dilution. Moreover, the SBM was capable of reproducing the variation of INAS surface density ns(T) with concentration of ice-nucleating particles in the suspension droplets and correctly predicting the leveling-off of ns(T) at low temperature. The freeze-thaw experiments have clearly shown that the heterogeneous freezing induced even by very active ice-nucleating species still possesses a stochastic nature, with the degree of randomness increasing towards homogeneous nucleation. A population of the high-temperature INAS has been identified in one of the K-rich feldspar samples. The freezing of 0.8 wt % suspension droplets of this particular feldspar was observed already at -5 °C. These high-temperature active sites could be deactivated by treating the sample with hydrogen peroxide but survived heating up to 90 °C. Given a high mass concentration of these high-temperature active sites (2.9 × 108 g-1) and a very low value of contact angle (0.56 rad) the possibility of biological contamination of the sample was concluded to be unlikely but could not be completely ruled out. The freezing efficacy of all feldspar samples has been shown to reduce only slightly after suspension in water for over 5 months.

Effect of cryoprotectants on the porosity and stability of insulin-loaded PLGA nanoparticles after freeze-drying

PubMed Central

Fonte, Pedro; Soares, Sandra; Costa, Ana; Andrade, José Carlos; Seabra, Vítor; Reis, Salette; Sarmento, Bruno

2012-01-01

PLGA nanoparticles are useful to protect and deliver proteins in a localized or targeted manner, with a long-term systemic delivery pattern intended to last for a period of time, depending on polymer bioerosion and biodegradability. However, the principal concern regarding these carriers is the hydrolytic instability of polymer in aqueous suspension. Freeze-drying is a commonly used method to stabilize nanoparticles, and cryoprotectants may be also used, to even increase its physical stability. The aim of the present work was to analyze the influence of cryoprotectants on nanoparticle stability and porosity after freeze-drying, which may influence protein release and stability. It was verified that freeze-drying significantly increased the number of pores on PLGA-NP surface, being more evident when cryoprotectants are added. The presence of pores is important in a lyophilizate to facilitate its reconstitution in water, although this may have consequences to protein release and stability. The release profile of insulin encapsulated into PLGA-NP showed an initial burst in the first 2 h and a sustained release up to 48 h. After nanoparticles freeze-drying the insulin release increased about 18% in the first 2 h due to the formation of pores, maintaining a sustained release during time. After freeze-drying with cryoprotectants, the amount of insulin released was higher for trehalose and lower for sucrose, glucose, fructose and sorbitol comparatively to freeze-dried PLGA-NP with no cryoprotectant added. Besides the porosity, the ability of cryoprotectants to be adsorbed on the nanoparticles surface may also play an important role on insulin release and stability. PMID:23507897

Practical Considerations for Determination of Glass Transition Temperature of a Maximally Freeze Concentrated Solution.

PubMed

Pansare, Swapnil K; Patel, Sajal Manubhai

2016-08-01

Glass transition temperature is a unique thermal characteristic of amorphous systems and is associated with changes in physical properties such as heat capacity, viscosity, electrical resistance, and molecular mobility. Glass transition temperature for amorphous solids is referred as (T g), whereas for maximally freeze concentrated solution, the notation is (T g'). This article is focused on the factors affecting determination of T g' for application to lyophilization process design and frozen storage stability. Also, this review provides a perspective on use of various types of solutes in protein formulation and their effect on T g'. Although various analytical techniques are used for determination of T g' based on the changes in physical properties associated with glass transition, the differential scanning calorimetry (DSC) is the most commonly used technique. In this article, an overview of DSC technique is provided along with brief discussion on the alternate analytical techniques for T g' determination. Additionally, challenges associated with T g' determination, using DSC for protein formulations, are discussed. The purpose of this review is to provide a practical industry perspective on determination of T g' for protein formulations as it relates to design and development of lyophilization process and/or for frozen storage; however, a comprehensive review of glass transition temperature (T g, T g'), in general, is outside the scope of this work.

Bacterial Ice Crystal Controlling Proteins

PubMed Central

Lorv, Janet S. H.; Rose, David R.; Glick, Bernard R.

2014-01-01

Across the world, many ice active bacteria utilize ice crystal controlling proteins for aid in freezing tolerance at subzero temperatures. Ice crystal controlling proteins include both antifreeze and ice nucleation proteins. Antifreeze proteins minimize freezing damage by inhibiting growth of large ice crystals, while ice nucleation proteins induce formation of embryonic ice crystals. Although both protein classes have differing functions, these proteins use the same ice binding mechanisms. Rather than direct binding, it is probable that these protein classes create an ice surface prior to ice crystal surface adsorption. Function is differentiated by molecular size of the protein. This paper reviews the similar and different aspects of bacterial antifreeze and ice nucleation proteins, the role of these proteins in freezing tolerance, prevalence of these proteins in psychrophiles, and current mechanisms of protein-ice interactions. PMID:24579057

Bacterial ice crystal controlling proteins.

PubMed

Lorv, Janet S H; Rose, David R; Glick, Bernard R

2014-01-01

Across the world, many ice active bacteria utilize ice crystal controlling proteins for aid in freezing tolerance at subzero temperatures. Ice crystal controlling proteins include both antifreeze and ice nucleation proteins. Antifreeze proteins minimize freezing damage by inhibiting growth of large ice crystals, while ice nucleation proteins induce formation of embryonic ice crystals. Although both protein classes have differing functions, these proteins use the same ice binding mechanisms. Rather than direct binding, it is probable that these protein classes create an ice surface prior to ice crystal surface adsorption. Function is differentiated by molecular size of the protein. This paper reviews the similar and different aspects of bacterial antifreeze and ice nucleation proteins, the role of these proteins in freezing tolerance, prevalence of these proteins in psychrophiles, and current mechanisms of protein-ice interactions.

Hyperprolinemic larvae of the drosophilid fly, Chymomyza costata, survive cryopreservation in liquid nitrogen

PubMed Central

Koštál, Vladimír; Zahradníčková, Helena; Šimek, Petr

2011-01-01

The larva of the drosophilid fly, Chymomyza costata, is probably the most complex metazoan organism that can survive submergence in liquid nitrogen (-196 °C) in a fully hydrated state. We examined the associations between the physiological and biochemical parameters of differently acclimated larvae and their freeze tolerance. Entering diapause is an essential and sufficient prerequisite for attaining high levels of survival in liquid nitrogen (23% survival to adult stage), although cold acclimation further improves this capacity (62% survival). Profiling of 61 different metabolites identified proline as a prominent compound whose concentration increased from 20 to 147 mM during diapause transition and subsequent cold acclimation. This study provides direct evidence for the essential role of proline in high freeze tolerance. We increased the levels of proline in the larval tissues by feeding larvae proline-augmented diets and found that this simple treatment dramatically improved their freeze tolerance. Cell and tissue survival following exposure to liquid nitrogen was evident in proline-fed nondiapause larvae, and survival to adult stage increased from 0% to 36% in proline-fed diapause-destined larvae. A significant statistical correlation was found between the whole-body concentration of proline, either natural or artificial, and survival to the adult stage in liquid nitrogen for diapause larvae. Differential scanning calorimetry analysis suggested that high proline levels, in combination with a relatively low content of osmotically active water and freeze dehydration, increased the propensity of the remaining unfrozen water to undergo a glass-like transition (vitrification) and thus facilitated the prevention of cryoinjury. PMID:21788482

Hyperprolinemic larvae of the drosophilid fly, Chymomyza costata, survive cryopreservation in liquid nitrogen.

PubMed

Kostál, Vladimír; Zahradnícková, Helena; Šimek, Petr

2011-08-09

The larva of the drosophilid fly, Chymomyza costata, is probably the most complex metazoan organism that can survive submergence in liquid nitrogen (-196 °C) in a fully hydrated state. We examined the associations between the physiological and biochemical parameters of differently acclimated larvae and their freeze tolerance. Entering diapause is an essential and sufficient prerequisite for attaining high levels of survival in liquid nitrogen (23% survival to adult stage), although cold acclimation further improves this capacity (62% survival). Profiling of 61 different metabolites identified proline as a prominent compound whose concentration increased from 20 to 147 mM during diapause transition and subsequent cold acclimation. This study provides direct evidence for the essential role of proline in high freeze tolerance. We increased the levels of proline in the larval tissues by feeding larvae proline-augmented diets and found that this simple treatment dramatically improved their freeze tolerance. Cell and tissue survival following exposure to liquid nitrogen was evident in proline-fed nondiapause larvae, and survival to adult stage increased from 0% to 36% in proline-fed diapause-destined larvae. A significant statistical correlation was found between the whole-body concentration of proline, either natural or artificial, and survival to the adult stage in liquid nitrogen for diapause larvae. Differential scanning calorimetry analysis suggested that high proline levels, in combination with a relatively low content of osmotically active water and freeze dehydration, increased the propensity of the remaining unfrozen water to undergo a glass-like transition (vitrification) and thus facilitated the prevention of cryoinjury.

Freeze-dried snake antivenoms formulated with sorbitol, sucrose or mannitol: comparison of their stability in an accelerated test.

PubMed

Herrera, María; Tattini, Virgilio; Pitombo, Ronaldo N M; Gutiérrez, José María; Borgognoni, Camila; Vega-Baudrit, José; Solera, Federico; Cerdas, Maykel; Segura, Alvaro; Villalta, Mauren; Vargas, Mariángela; León, Guillermo

2014-11-01

Freeze-drying is used to improve the long term stability of pharmaceutical proteins. Sugars and polyols have been successfully used in the stabilization of proteins. However, their use in the development of freeze-dried antivenoms has not been documented. In this work, whole IgG snake antivenom, purified from equine plasma, was formulated with different concentrations of sorbitol, sucrose or mannitol. The glass transition temperatures of frozen formulations, determined by Differential Scanning Calorimetry (DSC), ranged between -13.5 °C and -41 °C. In order to evaluate the effectiveness of the different stabilizers, the freeze-dried samples were subjected to an accelerated stability test at 40 ± 2 °C and 75 ± 5% relative humidity. After six months of storage at 40 °C, all the formulations presented the same residual humidity, but significant differences were observed in turbidity, reconstitution time and electrophoretic pattern. Moreover, all formulations, except antivenoms freeze-dried with mannitol, exhibited the same potency for the neutralization of lethal effect of Bothrops asper venom. The 5% (w:v) sucrose formulation exhibited the best stability among the samples tested, while mannitol and sorbitol formulations turned brown. These results suggest that sucrose is a better stabilizer than mannitol and sorbitol in the formulation of freeze-dried antivenoms under the studied conditions. Copyright © 2014 Elsevier Ltd. All rights reserved.

Chemistry and Spectroscopy of Frozen Chloride Salts on Icy Bodies

NASA Astrophysics Data System (ADS)

Johnson, Paul; Thomas, Elena C.; Hodyss, Robert; Vu, Tuan; Choukroun, Mathieu

2016-10-01

Currently, our understanding of the chemical composition of Europa's surface is our best means of inferring constraints on the subsurface ocean composition and its subsequent habitability. The bulk of our knowledge of Europa surface chemistry can be traced to near infrared spectra recorded by the Near Infrared Mapping Spectrometer on the Galileo spacecraft. However, the usefulness of this and other remote sensing data is limited by the availability of spectral libraries of candidate materials under relevant conditions (temperature, thermal/radiation history, etc.). Chloride salts are expected to exist on the surface of Europa, and other icy bodies, based on geochemical predictions of the ocean composition. In order to help improve our understanding of Europa's surface composition, we have conducted a study of frozen chloride-salt brines prepared under simulated Europa surface conditions (vacuum, temperature, and UV irradiation) using both near IR and Raman spectroscopies. Specifically, Raman spectroscopy was used to determine the hydration states of various chloride salts as a function of temperature. Near IR spectroscopy of identically prepared samples was used to provide reference reflectance spectra of the identified hydrated salts. Our results indicate that at temperatures ranging from 80 K to 233 K, hydrohalite is formed from the freezing of NaCl brines, while the freezing of KCl solutions does not form KCl hydrates. In addition, the freezing of MgCl2 solutions forms a stable hexahydrate, and the freezing of CaCl2 solutions forms a hexahydrate, a tetrahydrate, and a dihydrate. Dehydration of the salts was observed as temperatures were increased, leading to a succession of hydration states in the case of CaCl2.

Surface Crystallization of Cloud Droplets: Implications for Climate Change and Ozone Depletion

NASA Technical Reports Server (NTRS)

Tabazadeh, A.; Djikaev, Y. S.; Reiss, H.; Gore, Warren J. (Technical Monitor)

2002-01-01

The process of supercooled liquid water crystallization into ice is still not well understood. Current experimental data on homogeneous freezing rates of ice nucleation in supercooled water droplets show considerable scatter. For example, at -33 C, the reported freezing nucleation rates vary by as much as 5 orders of magnitude, which is well outside the range of measurement uncertainties. Until now, experimental data on the freezing of supercooled water has been analyzed under the assumption that nucleation of ice took place in the interior volume of a water droplet. Here, the same data is reanalyzed assuming that the nucleation occurred "pseudoheterogeneously" at the air (or oil)-liquid water interface of the droplet. Our analysis suggest that the scatter in the nucleation data can be explained by two main factors. First, the current assumption that nucleation occurs solely inside the volume of a water droplet is incorrect. Second, because the nucleation process most likely occurs on the surface, the rates of nuclei formation could differ vastly when oil or air interfaces are involved. Our results suggest that ice freezing in clouds may initiate on droplet surfaces and such a process can allow for low amounts of liquid water (approx. 0.002 g per cubic meters) to remain supercooled down to -40 C as observed in the atmosphere.

Freeze-Thaw Durability of Air-Entrained Concrete

PubMed Central

Shang, Huai-Shuai; Yi, Ting-Hua

2013-01-01

One of the most damaging actions affecting concrete is the abrupt temperature change (freeze-thaw cycles). The types of deterioration of concrete structures by cyclic freeze-thaw can be largely classified into surface scaling (characterized by the weight loss) and internal crack growth (characterized by the loss of dynamic modulus of elasticity). The present study explored the durability of concrete made with air-entraining agent subjected to 0, 100, 200, 300, and 400 cycles of freeze-thaw. The experimental study of C20, C25, C30, C40, and C50 air-entrained concrete specimens was completed according to “the test method of long-term and durability on ordinary concrete” GB/T 50082-2009. The dynamic modulus of elasticity and weight loss of specimens were measured after different cycles of freeze-thaw. The influence of freeze-thaw cycles on the relative dynamic modulus of elasticity and weight loss was analyzed. The findings showed that the dynamic modulus of elasticity and weight decreased as the freeze-thaw cycles were repeated. They revealed that the C30, C40, and C50 air-entrained concrete was still durable after 300 cycles of freeze-thaw according to the experimental results. PMID:23576906

Freeze-thaw durability of air-entrained concrete.

PubMed

Shang, Huai-Shuai; Yi, Ting-Hua

2013-01-01

One of the most damaging actions affecting concrete is the abrupt temperature change (freeze-thaw cycles). The types of deterioration of concrete structures by cyclic freeze-thaw can be largely classified into surface scaling (characterized by the weight loss) and internal crack growth (characterized by the loss of dynamic modulus of elasticity). The present study explored the durability of concrete made with air-entraining agent subjected to 0, 100, 200, 300, and 400 cycles of freeze-thaw. The experimental study of C20, C25, C30, C40, and C50 air-entrained concrete specimens was completed according to "the test method of long-term and durability on ordinary concrete" GB/T 50082-2009. The dynamic modulus of elasticity and weight loss of specimens were measured after different cycles of freeze-thaw. The influence of freeze-thaw cycles on the relative dynamic modulus of elasticity and weight loss was analyzed. The findings showed that the dynamic modulus of elasticity and weight decreased as the freeze-thaw cycles were repeated. They revealed that the C30, C40, and C50 air-entrained concrete was still durable after 300 cycles of freeze-thaw according to the experimental results.

Gap-freezing approach for shortening the lyophilization cycle time of pharmaceutical formulations-demonstration of the concept.

PubMed

Kuu, Wei Y; Doty, Mark J; Rebbeck, Christine L; Hurst, William S; Cho, Yong K

2013-08-01

During gap freezing, vials are placed on a metal tray, which is separated from the shelf surface with a small air gap that eliminates significant conductive heat transfer from the shelf to the bottom of the vial. The purpose of this freezing approach is to reduce the lyophilization cycle time of various amorphous formulations by nearly isothermal freezing. Such isothermal freezing promotes the formation of large ice crystals, and thus large pores throughout the cake, which subsequently accelerates the primary drying rate. The nucleation temperature using gap freezing, for the experimental conditions tested, was in the range of -1°C to -6°C, much higher than the range of -10°C to -14°C found using conventional shelf freezing. Isothermal freezing becomes effective when the gap is greater than 3 mm. The pore sizes and cake resistance during primary drying for various formulations were determined using the pore diffusion model developed by Kuu et al. (Pharm Dev Technol, 2011, 16(4): 343-357). Reductions in primary drying time were 42% (for 10% sucrose), 45% (for 10% trehalose), and 33% (for 5% sucrose). Copyright © 2013 Wiley Periodicals, Inc.

Impact of heat treatment on miscibility of proteins and disaccharides in frozen solutions.

PubMed

Izutsu, Ken-ichi; Yomota, Chikako; Okuda, Haruhiro; Kawanishi, Toru; Randolph, Theodore W; Carpenter, John F

2013-10-01

The purpose of this study was to elucidate the effect of heat treatment (annealing) on the miscibility of concentrated protein and disaccharide mixtures in the freezing segment of lyophilization. Frozen solutions containing a protein (e.g., recombinant human albumin, chicken egg lysozyme, bovine plasma immunoglobulin G, or a humanized IgG1k monoclonal antibody) and a non-reducing disaccharide (e.g., sucrose or trehalose) showed single thermal transitions of the solute mixtures (glass transition temperature of maximally freeze-concentrated solutes: T(g)(')) in their first heating scans. Heat treatment (e.g., -5 °C, 30 min) of some disaccharide-rich mixture frozen solutions at temperatures far above their T(g)(') induced two-step T(g)(') transitions in the subsequent scans, suggesting the separation of the solutes into concentrated protein-disaccharide mixture phase and disaccharide phase. Other frozen solutions showed a single transition of the concentrated solute mixture both before and after heat treatment. The apparent effects of the heat treatment temperature and time on the changes in thermal properties suggest molecular reordering of the concentrated solutes from a kinetically fixed mixture state to a more thermodynamically favorable state as a result of increased mobility. The implications of these phenomena on the quality of protein formulations are discussed. Copyright © 2013 Elsevier B.V. All rights reserved.

(abstract) Monitoring Seasonal State and Mapping Species in Alaskan Taiga Using Imaging Radar as Input to CO(sub 2) Flux Models

NASA Technical Reports Server (NTRS)

Way, J. B.; Rignot, E.; McDonald, K.; Adams, P.; Viereck, L.

1993-01-01

Changes in the seasonal CO(sub 2) flux of the boreal forests may result from increased atmospheric CO(sub 2) concentrations and associated atmospheric warming. To monitor this potential change, a combination of remote sensing information and ecophysiological models are required. In this paper we address the use of synthetic aperture radar (SAR) data to provide some of the input to the ecophysiological models: forest type, freeze/thaw state which limits the growing season for conifers, and leaf on/off state which limits the growing season for deciduous species. AIRSAR data collected in March 1988 during an early thaw event and May 1991 during spring breakup are used to generate species maps and to determine the sensitivity of SAR to canopy freeze/thaw transitions. These data are also used to validate a microwave scattering model which is then used to determine the sensitivity of SAR to leaf on/off and soil freeze/thaw transitions. Finally, a CO(sub 2) flux algorithm which utilizes SAR data and an ecophysiological model to estimate CO(sub 2) flux is presented. CO(sub 2) flux maps are generated from which areal estimates of CO(sub 2) flux are derived.

Freezing Directed Construction of Bio/Nano Interfaces: Reagentless Conjugation, Denser Spherical Nucleic Acids, and Better Nanoflares.

PubMed

Liu, Biwu; Liu, Juewen

2017-07-19

While nanoparticle solutions cannot freeze in general, they may remain stable in the presence of polymer stabilizers. We herein communicate that gold nanoparticles (AuNPs) are stable in the presence of thiolated DNA after a freeze-thaw cycle. The DNA is conjugated to AuNPs during freezing without additional reagents and the conjugation can be completed in a few minutes. More importantly, the DNA density is 20-30% higher than that prepared by the typical salt-aging method. By lowering temperature, DNA hybridization is also promoted, allowing the construction of better nanoflares with doubled probe density and signaling sensitivity. This freezing method works for AuNPs from 5 to 100 nm and all tested DNA sequences. The mechanism was studied by separating the effect of temperature, freezing and thawing, where the exclusion of salt and AuNPs by the growing ice crystals is deemed critical. In addition to developing a simple method, this study articulates unique physical processes during freezing with important fundamental surface science implications, and it could be extended to other systems.

A comparative study of sodium dodecyl sulfate and freezing/thawing treatment on wheat starch: The role of water absorption.

PubMed

Tao, Han; Wang, Pei; Zhang, Bao; Wu, Fengfeng; Jin, Zhengyu; Xu, Xueming

2016-06-05

The effect of freezing on functionality of native and sodium dodecyl sulfate (SDS)-treated wheat starches was investigated, with the aim of understanding the role of water absorption during freezing process. SDS is one of most efficient detergents to remove non-starch components (such as proteins and lipids) for starches but does not cause any apparent damage on granular structure. Slow swelling could be converted to rapid swelling by SDS washing, indicating higher water absorption. Freezing process induced slight roughness on starch granules but the non-starch components content was little affected. Combined SDS+freezing treatment significantly decreased both amylose and proteins non-starch components contents, which was accompanied with high gelatinization temperatures, melting enthalpy, and pasting viscosities. A smaller bread specific volume was obtained from SDS+freezing-treated starches while the crumb firmness significantly increased (p<0.05). SDS mainly extracted the surface components from starch granules, leading to high water absorption and making granules sensitive to the freezing treatment. Copyright © 2016 Elsevier Ltd. All rights reserved.

Impact of the Hydration States of Polymers on Their Hemocompatibility for Medical Applications: A Review

PubMed Central

Bag, Min A.

2017-01-01

Water has a key role in the functioning of all biological systems, it mediates many biochemical reactions, as well as other biological activities such as material biocompatibility. Water is often considered as an inert solvent, however at the molecular level, it shows different behavior when sorbed onto surfaces like polymeric implants. Three states of water have been recognized: non-freezable water, which does not freeze even at −100 °C; intermediate water, which freezes below 0 °C; and, free water, which freezes at 0 °C like bulk water. This review describes the different states of water and the techniques for their identification and quantification, and analyzes their relationship with hemocompatibility in polymer surfaces. Intermediate water content higher than 3 wt % is related to better hemocompatibility for poly(ethylene glycol), poly(meth)acrylates, aliphatic carbonyls, and poly(lactic-co-glycolic acid) surfaces. Therefore, characterizing water states in addition to water content is key for polymer selection and material design for medical applications. PMID:28771174

Closed-system freezing of soils in linings and earth embankment dams

NASA Astrophysics Data System (ADS)

Jones, C. W.

1981-03-01

A brief review of studies of closed-system freezing (no source of water except that in voids) of compacted soil canal linings, laboratory and field test results show that under certain soil and temperature conditions, freezing decreases soil density near the surface, but increases density at depth. In two linings, the average density increased slightly during a 20-year period. Frost penetration measurements made during the 1978-79 winter on a 1,5-thick reservoir lining, on three earth dams under construction, and on the Teton Dam remnant are shown along with associated soil conditions, air freezing indexes, and insulating effects of snow and, for one dam, a loose soil cover.

Freezing of Water Droplet due to Evaporation

NASA Astrophysics Data System (ADS)

Satoh, Isao; Fushinobu, Kazuyoshi; Hashimoto, Yu

In this study, the feasibility of cooling/freezing of phase change.. materials(PCMs) due to evaporation for cold storage systems was experimentally examined. A pure water was used as the test PCM, since the latent heat due to evaporation of water is about 7 times larger than that due to freezing. A water droplet, the diameter of which was 1-4 mm, was suspended in a test cell by a fine metal wire (O. D.= 100μm),and the cell was suddenly evacuated up to the pressure lower than the triple-point pressure of water, so as to enhance the evaporation from the water surface. Temperature of the droplet was measured by a thermocouple, and the cooling/freezing behavior and the temperature profile of the droplet surface were captured by using a video camera and an IR thermo-camera, respectively. The obtained results showed that the water droplet in the evacuated cell is effectively cooled by the evaporation of water itself, and is frozen within a few seconds through remarkable supercooling state. When the initial temperature of the droplet is slightly higher than the room temperature, boiling phenomena occur in the droplet simultaneously with the freezing due to evaporation. Under such conditions, it was shown that the degree of supercooling of the droplet is reduced by the bubbles generated in the droplet.

Thermotropic phase transition in an adsorbed melissic acid film at the n-hexane-water interface

NASA Astrophysics Data System (ADS)

Tikhonov, A. M.

2017-06-01

A reversible thermotropic phase transition in an adsorption melissic acid film at the interface between n-hexane and an aqueous solution of potassium hydroxide (pH ≈ 10) is investigated by X-ray reflectometry and diffuse scattering using synchrotron radiation. The experimental data indicate that the interface "freezing" transition is accompanied not only by the crystallization of the Gibbs monolayer but also by the formation of a planar smectic structure in the 300-Å-thick adsorption film; this structure is formed by 50-Å-thick layers.

Low temperature self-cleaning properties of superhydrophobic surfaces

NASA Astrophysics Data System (ADS)

Wang, Fajun; Shen, Taohua; Li, Changquan; Li, Wen; Yan, Guilong

2014-10-01

Outdoor surfaces are usually dirty surfaces. Ice accretion on outdoor surfaces could lead to serious accidents. In the present work, the superhydrophobic surface based on 1H, 1H, 2H, 2H-Perfluorodecanethiol (PFDT) modified Ag/PDMS composite was prepared to investigate the anti-icing property and self-cleaning property at temperatures below freezing point. The superhydrophobic surface was deliberately polluted with activated carbon before testing. It was observed that water droplet picked up dusts on the cold superhydrophobic surface and took it away without freezing at a measuring temperature of -10 °C. While on a smooth PFDT surface and a rough surface base on Ag/PDMS composite without PFDT modification, water droplets accumulated and then froze quickly at the same temperature. However, at even lower temperature of -12 °C, the superhydrophobic surface could not prevent the surface water from icing. In addition, it was observed that the frost layer condensed from the moisture pay an important role in determining the low temperature self-cleaning properties of a superhydrophobic surface.

Experimental analysis and modeling of ultrasound assisted freezing of potato spheres.

PubMed

Kiani, Hossein; Zhang, Zhihang; Sun, Da-Wen

2015-09-01

In recent years, innovative methods such as ultrasound assisted freezing have been developed in order to improve the freezing process. During freezing of foods, accurate prediction of the temperature distribution, phase ratios, and process time is very important. In the present study, ultrasound assisted immersion freezing process (in 1:1 ethylene glycol-water solution at 253.15K) of potato spheres (0.02 m diameter) was evaluated using experimental, numerical and analytical approaches. Ultrasound (25 kHz, 890 W m(-2)) was irradiated for different duty cycles (DCs=0-100%). A finite volume based enthalpy method was used in the numerical model, based on which temperature and liquid fraction profiles were simulated by a program developed using OpenFOAM® CFD software. An analytical technique was also employed to calculate freezing times. The results showed that ultrasound irradiation could decrease the characteristic freezing time of potatoes. Since ultrasound irradiation increased the heat transfer coefficient but simultaneously generated heat at the surface of the samples, an optimum DC was needed for the shortest freezing time which occurred in the range of 30-70% DC. DCs higher than 70% increased the freezing time. DCs lower than 30% did not provide significant effects on the freezing time compared to the control sample. The numerical model predicted the characteristic freezing time in accordance with the experimental results. In addition, analytical calculation of characteristic freezing time exhibited qualitative agreement with the experimental results. As the numerical simulations provided profiles of temperature and water fraction within potatoes frozen with or without ultrasound, the models can be used to study and control different operation situations, and to improve the understanding of the freezing process. Copyright © 2015 Elsevier B.V. All rights reserved.

Ambient temperature enhanced freezing tolerance of Chrysanthemum dichrum CdICE1 Arabidopsis via miR398.

PubMed

Chen, Yu; Jiang, Jiafu; Song, Aiping; Chen, Sumei; Shan, Hong; Luo, Huolin; Gu, Chunsun; Sun, Jing; Zhu, Lu; Fang, Weimin; Chen, Fadi

2013-12-19

ICE (Inducer of CBF Expression) family genes play an important role in the regulation of cold tolerance pathways. In an earlier study, we isolated the gene CdICE1 from Chrysanthemum dichrum and demonstrated that freezing tolerance was enhanced by CdICE1 overexpression. Therefore, we sought to determine the mechanism by which ICE1 family genes participate in freezing tolerance. Using EMSA (Electrophoretic Mobility Shift Assay) and yeast one-hybrid assays, we confirmed that CdICE1 binds specifically to the MYC element in the CdDREBa promoter and activates transcription. In addition, overexpression of CdICE1 enhanced Arabidopsis freezing tolerance after transition from 23°C to 4°C or 16°C. We found that after acclimation to 4°C, CdICE1, like Arabidopsis AtICE1, promoted expression of CBFs (CRT/DRE Binding Factor) and their genes downstream involved in freezing tolerance, including COR15a (Cold-Regulated 15a), COR6.6, and RD29a (Responsive to Dessication 29a). Interestingly, we observed that CdICE1-overexpressing plants experienced significant reduction in miR398. In addition, its target genes CSD1 (Copper/zinc Superoxide Dismutase 1) and CSD2 showed inducible expression under acclimation at 16°C, indicating that the miR398-CSD pathway was involved in the induction of freezing tolerance. Our data indicate that CdICE1-mediated freezing tolerance occurs via different pathways, involving either CBF or miR398, under acclimation at two different temperatures.

Ambient temperature enhanced freezing tolerance of Chrysanthemum dichrum CdICE1 Arabidopsis via miR398

PubMed Central

2013-01-01

Background ICE (Inducer of CBF Expression) family genes play an important role in the regulation of cold tolerance pathways. In an earlier study, we isolated the gene CdICE1 from Chrysanthemum dichrum and demonstrated that freezing tolerance was enhanced by CdICE1 overexpression. Therefore, we sought to determine the mechanism by which ICE1 family genes participate in freezing tolerance. Results Using EMSA (Electrophoretic Mobility Shift Assay) and yeast one-hybrid assays, we confirmed that CdICE1 binds specifically to the MYC element in the CdDREBa promoter and activates transcription. In addition, overexpression of CdICE1 enhanced Arabidopsis freezing tolerance after transition from 23°C to 4°C or 16°C. We found that after acclimation to 4°C, CdICE1, like Arabidopsis AtICE1, promoted expression of CBFs (CRT/DRE Binding Factor) and their genes downstream involved in freezing tolerance, including COR15a (Cold-Regulated 15a), COR6.6, and RD29a (Responsive to Dessication 29a). Interestingly, we observed that CdICE1-overexpressing plants experienced significant reduction in miR398. In addition, its target genes CSD1 (Copper/zinc Superoxide Dismutase 1) and CSD2 showed inducible expression under acclimation at 16°C, indicating that the miR398-CSD pathway was involved in the induction of freezing tolerance. Conclusions Our data indicate that CdICE1-mediated freezing tolerance occurs via different pathways, involving either CBF or miR398, under acclimation at two different temperatures. PMID:24350981

The ins and outs of water dynamics in cold tolerant soil invertebrates.

PubMed

Holmstrup, Martin

2014-10-01

Many soil invertebrates have physiological characteristics in common with freshwater animals and represent an evolutionary transition from aquatic to terrestrial life forms. Their high cuticular permeability and ability to tolerate large modifications of internal osmolality are of particular importance for their cold tolerance. A number of cold region species that spend some or most of their life-time in soil are in more or less intimate contact with soil ice during overwintering. Unless such species have effective barriers against cuticular water-transport, they have only two options for survival: tolerate internal freezing or dehydrate. The risk of internal ice formation may be substantial due to inoculative freezing and many species rely on freeze-tolerance for overwintering. If freezing does not occur, the desiccating power of external ice will cause the animal to dehydrate until vapor pressure equilibrium between body fluids and external ice has been reached. This cold tolerance mechanism is termed cryoprotective dehydration (CPD) and requires that the animal must be able to tolerate substantial dehydration. Even though CPD is essentially a freeze-avoidance strategy the associated physiological traits are more or less the same as those found in freeze tolerant species. The most well-known are accumulation of compatible osmolytes and molecular chaperones reducing or protecting against the stress caused by cellular dehydration. Environmental moisture levels of the habitat are important for which type of cold tolerance is employed, not only in an evolutionary context, but also within a single population. Some species use CPD under relatively dry conditions, but freeze tolerance when soil moisture is high. Copyright © 2014 Elsevier Ltd. All rights reserved.

Supramolecular "Big Bang" in a Single-Ionic Surfactant/Water System Driven by Electrostatic Repulsion: From Vesicles to Micelles.

PubMed

Leclercq, Loïc; Bauduin, Pierre; Nardello-Rataj, Véronique

2017-04-11

In aqueous solution, dimethyldi-n-octylammonium chloride, [DiC 8 ][Cl], spontaneously forms dimers at low concentrations (1-10 mM) to decrease the strength of the hydrophobic-water contact. Dimers represent ideal building blocks for the abrupt edification of vesicles at 10 mM. These vesicles are fully characterized by dynamic and static light scattering, self-diffusion nuclear magnetic resonance, and freeze-fracture transmission electron microscopy. An increase in concentration leads to electrostatic repulsion between vesicles that explode into small micelles at 30 mM. These transitions are detected by means of surface tension, conductivity, and solubility of hydrophobic solutes as well as by isothermal titration microcalorimetry. These unusual supramolecular transitions emerge from the surfactant chemical structure that combines two contradictory features: (i) the double-chain structure tending to form low planar aggregates with low water solubility and (ii) the relatively short chains giving high hydrophilicity. The well-balanced hydrophilic-hydrophobic character of [DiC 8 ][Cl] is then believed to be at the origin of the unusual supramolecular sequence offering new opportunities for drug delivery systems.

Calorimetric analysis of cryopreservation and freeze-drying formulations.

PubMed

Sun, Wendell Q

2015-01-01

Differential scanning calorimetry (DSC) is a commonly used thermal analysis technique in cryopreservation and freeze-drying research. It has been used to investigate crystallization, eutectic formation, glass transition, devitrification, recrystallization, melting, polymorphism, molecular relaxation, phase separation, water transport, thermochemistry, and kinetics of complex reactions (e.g., protein denaturation). Such information can be used for the optimization of protective formulations and process protocols. This chapter gives an introduction to beginners who are less familiar with this technique. It covers the instrument and its basic principles, followed by a discussion of the methods as well as examples of specific applications.

Why does radar reflectivity tend to increase downward toward the ocean surface, but decrease downward toward the land surface?

NASA Astrophysics Data System (ADS)

Liu, Chuntao; Zipser, Edward J.

2013-01-01

Both ground and space borne radars have shown that radar reflectivity profiles below the freezing level have different slopes over land and ocean in general. This is critical in correctly estimating the surface precipitation rate in the usual situation in which the radar reflectivity cannot be measured as close to the surface as one would like. Using 14 years of Tropical Rainfall Measuring Mission precipitation radar observations, the variations of slopes of the radar reflectivity in the low troposphere are examined over the stratiform and convective precipitation regions. Radar reflectivity below the freezing level usually decreases toward the surface over land, but increases toward the surface over the ocean. Increasing reflectivity toward the surface is hypothesized to occur mainly when raindrops grow while falling through low clouds, which is favored by high humidity at low levels, and by updraft speeds lower than the fall speed of raindrops, both more likely over oceans. Other things being equal, proxy evidence is presented that the more intense the convection, the more likely reflectivity is to decrease toward the surface, and that this is at least as important as low-level relative humidity. Over monsoon regions with more moderate convection but higher humidity, such as southeast China and the Amazon, there are more profiles with reflectivity increasing toward the surface than over other continental regions such as Africa. Radar reflectivity tends to increase toward the surface in shallow warm rain systems in trade cumulus regions, but tends to decrease toward the surface when high reflectivity values are present at or above the freezing level.

Wetlands: Crop freezes and land-use change in Florida

USGS Publications Warehouse

Marshall, C.H.; Pielke, R.A.; Steyaert, L.T.

2003-01-01

South Florida experienced a significant change in land usage during the twentieth century, including the conversion of natural wetlands into agricultural land for the cultivation of winter vegetable, sugar cane and citrus crops. This movement of agriculture from more northerly areas was intended partly to escape the risk of damaging winter freezes. Here we present evidence from a case study using a coupled atmosphere and land-surface computer-modelling system that suggests that the draining of wetlands may have inadvertently increased the frequency and severity of agriculturally damaging freezes in the south of Florida.

Freezing Temperatures, Ice Nanotubes Structures, and Proton Ordering of TIP4P/ICE Water inside Single Wall Carbon Nanotubes.

PubMed

Pugliese, P; Conde, M M; Rovere, M; Gallo, P

2017-11-16

A very recent experimental paper importantly and unexpectedly showed that water in carbon nanotubes is already in the solid ordered phase at the temperature where bulk water boils. The water models used so far in literature for molecular dynamics simulations in carbon nanotubes show freezing temperatures lower than the experiments. We present here results from molecular dynamics simulations of water inside single walled carbon nanotubes using an extremely realistic model for both liquid and icy water, the TIP4P/ICE. The water behavior inside nanotubes of different diameters has been studied upon cooling along the isobars at ambient pressure starting from temperatures where water is in a liquid state. We studied the liquid/solid transition, and we observed freezing temperatures higher than in bulk water and that depend on the diameter of the nanotube. The maximum freezing temperature found is 390 K, which is in remarkable agreement with the recent experimental measurements. We have also analyzed the ice structure called "ice nanotube" that water forms inside the single walled carbon nanotubes when it freezes. The ice forms observed are in agreement with previous results obtained with different water models. A novel finding, a partial proton ordering, is evidenced in our ice nanotubes at finite temperature.

Simulation studies of glassy nanoclusters

NASA Astrophysics Data System (ADS)

Bowles, Richard

2015-03-01

Glassy materials are amorphous solids usually formed by rapidly cooling a liquid below its equilibrium freezing temperature, trapping the particles in a liquid-like structure at the glass transition temperature. While appearing throughout nature and industry, these systems continue to challenge the way we think about the dynamics and thermodynamics of condensed matter and a fundamental understanding of the glass state remains elusive. This talk describes molecular simulation studies of glassy behaviour in binary Lennard-Jones nanoclusters. We show that the relaxation dynamics of the clusters is nonuniform and the core of the cluster goes through a glass transition at higher temperatures than at the surface. As the nanoclusters are cooled, they also exhibit a fragile-strong crossover in their dynamics and we explore how this phenomena is linked to the potential energy landscape of the clusters. Finally, we compare the properties of nanoclusters formed through vapour condensation, directly to the glassy state, with those of glassy clusters formed through traditional supercooling. The condensation clusters are shown to form ultra-stable glassy states analogous to the ultra-stable glasses formed by thin film vapour deposition onto a cold substrate. In all, our work suggests that nanoscale clusters exhibit some unique glassy features, while also offering potential insights into the fundamental nature of the glass transition.

Stabilization of tetanus toxoid formulation containing aluminium hydroxide adjuvant against freeze-thawing.

PubMed

Solanki, Vipul A; Jain, Nishant K; Roy, Ipsita

2011-07-29

Exposure to subzero temperature leads to loss of vaccine potency. This can happen due to degradation of adjuvant surface and/or inactivation of the antigen. When adsorbed on aluminium hydroxide and subjected to freeze-thawing, tetanus toxoid was desorbed from the gel matrix and the preparation was found to lose its antigenicity. Analyses showed that the gel particles were denatured after freezing. When freeze-thawing was carried out in the presence of glucose, sorbitol and arginine, the degradation of gel particles was inhibited. A higher fraction of the protein could be retained on the gel. However, the antigenicity of these preparations was quite low. In the presence of trehalose, the protein could be partially retained on aluminium hydroxide. Being a cryoprotectant, trehalose was also able to inhibit the freezing-induced denaturation of tetanus toxoid, which resulted in retention of antigenicity of the adjuvanted toxoid. Copyright © 2011 Elsevier B.V. All rights reserved.

Microphysical Modelling of the 1999-2000 Arctic Winter. 3; Impact of Homogeneous Freezing on PSCs

NASA Technical Reports Server (NTRS)

Drdla, K.

2003-01-01

Simulations of the 1999-2000 winter have tested the effect on polar stratospheric clouds (PSCs) of the homogeneous freezing of liquid ternary solutions into nitric acid trihydrate (NAT) and nitric acid dihydrate (NAD). Proposed laboratory-derived volume-based and surface-based homogeneous freezing rates have both been examined, including different assumptions about the extrapolation of laboratory measurements to atmospheric conditions. Widespread PSC formation and denitrification are possible in several of the scenarios examined. However, the simulations are all unable to explain the solid-phase PSCs observed early in the 1999-2000 winter, and are unable to reproduce the measured extent of vortex denitrification. These problems can both be attributed to the relatively cold temperatures, more than 5 K below the NAT condensation point, necessary for effective homogeneous freezing. Therefore synoptic-scale homogeneous freezing appears unlikely to be the primary mechanism responsible for solid-phase PSC formation.

Effect of food additives on egg yolk gelation induced by freezing.

PubMed

Primacella, Monica; Fei, Tao; Acevedo, Nuria; Wang, Tong

2018-10-15

This study demonstrates technological advances in preventing yolk gelation during freezing and thawing. Gelation negatively affects yolk functionality in food formulation. Preventing gelation using 10% salt or sugar limits the application of the yolk. Novel food additives were tested to prevent gelation induced by freezing. Significant reduction (p < 0.05) in gel hardness of frozen-thawed yolk (45 h freezing at -20 °C) indicates that hydrolyzed carboxymethyl cellulose (HCMC), proline, and hydrolyzed egg white and yolk (HEW and HEY) are effective gelation inhibitors. The mechanisms in which these additives prevented gelation were further studied through measuring the changes in the amount of freezable water, lipoprotein particle size, and protein surface hydrophobicity. Overall, this study provides several alternatives of gelation inhibitor that have great potentials in replacing the use of salt or sugar in commercial operation of freezing egg yolk for shelf-life extension. Copyright © 2018 Elsevier Ltd. All rights reserved.

Evaluation of spin freezing versus conventional freezing as part of a continuous pharmaceutical freeze-drying concept for unit doses.

PubMed

De Meyer, L; Van Bockstal, P-J; Corver, J; Vervaet, C; Remon, J P; De Beer, T

2015-12-30

Spin-freezing as alternative freezing approach was evaluated as part of an innovative continuous pharmaceutical freeze-drying concept for unit doses. The aim of this paper was to compare the sublimation rate of spin-frozen vials versus traditionally frozen vials in a batch freeze-dryer, and its impact on total drying time. Five different formulations, each having a different dry cake resistance, were tested. After freezing, the traditionally frozen vials were placed on the shelves while the spin-frozen vials were placed in aluminum vial holders providing radial energy supply during drying. Different primary drying conditions and chamber pressures were evaluated. After 2h of primary drying, the amount of sublimed ice was determined in each vial. Each formulation was monitored in-line using NIR spectroscopy during drying to determine the sublimation endpoint and the influence of drying conditions upon total drying time. For all tested formulations and applied freeze-drying conditions, there was a significant higher sublimation rate in the spin-frozen vials. This can be explained by the larger product surface and the lower importance of product resistance because of the much thinner product layers in the spin frozen vials. The in-line NIR measurements allowed evaluating the influence of applied drying conditions on the drying trajectories. Copyright © 2015 Elsevier B.V. All rights reserved.

The observation of the physicochemical change of rock under freeze-thawing experiment: CLSM, XRD and ICP analysis

NASA Astrophysics Data System (ADS)

Choi, J.; Chae, B.; Chon, C.; Jeong, J.

2013-12-01

Abstract : In order to understand the progress of the physical weathering of rock sample, we managed freeze-thawing experiment at temperature of up to 40C from -20C taking into account of South Korea. In this study, the time was held by two hours the temperature of the maximum (40C) and minimum (-20C) and the experiments were carried out at intervals of one hour rising and falling. We have run the experiment about 120 cycle with the cycle of -20C from 40C experiment. We measured the physical properties of rock samples after each 20 cycle has elapsed by using confocal laser scanning microscope (CLSM) and observed changes in roughness of rock samples surface. We also analyzed the mineral of rock sample using the XRD analysis and observing the change in chemical composition of solution used in the experiment by using ICP analysis. Through the above process, we observed physico-chemical changes in the rock sample due to freeze-thaw cycles. To analysis of the line roughness parameter we used set by the 10 vertical and horizontal cross section line on the surface and surface roughness parameter was analyzed by using the area on the surface. Through such a process, while the freeze-thawing experiment is advanced, it was studied how the physical roughness and chemical composition were changed. As a result, it was possible to observe a change in the mineral component of the particular dissolved in the solution and it was able to observe the characteristic changes of the parameters of the roughness of the lines and surfaces.

Monitoring of Freezing Dynamics in Trees: A Simple Phase Shift Causes Complexity1[OPEN

PubMed Central

Charra-Vaskou, Katline

2017-01-01

During winter, trees have to cope with harsh conditions, including extreme freeze-thaw stress. This study focused on ice nucleation and propagation, related water shifts and xylem cavitation, as well as cell damage and was based on in situ monitoring of xylem (thermocouples) and surface temperatures (infrared imaging), ultrasonic emissions, and dendrometer analysis. Field experiments during late winter on Picea abies growing at the alpine timberline revealed three distinct freezing patterns: (1) from the top of the tree toward the base, (2) from thin branches toward the main stem’s top and base, and (3) from the base toward the top. Infrared imaging showed freezing within branches from their base toward distal parts. Such complex freezing causes dynamic and heterogenous patterns in water potential and probably in cavitation. This study highlights the interaction between environmental conditions upon freezing and thawing and demonstrates the enormous complexity of freezing processes in trees. Diameter shrinkage, which indicated water fluxes within the stem, and acoustic emission analysis, which indicated cavitation events near the ice front upon freezing, were both related to minimum temperature and, upon thawing, related to vapor pressure deficit and soil temperature. These complex patterns, emphasizing the common mechanisms between frost and drought stress, shed new light on winter tree physiology. PMID:28242655

NASA Soil Moisture Active Passive Mission Status and Science Highlights

NASA Technical Reports Server (NTRS)

Yueh, Simon; Entekhabi, Dara; O'Neill, Peggy; Entin, Jared

2017-01-01

The Soil Moisture Active Passive (SMAP) observatory was launched January 31, 2015, and its L-band radiometer and radar instruments became operational during April 2015. This paper provides a summary of the quality assessment of its baseline soil moisture and freeze/thaw products as well as an overview of new products. The first new product explores the Backus Gilbert optimum interpolation based on the oversampling characteristics of the SMAP radiometer. The second one investigates the disaggregation of the SMAP radiometer data using the European Space Agency's Sentinel-1 C-band synthetic aperture radar (SAR) data to obtain soil moisture products at about 1 to 3 km resolution. In addition, SMAPs L-band data have been found useful for many scientific applications, including depictions of water cycles, vegetation opacity, ocean surface salinity and hurricane ocean surface wind mapping. Highlights of these new applications will be provided.The SMAP soil moisture, freeze/taw state and SSSprovide a synergistic view of water cycle. For example, Fig.7 illustrates the transition of freeze/thaw state, change of soilmoisture near the pole and SSS in the Arctic Ocean fromApril to October in 2015 and 2016. In April, most parts ofAlaska, Canada, and Siberia remained frozen. Melt onsetstarted in May. Alaska, Canada, and a big part of Siberia havebecome thawed at the end of May; some freshwater dischargecould be found near the mouth of Mackenzie in 2016, but notin 2015. The soil moisture appeared to be higher in the Oband Yenisei river basins in Siberia in 2015. As a result,freshwater discharge was more widespread in the Kara Seanear the mouths of both rivers in June 2015 than in 2016. TheNorth America and Siberia have become completely thawedin July. After June, the freshwater discharge from other riversinto the Arctic, indicated by blue, also became visible. Thefreeze-up started in September and the high latitude regionsin North America and Eurasia became frozen. Comparing thespread of freshwater in August 2015 and 2016 suggests thatthere was more discharge from Ob and Yenisei in 2015,which appeared to correspond to a higher soil moisturecontent in the Ob and Yenisei basins. In contrast, Mackenzieappeared to have more discharge in September 2016.

Freezing tolerance of conifer seeds and germinants.

PubMed

Hawkins, B J; Guest, H J; Kolotelo, D

2003-12-01

Survival after freezing was measured for seeds and germinants of four seedlots each of interior spruce (Picea glauca x engelmannii complex), lodgepole pine (Pinus contorta Dougl. ex Loud.), Douglas-fir (Pseudotsuga menziesii (Mirb.) Franco) and western red cedar (Thuja plicata Donn ex D. Donn). Effects of eight seed treatments on post-freezing survival of seeds and germinants were tested: dry, imbibed and stratified seed, and seed placed in a growth chamber for 2, 5, 10, 15, 20 or 30 days in a 16-h photoperiod and a 22/17 degrees C thermoperiod. Survival was related to the water content of seeds and germinants, germination rate and seedlot origin. After freezing for 3 h at -196 degrees C, dry seed of most seedlots of interior spruce, Douglas-fir and western red cedar had 84-96% germination, whereas lodgepole pine seedlots had 53-82% germination. Freezing tolerance declined significantly after imbibition in lodgepole pine, Douglas-fir and interior spruce seed (western red cedar was not tested), and mean LT50 of imbibed seed of these species was -30, -24.5 and -20 degrees C, respectively. Freezing tolerance continued to decline to a minimum LT50 of -4 to -7 degrees C after 10 days in a growth chamber for interior spruce, Douglas-fir and lodgepole pine, or after 15 days for western red cedar. Minimum freezing tolerance was reached at the stage of rapid hypocotyl elongation. In all species, a slight increase in freezing tolerance of germinants was observed once cotyledons emerged from the seed coat. The decrease in freezing tolerance during the transition from dry to germinating seed correlated with increases in seed water content. Changes in freezing tolerance between 10 and 30 days in the growth chamber were not correlated with seedling water content. Within a species, seedlots differed significantly in freezing tolerance after 2 or 5 days in the growth chamber. Because all seedlots of interior spruce and lodgepole pine germinated quickly, there was no correlation between seedlot hardiness and rate of germination. Germination rate and freezing tolerance of Douglas-fir and western red cedar seedlots was negatively correlated. There was a significant correlation between LT50 after 10 days in the growth chamber and minimum spring temperature at the location of seedlot origin for interior spruce and three seedlots of western red cedar, but no relationship was apparent for lodgepole pine and Douglas-fir.

Structure and collective dynamics of hydrated anti-freeze protein type III from 180 K to 298 K by X-ray diffraction and inelastic X-ray scattering

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yoshida, Koji; Baron, Alfred Q. R.; Uchiyama, Hiroshi

We investigated hydrated antifreeze protein type III (AFP III) powder with a hydration level h (=mass of water/mass of protein) of 0.4 in the temperature range between 180 K and 298 K using X-ray diffraction and inelastic X-ray scattering (IXS). The X-ray diffraction data showed smooth, largely monotonic changes between 180 K and 298 K without freezing water. Meanwhile, the collective dynamics observed by IXS showed a strong change in the sound velocity at 180 K, after being largely temperature independent at higher temperatures (298–220 K). We interpret this change in terms of the dynamic transition previously discussed using othermore » probes including THz IR absorption spectroscopy and incoherent elastic and quasi-elastic neutron scattering. This finding suggests that the dynamic transition of hydrated proteins is observable on the subpicosecond time scale as well as nano- and pico-second scales, both in collective dynamics from IXS and single particle dynamics from neutron scattering. Moreover, it is most likely that the dynamic transition of hydrated AFP III is not directly correlated with its hydration structure.« less

Structure and collective dynamics of hydrated anti-freeze protein type III from 180 K to 298 K by X-ray diffraction and inelastic X-ray scattering

NASA Astrophysics Data System (ADS)

Yoshida, Koji; Baron, Alfred Q. R.; Uchiyama, Hiroshi; Tsutsui, Satoshi; Yamaguchi, Toshio

2016-04-01

We investigated hydrated antifreeze protein type III (AFP III) powder with a hydration level h (=mass of water/mass of protein) of 0.4 in the temperature range between 180 K and 298 K using X-ray diffraction and inelastic X-ray scattering (IXS). The X-ray diffraction data showed smooth, largely monotonic changes between 180 K and 298 K without freezing water. Meanwhile, the collective dynamics observed by IXS showed a strong change in the sound velocity at 180 K, after being largely temperature independent at higher temperatures (298-220 K). We interpret this change in terms of the dynamic transition previously discussed using other probes including THz IR absorption spectroscopy and incoherent elastic and quasi-elastic neutron scattering. This finding suggests that the dynamic transition of hydrated proteins is observable on the subpicosecond time scale as well as nano- and pico-second scales, both in collective dynamics from IXS and single particle dynamics from neutron scattering. Moreover, it is most likely that the dynamic transition of hydrated AFP III is not directly correlated with its hydration structure.

Structure and collective dynamics of hydrated anti-freeze protein type III from 180 K to 298 K by X-ray diffraction and inelastic X-ray scattering.

PubMed

Yoshida, Koji; Baron, Alfred Q R; Uchiyama, Hiroshi; Tsutsui, Satoshi; Yamaguchi, Toshio

2016-04-07

We investigated hydrated antifreeze protein type III (AFP III) powder with a hydration level h (=mass of water/mass of protein) of 0.4 in the temperature range between 180 K and 298 K using X-ray diffraction and inelastic X-ray scattering (IXS). The X-ray diffraction data showed smooth, largely monotonic changes between 180 K and 298 K without freezing water. Meanwhile, the collective dynamics observed by IXS showed a strong change in the sound velocity at 180 K, after being largely temperature independent at higher temperatures (298-220 K). We interpret this change in terms of the dynamic transition previously discussed using other probes including THz IR absorption spectroscopy and incoherent elastic and quasi-elastic neutron scattering. This finding suggests that the dynamic transition of hydrated proteins is observable on the subpicosecond time scale as well as nano- and pico-second scales, both in collective dynamics from IXS and single particle dynamics from neutron scattering. Moreover, it is most likely that the dynamic transition of hydrated AFP III is not directly correlated with its hydration structure.

Low-temperature magnetic properties of Heusler compounds Ru2-xFexCrSi (x=0.1,0.3,and0.5)

NASA Astrophysics Data System (ADS)

Ito, Masakazu; Hisamatsu, Toru; Rokkaku, Tsugumi; Shigeta, Iduru; Manaka, Hirotaka; Terada, Norio; Hiroi, Masahiko

2010-07-01

We carried out magnetization M(T) and specific-heat CP(T) measurements of the new Heusler compounds Ru2-xFexCrSi (x=0.1,0.3,and0.5) , which exhibit spin-glass freezing. M(T) has peak- and irreversibility-type anomalies. The temperatures at which these anomalies appear have magnetic field dependence described by the Gabay-Toulouse and de Almeida-Thouless lines in the low-field range. For the magnetic specific heat Cm(T) , we did not observe a discontinuity indicating long-range magnetic phase transition but a broad hump characteristic of spin-glass freezing. Cm(T) in the low-temperature range is described as a combination of linear- and quadratic- T terms. The quadratic- T dependence of Cm(T) is probably associated with excitation of the Ising component of the freezing spins.

Persistent free radical ESR signals in marine bivalve tissues

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mehlorn, R.J.; Mendez, A.T.; Higashi, R.

1992-08-01

Freeze-dried homogenates of the oyster Crassostrea rhizophorae collected from waters in Puerto Rico near urban and industrial sites as well as at relatively pristine locations yielded electron spin resonance (ESR) spectra characteristic of free radicals as well as spectral components of transition metal ions, dominated by manganese. The magnitudes of these ESR signals and the concentrations of trace elements (determined by X-ray fluorescence) varied considerably among oyster samples, masking any potential correlation with polluted waters. Laboratory studies were initiated to identify the factors controlling the magnitudes of the tissue free radical ESR signals. Another mollusc, Mytilus californianus collected at themore » Bodega Marine laboratory in northern California, was fractionated into goneds and remaining tissue. Freeze-dried homogenates of both fractions exhibited ESR signals that increased gradually with time. ESR signals were observed in freeze-dried perchloric acid (PCA) precipitates of the homogenates, delipidated PCA precipitates, and in chloroform extracts of these precipitates. Acid hydrolysis to degrade proteins to amino acids produced a residue, which yielded much larger ESR free radical signals after freeze-drying. Freshly thawed homogenates of Crassostrea rhizophorae also exhibited ESR signals. A laboratory model of copper stress in Crassostrea rhizophorae was developed to study the effect of this transition metal on dssue free radicals. Preliminary results suggested that sublethal copper exposure had little effect on tissue fire radicals, except possibly for a signal enhancement in an oyster fraction that was enriched in kidney granules. Since kidney granules are known to accumulate heavy metals in mussels and probably other marine bivalves, this signal enhancement may prove to be an indicator of free radical processes associated with heavy metal deposition in molluscs.« less

Persistent free radical ESR signals in marine bivalve tissues. [Electron Spin Resonance (ESR)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mehlorn, R.J.; Mendez, A.T.; Higashi, R.

1992-08-01

Freeze-dried homogenates of the oyster Crassostrea rhizophorae collected from waters in Puerto Rico near urban and industrial sites as well as at relatively pristine locations yielded electron spin resonance (ESR) spectra characteristic of free radicals as well as spectral components of transition metal ions, dominated by manganese. The magnitudes of these ESR signals and the concentrations of trace elements (determined by X-ray fluorescence) varied considerably among oyster samples, masking any potential correlation with polluted waters. Laboratory studies were initiated to identify the factors controlling the magnitudes of the tissue free radical ESR signals. Another mollusc, Mytilus californianus collected at themore » Bodega Marine laboratory in northern California, was fractionated into goneds and remaining tissue. Freeze-dried homogenates of both fractions exhibited ESR signals that increased gradually with time. ESR signals were observed in freeze-dried perchloric acid (PCA) precipitates of the homogenates, delipidated PCA precipitates, and in chloroform extracts of these precipitates. Acid hydrolysis to degrade proteins to amino acids produced a residue, which yielded much larger ESR free radical signals after freeze-drying. Freshly thawed homogenates of Crassostrea rhizophorae also exhibited ESR signals. A laboratory model of copper stress in Crassostrea rhizophorae was developed to study the effect of this transition metal on dssue free radicals. Preliminary results suggested that sublethal copper exposure had little effect on tissue fire radicals, except possibly for a signal enhancement in an oyster fraction that was enriched in kidney granules. Since kidney granules are known to accumulate heavy metals in mussels and probably other marine bivalves, this signal enhancement may prove to be an indicator of free radical processes associated with heavy metal deposition in molluscs.« less

47 CFR 73.616 - Post-transition DTV station interference protection.

Code of Federal Regulations, 2012 CFR

2012-10-01

... 28 dB or greater. At the edge of the noise-limited service area, where the signal-to-noise (S/N... 2004)) remained in effect. For a short period of time after the filing freeze is lifted, until a date...

47 CFR 73.616 - Post-transition DTV station interference protection.

Code of Federal Regulations, 2010 CFR

2010-10-01

... 28 dB or greater. At the edge of the noise-limited service area, where the signal-to-noise (S/N... 2004)) remained in effect. For a short period of time after the filing freeze is lifted, until a date...

47 CFR 73.616 - Post-transition DTV station interference protection.

Code of Federal Regulations, 2011 CFR

2011-10-01

... 28 dB or greater. At the edge of the noise-limited service area, where the signal-to-noise (S/N... 2004)) remained in effect. For a short period of time after the filing freeze is lifted, until a date...

Distinguishing magnetic blocking and surface spin-glass freezing in nickel ferrite nanoparticles

NASA Astrophysics Data System (ADS)

Nadeem, K.; Krenn, H.; Traussing, T.; Letofsky-Papst, I.

2011-01-01

Nickel ferrite nanoparticles dispersed in SiO2 matrix have been synthesized by sol-gel method. Structural analysis has been performed by using x-ray diffraction and transmission electron microscopy. Magnetic properties have been investigated by using superconducting quantum interference device magnetometry. In addition to the average blocking temperature peak at TB=120 K measured by a zero field cooled temperature scan of the dc susceptibility, an additional hump near 15 K is observed. Temperature dependent out-of-phase ac susceptibility shows the same features: one broad peak at high temperature and a second narrow peak at low temperature. The high temperature peak corresponds to magnetic blocking of individual nanoparticles, while the low temperature peak is attributed to surface spin-glass freezing which becomes dominant for decreasing particle diameter. To prove the dynamics of the spin (dis)order in both regimes of freezing and blocking, the frequency dependent ac susceptibility is investigated under a biasing dc field. The frequency shift in the "frozen" low-temperature ac susceptibility peak is fitted to a dynamic scaling law with a critical exponent zv=7.5, which indicates a spin-glass phase. Exchange bias is turned on at low temperature which signifies the existence of a strong core-shell interaction. Aging and memory effects are further unique fingerprints of a spin-glass freezing on the surface of isolated magnetic nanoparticles.

Simulations of Polar Stratospheric Clouds and Denitrification Using Laboratory Freezing Rates

NASA Technical Reports Server (NTRS)

Drdla, Katja; Tabazadeh, Azadeh; Gore, Warren J. (Technical Monitor)

2001-01-01

During the 1999-2000 Arctic winter, the SAGE (Stratospheric Aerosol and Gas Experiment) III Ozone Loss and Validation Experiment (SOLVE) provided evidence of widespread solid-phase polar stratospheric clouds (PSCs) accompanied by severe nitrification. Previous simulations have shown that a freezing process occurring at temperatures above the ice frost point is necessary to explain these observations. In this work, the nitric acid freezing rates measured by Salcedo et al. and discussed by Tabazadeh et al. have been examined. These freezing rates have been tested in winter-long microphysical simulations of the 1999-2000 Arctic vortex evolution in order to determine whether they can explain the observations. A range of cases have been explored, including whether the PSC particles are composed of nitric acid dihydrate or trihydrate, whether the freezing process is a bulk process or occurs only on the particle surfaces, and uncertainties in the derived freezing rates. Finally, the possibility that meteoritic debris enhances the freezing rate has also been examined. The results of these simulations have been compared with key PSC and denitrification measurements made by the SOLVE campaign. The cases that best reproduce the measurements will he highlighted, with a discussion of the implications for our understanding of PSCs.

Modelling Cryovolcanism Due to Subsurface Ocean Freezing on Pluto and Charon

NASA Astrophysics Data System (ADS)

Conrad, J. W.; Nimmo, F.; Singer, K. N.

2016-12-01

The New Horizons spacecraft identified various possible cryovolcanic features on the surfaces of both Pluto and Charon [1]. However, there are major differences between the cryovolcanism on Pluto and Charon. Pluto has two mound-flanked depressions which are possibly cryovolcanic [2], while Charon's putative cryovolcanism is more widespread within its smooth southern plains. If Pluto or Charon have (or had) subsurface oceans, slow refreezing of these oceans would lead to extensional surface tectonics [3,4] and pressurization of the ocean [5]. Sufficiently large pressurization can overcome the overburden pressure and cause an eruption. We applied thermal evolution models based on [3] to determine likely freezing scenarios. Eruptions on Charon are possible under most conditions, and occur after tens of kilometers of freezing of an ice shell initially 100 km thick. This would produce an areal extensional strain of 1%. The implied globally-averaged thickness of erupted material is a few hundred meters and the critical crack width for propagation through the entire ice shell [6] is about half a meter for all eruption scenarios. Eruptions on Pluto require probably unrealistic freezing scenarios, because of the larger body size and higher overburden pressure. We conclude that ocean freezing is a possible source of cryovolcanism on Charon and may explain the smooth plains in its southern hemisphere [1]. Pluto, on the other hand, requires more complex models to explain the putative cryovolcanic features on its surface. [1] Moore et al., Science 351 (2016): 1284-1293. [2] Singer et al., LPSC 47 (2016): 2276 [3] Robuchon and Nimmo, Icarus 216 (2011): 426-439. [4] Hammond et al., GRL 43 (2016). [5] Manga and Wang, GRL 34 (2007). [6] Porco et al., The Astronomical Journal 148 (2014): 45.

Cyclic phase change in a cylindrical thermal energy storage capsule

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hasan, M.; Mujumdar, A.S.; Weber, M.E.

1983-12-01

This paper is concerned with a practical melting/freezing problem in conjunction with the more realistic case of a cyclic phase change thermal energy storage device. In this model the phase change medium is encapsulated in long cylindrical tubes, the surface temperature of which is allowed to vary sinusoidally with time about the discrete freezing temperature. Initial temperature of the medium is assumed to be constant at a temperature above or below the freezing/melting temperature. Natural convection in the melt is assumed to be negligible and the variations in the depth of freezing and/or melting in each half cycle is ignored.more » Depending on the half-cycle parameters the problem is simplified to either freezing or melting. The governing one-dimensional heat diffusion equations for both phases are solved by the Finite Integral Transform techniques. The kernels for the transformation are the time-dependent eigen functions separately defined for each phases. This extended transform method can accomodate any time-dependent surface temperature variation. The application of the transform generated a series of coupled, nonlinear first order differential equations, which are solved by Runge Kutta-Verner fifth and sixth order method. Dimensionless solutions of temperature variations in both phases, fusion front position and the fraction solidified (or melted) are displayed graphically to aid in practical calculations. For the special case of a constant surface temperature, comparisons are made between the present results and the existing integral and purely numerical results. The results are found to compare favourably. Results for fractional solidification (or melting and interface position are also compared with the simple Conduction Shape Factor method, after allowing for the time-dependent boundary conditions. Once again the results agree reasonably well.« less

Habitable zone limits for dry planets.

PubMed

Abe, Yutaka; Abe-Ouchi, Ayako; Sleep, Norman H; Zahnle, Kevin J

2011-06-01

Most discussion of habitable planets has focused on Earth-like planets with globally abundant liquid water. For an "aqua planet" like Earth, the surface freezes if far from its sun, and the water vapor greenhouse effect runs away if too close. Here we show that "land planets" (desert worlds with limited surface water) have wider habitable zones than aqua planets. For planets at the inner edge of the habitable zone, a land planet has two advantages over an aqua planet: (i) the tropics can emit longwave radiation at rates above the traditional runaway limit because the air is unsaturated and (ii) the dry air creates a dry stratosphere that limits hydrogen escape. At the outer limits of the habitable zone, the land planet better resists global freezing because there is less water for clouds, snow, and ice. Here we describe a series of numerical experiments using a simple three-dimensional global climate model for Earth-sized planets. Other things (CO(2), rotation rate, surface pressure) unchanged, we found that liquid water remains stable at the poles of a low-obliquity land planet until net insolation exceeds 415 W/m(2) (170% that of modern Earth), compared to 330 W/m(2) (135%) for the aqua planet. At the outer limits, we found that a low-obliquity land planet freezes at 77%, while the aqua planet freezes at 90%. High-obliquity land and aqua planets freeze at 58% and 72%, respectively, with the poles offering the last refuge. We show that it is possible that, as the Sun brightens, an aqua planet like Earth can lose most of its hydrogen and become a land planet without first passing through a sterilizing runaway greenhouse. It is possible that Venus was a habitable land planet as recently as 1 billion years ago.

Metastable liquid-liquid transition in a molecular model of water

NASA Astrophysics Data System (ADS)

Palmer, Jeremy C.; Martelli, Fausto; Liu, Yang; Car, Roberto; Panagiotopoulos, Athanassios Z.; Debenedetti, Pablo G.

2014-06-01

Liquid water's isothermal compressibility and isobaric heat capacity, and the magnitude of its thermal expansion coefficient, increase sharply on cooling below the equilibrium freezing point. Many experimental, theoretical and computational studies have sought to understand the molecular origin and implications of this anomalous behaviour. Of the different theoretical scenarios put forward, one posits the existence of a first-order phase transition that involves two forms of liquid water and terminates at a critical point located at deeply supercooled conditions. Some experimental evidence is consistent with this hypothesis, but no definitive proof of a liquid-liquid transition in water has been obtained to date: rapid ice crystallization has so far prevented decisive measurements on deeply supercooled water, although this challenge has been overcome recently. Computer simulations are therefore crucial for exploring water's structure and behaviour in this regime, and have shown that some water models exhibit liquid-liquid transitions and others do not. However, recent work has argued that the liquid-liquid transition has been mistakenly interpreted, and is in fact a liquid-crystal transition in all atomistic models of water. Here we show, by studying the liquid-liquid transition in the ST2 model of water with the use of six advanced sampling methods to compute the free-energy surface, that two metastable liquid phases and a stable crystal phase exist at the same deeply supercooled thermodynamic condition, and that the transition between the two liquids satisfies the thermodynamic criteria of a first-order transition. We follow the rearrangement of water's coordination shell and topological ring structure along a thermodynamically reversible path from the low-density liquid to cubic ice. We also show that the system fluctuates freely between the two liquid phases rather than crystallizing. These findings provide unambiguous evidence for a liquid-liquid transition in the ST2 model of water, and point to the separation of time scales between crystallization and relaxation as being crucial for enabling it.

Metastable liquid-liquid transition in a molecular model of water.

PubMed

Palmer, Jeremy C; Martelli, Fausto; Liu, Yang; Car, Roberto; Panagiotopoulos, Athanassios Z; Debenedetti, Pablo G

2014-06-19

Liquid water's isothermal compressibility and isobaric heat capacity, and the magnitude of its thermal expansion coefficient, increase sharply on cooling below the equilibrium freezing point. Many experimental, theoretical and computational studies have sought to understand the molecular origin and implications of this anomalous behaviour. Of the different theoretical scenarios put forward, one posits the existence of a first-order phase transition that involves two forms of liquid water and terminates at a critical point located at deeply supercooled conditions. Some experimental evidence is consistent with this hypothesis, but no definitive proof of a liquid-liquid transition in water has been obtained to date: rapid ice crystallization has so far prevented decisive measurements on deeply supercooled water, although this challenge has been overcome recently. Computer simulations are therefore crucial for exploring water's structure and behaviour in this regime, and have shown that some water models exhibit liquid-liquid transitions and others do not. However, recent work has argued that the liquid-liquid transition has been mistakenly interpreted, and is in fact a liquid-crystal transition in all atomistic models of water. Here we show, by studying the liquid-liquid transition in the ST2 model of water with the use of six advanced sampling methods to compute the free-energy surface, that two metastable liquid phases and a stable crystal phase exist at the same deeply supercooled thermodynamic condition, and that the transition between the two liquids satisfies the thermodynamic criteria of a first-order transition. We follow the rearrangement of water's coordination shell and topological ring structure along a thermodynamically reversible path from the low-density liquid to cubic ice. We also show that the system fluctuates freely between the two liquid phases rather than crystallizing. These findings provide unambiguous evidence for a liquid-liquid transition in the ST2 model of water, and point to the separation of time scales between crystallization and relaxation as being crucial for enabling it.

Role of mono- and oligosaccharides from FOS as stabilizing agents during freeze-drying and storage of Lactobacillus delbrueckii subsp. bulgaricus.

PubMed

Romano, Nelson; Schebor, Carolina; Mobili, Pablo; Gómez-Zavaglia, Andrea

2016-12-01

The aim of this work was to assess the role of mono- and oligosaccharides present in fructo-oligosaccharides (FOS) mixtures as protective agents during freeze-drying and storage of Lactobacillus delbrueckii subsp. bulgaricus CIDCA 333. Different FOS mixtures were enzymatically obtained from sucrose and further purified by removing the monosaccharides produced as secondary products. Their glass transition temperatures (T g ) were determined at 11, 22 and 33% relative humidity (RH). Bacterial cultures were freeze-dried in the presence of 20% w/v solutions of the studied FOS. Their protective effect during freeze-drying was assessed by bacterial plate counting, and by determining the lag time from growth kinetics and the uptake of propidium iodide (PI). Plate counting during bacterial storage at 4°C, and 11, 22 and 33% RH for 80days completed this rational analysis of the protective effect of FOS. Purification of FOS led to an increase of T g in all the conditions assayed. Microorganisms freeze-dried in the presence of non-purified FOS were those with the shortest lag times. Bacteria freeze-dried with pure or commercial FOS (92% of total FOS) showed larger lag times (8.9-12.6h). The cultivability of microorganisms freeze-dried with non-purified FOS and with sucrose was not significantly different from that of bacteria before freeze-drying (8.74±0.14logCFU/mL). Pure or commercial FOS were less efficient in protecting bacteria during freeze-drying. All the protectants prevented membrane damage. The cultivability of bacteria freeze-dried with FOS decayed <1logarithmicunit after 80days of storage at 11% RH. When storing at 22 and 33% RH, pure and commercial FOS were those that best protected bacteria, and FOS containing monosaccharides were less efficient. The effect of FOS on bacterial protection is the result of a balance between monosaccharides, sucrose and larger FOS in the mixtures: the smallest sugars are more efficient in protecting lipid membranes, and the larger ones favor the formation of vitreous states. Copyright © 2016 Elsevier Ltd. All rights reserved.

Influence of freeze-thaw events on carbon dioxide emission from soils at different moisture and land use.

PubMed

Kurganova, Irina; Teepe, Robert; Loftfield, Norman

2007-02-19

The repeated freeze-thaw events during cold season, freezing of soils in autumn and thawing in spring are typical for the tundra, boreal, and temperate soils. The thawing of soils during winter-summer transitions induces the release of decomposable organic carbon and acceleration of soil respiration. The winter-spring fluxes of CO2 from permanently and seasonally frozen soils are essential part of annual carbon budget varying from 5 to 50%. The mechanisms of the freeze-thaw activation are not absolutely clear and need clarifying. We investigated the effect of repeated freezing-thawing events on CO2 emission from intact arable and forest soils (Luvisols, loamy silt; Central Germany) at different moisture (65% and 100% of WHC). Due to the measurement of the CO2 flux in two hours intervals, the dynamics of CO2 emission during freezing-thawing events was described in a detailed way. At +10 degrees C (initial level) in soils investigated, carbon dioxide emission varied between 7.4 to 43.8 mg C m-2h-1 depending on land use and moisture. CO2 flux from the totally frozen soil never reached zero and amounted to 5 to 20% of the initial level, indicating that microbial community was still active at -5 degrees C. Significant burst of CO2 emission (1.2-1.7-fold increase depending on moisture and land use) was observed during thawing. There was close linear correlation between CO2 emission and soil temperature (R2 = 0.86-0.97, P < 0.001). Our investigations showed that soil moisture and land use governed the initial rate of soil respiration, duration of freezing and thawing of soil, pattern of CO2 dynamics and extra CO2 fluxes. As a rule, the emissions of CO2 induced by freezing-thawing were more significant in dry soils and during the first freezing-thawing cycle (FTC). The acceleration of CO2 emission was caused by different processes: the liberation of nutrients upon the soil freezing, biological activity occurring in unfrozen water films, and respiration of cold-adapted microflora.

Recent tectonic activity on Pluto driven by phase changes in the ice shell

NASA Astrophysics Data System (ADS)

Hammond, Noah P.; Barr, Amy C.; Parmentier, Edgar M.

2016-07-01

The New Horizons spacecraft has found evidence for geologic activity on the surface of Pluto, including extensional tectonic deformation of its water ice bedrock see Moore et al. (2016). One mechanism that could drive extensional tectonic activity is global surface expansion due to the partial freezing of an ocean. We use updated physical properties for Pluto and simulate its thermal evolution to understand the survival of a possible subsurface ocean. For thermal conductivities of rock less than 3 W m-1 K-1, an ocean forms and at least partially freezes, leading to recent extensional stresses in the ice shell. In scenarios where the ocean freezes and the ice shell is thicker than 260 km, ice II forms and causes global volume contraction. Since there is no evidence for recent compressional tectonic features, we argue that ice II has not formed and that Pluto's ocean has likely survived to present day.

Induction of DREB2A pathway with repression of E2F, jasmonic acid biosynthetic and photosynthesis pathways in cold acclimation-specific freeze-resistant wheat crown.

PubMed

Karki, Amrit; Horvath, David P; Sutton, Fedora

2013-03-01

Winter wheat lines can achieve cold acclimation (development of tolerance to freezing temperatures) and vernalization (delay in transition from vegetative to reproductive phase) in response to low non-freezing temperatures. To describe cold-acclimation-specific processes and pathways, we utilized cold acclimation transcriptomic data from two lines varying in freeze survival but not vernalization. These lines, designated freeze-resistant (FR) and freeze-susceptible (FS), were the source of crown tissue RNA. Well-annotated differentially expressed genes (p ≤ 0.005 and fold change ≥ 2 in response to 4 weeks cold acclimation) were used for gene ontology and pathway analysis. "Abiotic stimuli" was identified as the most enriched and unique for FR. Unique to FS was "cytoplasmic components." Pathway analysis revealed the "triacylglycerol degradation" pathway as significantly downregulated and common to both FR and FS. The most enriched of FR pathways was "neighbors of DREB2A," with the highest positive median fold change. The "13-LOX and 13-HPL" and the "E2F" pathways were enriched in FR only with a negative median fold change. The "jasmonic acid biosynthesis" pathway and four "photosynthetic-associated" pathways were enriched in both FR and FS but with a more negative median fold change in FR than in FS. A pathway unique to FS was "binding partners of LHCA1," which was enriched only in FS with a significant negative median fold change. We propose that the DREB2A, E2F, jasmonic acid biosynthesis, and photosynthetic pathways are critical for discrimination between cold-acclimated lines varying in freeze survival.

Impact of heat treatment on the physical properties of noncrystalline multisolute systems concentrated in frozen aqueous solutions.

PubMed

Izutsu, Ken-ichi; Yomota, Chikako; Kawanishi, Toru

2011-12-01

The purpose of this study was to elucidate the effect of heat treatment on the miscibility of multiple concentrated solutes that mimic biopharmaceutical formulations in frozen solutions. The first heating thermal analysis of frozen solutions containing either a low-molecular-weight saccharide (e.g., sucrose, trehalose, and glucose) or a polymer (e.g., polyvinylpyrrolidone and dextran) and their mixtures from -70°C showed a single transition at glass transition temperature of maximally freeze-concentrated solution (T(g) ') that indicated mixing of the freeze-concentrated multiple solutes. The heat treatment of single-solute and various polymer-rich mixture frozen solutions at temperatures far above their T(g) ' induced additional ice crystallization that shifted the transitions upward in the following scan. Contrarily, the heat treatment of frozen disaccharide-rich solutions induced two-step heat flow changes (T(g) ' splitting) that suggested separation of the solutes into multiple concentrated noncrystalline phases, different in the solute compositions. The extent of the T(g) ' splitting depended on the heat treatment temperature and time. Two-step glass transition was observed in some sucrose and dextran mixture solids, lyophilized after the heat treatment. Increasing mobility of solute molecules during the heat treatment should allow spatial reordering of some concentrated solute mixtures into thermodynamically favorable multiple phases. Copyright © 2011 Wiley-Liss, Inc.

Energy exchange of an alpine grassland on the northeastern Qinghai-Tibetan Plateau

NASA Astrophysics Data System (ADS)

Shang, Lunyu; Zhang, Yu; Lv, Shihua; Wang, Shaoying

2014-05-01

The seasonal variability in the surface energy exchange of an alpine grassland on the northeastern Qinghai-Tibetan Plateau was investigated using eddy covariance measurements. Based on the change of air temperature and the seasonal distribution of precipitation, a winter season and wet season were identified, which were separated by transitional periods. For each period, the surface energy exchange exhibited distinct patterns. Daily mean net radiation (Rn) was almost always positive throughout the year. Sensible heat flux (H) was almost always greater than latent heat flux (LE) during the winter season, and LE was always greater than H during the wet season. Ground heat flux (G0) was relatively low throughout the year. The annual mean net radiation was about 39% of the annual mean solar radiation (Rs). Rn was relatively low during the winter season (21% of Rs) compared to the wet season (55% of Rs), which can be explained by the difference in surface albedo and moisture condition between the two seasons. H and LE had different roles during different periods of the year. Annually, the main consumer of net radiation was LE. During the winter season, H was dominant because of the frozen soil condition and lack of precipitation. During the wet season LE was dominant due to increased temperature and sufficient rainfall coupling with vegetation development. LE was strongly controlled by Rn from June to August though surface conductance (gc) and soil water content (θv) were high. During the transitional periods, H and LE were nearly equally partitioned in the energy balance. The results also suggested that the freeze-thaw condition of soil and the seasonal distribution of precipitation had important impacts on the energy exchange in this alpine grassland.

Analysis of isothermal and cooling rate dependent immersion freezing by a unifying stochastic ice nucleation model

NASA Astrophysics Data System (ADS)

Alpert, P. A.; Knopf, D. A.

2015-05-01

Immersion freezing is an important ice nucleation pathway involved in the formation of cirrus and mixed-phase clouds. Laboratory immersion freezing experiments are necessary to determine the range in temperature (T) and relative humidity (RH) at which ice nucleation occurs and to quantify the associated nucleation kinetics. Typically, isothermal (applying a constant temperature) and cooling rate dependent immersion freezing experiments are conducted. In these experiments it is usually assumed that the droplets containing ice nuclei (IN) all have the same IN surface area (ISA), however the validity of this assumption or the impact it may have on analysis and interpretation of the experimental data is rarely questioned. A stochastic immersion freezing model based on first principles of statistics is presented, which accounts for variable ISA per droplet and uses physically observable parameters including the total number of droplets (Ntot) and the heterogeneous ice nucleation rate coefficient, Jhet(T). This model is applied to address if (i) a time and ISA dependent stochastic immersion freezing process can explain laboratory immersion freezing data for different experimental methods and (ii) the assumption that all droplets contain identical ISA is a valid conjecture with subsequent consequences for analysis and interpretation of immersion freezing. The simple stochastic model can reproduce the observed time and surface area dependence in immersion freezing experiments for a variety of methods such as: droplets on a cold-stage exposed to air or surrounded by an oil matrix, wind and acoustically levitated droplets, droplets in a continuous flow diffusion chamber (CFDC), the Leipzig aerosol cloud interaction simulator (LACIS), and the aerosol interaction and dynamics in the atmosphere (AIDA) cloud chamber. Observed time dependent isothermal frozen fractions exhibiting non-exponential behavior with time can be readily explained by this model considering varying ISA. An apparent cooling rate dependence ofJhet is explained by assuming identical ISA in each droplet. When accounting for ISA variability, the cooling rate dependence of ice nucleation kinetics vanishes as expected from classical nucleation theory. The model simulations allow for a quantitative experimental uncertainty analysis for parameters Ntot, T, RH, and the ISA variability. In an idealized cloud parcel model applying variability in ISAs for each droplet, the model predicts enhanced immersion freezing temperatures and greater ice crystal production compared to a case when ISAs are uniform in each droplet. The implications of our results for experimental analysis and interpretation of the immersion freezing process are discussed.

Analysis of isothermal and cooling-rate-dependent immersion freezing by a unifying stochastic ice nucleation model

NASA Astrophysics Data System (ADS)

Alpert, Peter A.; Knopf, Daniel A.

2016-02-01

Immersion freezing is an important ice nucleation pathway involved in the formation of cirrus and mixed-phase clouds. Laboratory immersion freezing experiments are necessary to determine the range in temperature, T, and relative humidity, RH, at which ice nucleation occurs and to quantify the associated nucleation kinetics. Typically, isothermal (applying a constant temperature) and cooling-rate-dependent immersion freezing experiments are conducted. In these experiments it is usually assumed that the droplets containing ice nucleating particles (INPs) all have the same INP surface area (ISA); however, the validity of this assumption or the impact it may have on analysis and interpretation of the experimental data is rarely questioned. Descriptions of ice active sites and variability of contact angles have been successfully formulated to describe ice nucleation experimental data in previous research; however, we consider the ability of a stochastic freezing model founded on classical nucleation theory to reproduce previous results and to explain experimental uncertainties and data scatter. A stochastic immersion freezing model based on first principles of statistics is presented, which accounts for variable ISA per droplet and uses parameters including the total number of droplets, Ntot, and the heterogeneous ice nucleation rate coefficient, Jhet(T). This model is applied to address if (i) a time and ISA-dependent stochastic immersion freezing process can explain laboratory immersion freezing data for different experimental methods and (ii) the assumption that all droplets contain identical ISA is a valid conjecture with subsequent consequences for analysis and interpretation of immersion freezing. The simple stochastic model can reproduce the observed time and surface area dependence in immersion freezing experiments for a variety of methods such as: droplets on a cold-stage exposed to air or surrounded by an oil matrix, wind and acoustically levitated droplets, droplets in a continuous-flow diffusion chamber (CFDC), the Leipzig aerosol cloud interaction simulator (LACIS), and the aerosol interaction and dynamics in the atmosphere (AIDA) cloud chamber. Observed time-dependent isothermal frozen fractions exhibiting non-exponential behavior can be readily explained by this model considering varying ISA. An apparent cooling-rate dependence of Jhet is explained by assuming identical ISA in each droplet. When accounting for ISA variability, the cooling-rate dependence of ice nucleation kinetics vanishes as expected from classical nucleation theory. The model simulations allow for a quantitative experimental uncertainty analysis for parameters Ntot, T, RH, and the ISA variability. The implications of our results for experimental analysis and interpretation of the immersion freezing process are discussed.

Monitoring seasonal state and mapping species in Alaskan taiga using imaging radar as input to CO[sub 2] flux models

DOE Office of Scientific and Technical Information (OSTI.GOV)

Way, J.B.; Rignot, E.; McDonald, K.

1993-06-01

Changes in the seasonal CO[sub 2] flux of the boreal forests may result from increased atmospheric CO[sub 2] concentrations and associated atmospheric warming. To monitor this potential change, a combination of remote sensing information and ecophysiological models are required. In this paper we address the use of synthetic aperture radar (SAR) data to provide some of the input to the ecophysiological models: forest type, freeze/thaw state which limits the growing season for conifers, and leaf on/off state which limits the growing season for deciduous species. AIRSAR data collected in March 1988 during an early thaw event and May 1991 duringmore » spring breakup are used to generate species maps and to determine the sensitivity of SAR to canopy freeze/thaw transitions. These data are also used to validate a microwave scattering model which is then used to determine the sensitivity of SAR to leaf on/off and soil freeze/thaw transitions. Finally, a CO[sub 2] flux algorithm which utilizes SAR data and an ecophysiological model to estimate CO[sub 2] flux is presented. CO[sub 2] flux maps are generated from which areal estimates of CO[sub 2] flux are derived. This work was carried out at the Jet Propulsion Laboratory under contract to the NASA.« less

Induction of instability in water-in-oil-in-water double emulsions by freeze-thaw cycling.

PubMed

Rojas, Edith C; Papadopoulos, Kyriakos D

2007-06-19

Individual water-in-oil-in-water (W1/O/W2) double-emulsion globules loaded with fluorescently labeled bovine serum albumin (FITC-BSA) were optically monitored within cylindrical capillaries during freeze-thaw cycling. Coalescence of internal aqueous droplets (W1) and external aqueous phase (W2), termed external coalescence, was not observed before or during freezing of the oil phase (O). On the other hand, this instability mechanism was readily promoted during thawing. This realization confirms the previously suggested potential of W1/O/W2 double emulsions to trigger release upon oil thawing and demonstrates that it is a direct result of globule breakage through external coalescence. The presented results also identified a threshold in the relative W1 droplet size above which instability occurred, while smaller droplets remained unperturbed and therefore indicate that optimization of the delivery can be achieved by tuning the size of W1 droplets. In addition, we propose a possible explanation for the occurrence of instability during oil thawing and its dependence on the size of W1 droplets. Because this alternative globule-breakage mechanism simply uses temperature increase (solid-to-liquid-phase transition) as external stimulus, W1/O/W2 double-emulsion delivery systems can be easily tailored by choosing an oil phase with the appropriate phase-transition temperature.

Effects of ultrasonic pretreatments on quality, energy consumption and sterilization of barley grass in freeze drying.

PubMed

Cao, Xiaohuang; Zhang, Min; Mujumdar, Arun S; Zhong, Qifeng; Wang, Zhushang

2018-01-01

Barley grass is a plant resource for rehabilitation therapy. Its processing requires retaining nutrition well for rehabilitation cure of consumers. To meet the aim as well as low energy consumption and microbiological safety of products, ultrasonic treatments (UT) were applied to bathing materials at different power levels (10, 30, 45, 60W/L) for 10mins. After treatments, the bathed barley grass (100g) was freeze-dried under vacuum -0.09MPa with fixed power of 2W/g. Parameters of color, microbial colony, energy consumption, glass transition temperature, moisture content, water activity, taste substances, contents of flavonoid and chlorophyll were determined after drying. In contrast with no treatment case, UT (45W/L) decreased drying time by 14% and decreased energy consumption by 19%; UT (60W/L) decreased total microbial colonies by 33%. Also, UT (30W/L) yielded contents of flavonoid (9.2/kg) and chlorophyll (10.5g/kg) of dried sample; UT power (10W/L) yielded the highest L ∗ (51.5) and the lowest a ∗ (-9.3) value. Simultaneously, UT leads to a higher glass transition temperature (Tg), lower water activity and produces less sourness and bitterness of dried products. Ultra-sonication is an alternative to improve quality, flavor and energy consumption of barley grass in freeze drying. Copyright © 2017 Elsevier B.V. All rights reserved.

Miscibility as a factor for component crystallization in multisolute frozen solutions.

PubMed

Izutsu, Ken-Ichi; Shibata, Hiroko; Yoshida, Hiroyuki; Goda, Yukihiro

2014-07-01

The relationship between the miscibility of formulation ingredients and their crystallization during the freezing segment of the lyophilization process was studied. The thermal properties of frozen solutions containing myo-inositol and cosolutes were obtained by performing heating scans from -70 °C before and after heat treatment at -20 °C to -5 °C. Addition of dextran 40,000 reduced and prevented crystallization of myo-inositol. In the first scan, some frozen solutions containing an inositol-rich mixture with dextran showed single broad transitions (Tg's: transition temperatures of maximally freeze-concentrated solutes) that indicated incomplete mixing of the concentrated amorphous solutes. Heat treatment of these frozen solutions induced separation of the solutes into inositol-dominant and solute mixture phases (Tg' splitting) following crystallization of myo-inositol (Tg' shifting). The crystal growth involved myo-inositol molecules in the solute mixture phase. The amorphous-amorphous phase separation and resulting loss of the heteromolecular interaction in the freeze-concentrated inositol-dominant phase should allow ordered assembly of the solute molecules required for nucleation. Some dextran-rich and intermediate concentration ratio frozen solutions retained single Tg's of the amorphous solute mixture, both before and after heat treatments. The relevance of solute miscibility on the crystallization of myo-inositol was also indicated in the systems containing glucose or recombinant human albumin. © 2014 Wiley Periodicals, Inc. and the American Pharmacists Association.

An Improved Model for Nucleation-Limited Ice Formation in Living Cells during Freezing

PubMed Central

Zhao, Gang; He, Xiaoming

2014-01-01

Ice formation in living cells is a lethal event during freezing and its characterization is important to the development of optimal protocols for not only cryopreservation but also cryotherapy applications. Although the model for probability of ice formation (PIF) in cells developed by Toner et al. has been widely used to predict nucleation-limited intracellular ice formation (IIF), our data of freezing Hela cells suggest that this model could give misleading prediction of PIF when the maximum PIF in cells during freezing is less than 1 (PIF ranges from 0 to 1). We introduce a new model to overcome this problem by incorporating a critical cell volume to modify the Toner's original model. We further reveal that this critical cell volume is dependent on the mechanisms of ice nucleation in cells during freezing, i.e., surface-catalyzed nucleation (SCN) and volume-catalyzed nucleation (VCN). Taken together, the improved PIF model may be valuable for better understanding of the mechanisms of ice nucleation in cells during freezing and more accurate prediction of PIF for cryopreservation and cryotherapy applications. PMID:24852166

Solitosynthesis: Cosmological evolution of non-topological solitons

NASA Technical Reports Server (NTRS)

Griest, Kim; Kolb, Edward W.

1989-01-01

The thermal creation, fusion, evaporation, and destruction of non-topological solitons (NTS) after a phase transition in the early universe is considered. By defining and following NTS statistical equilibrium and departures from it, and depending on particle physics parameters, one of three possible scenarios occurs. If reaction rates are high enough, a period of equilibrium occurs and relic abundances are determined by the freeze-out temperature. Equilibrium first drives most NTS's into their constituents (free phi particles) and then causes rapid fusion into large NTS's. If freeze-out occurs during the first phase, the NTS's are almost entirely destroyed, while if it occurs during the second phase, solitosynthesis occurs and NTS's may be cosmically relevant. For slow reaction rates the NTS's are born frozen out and have the abundance determined by the phase transition. Analytic approximations for determining the abundances are developed, and tested by numerically integrating a reaction network in an expanding universe. Unfortunately, for most of the parameter space considered, solito-destruction/evaporation occurs.

Understanding the ice nucleation characteristics of feldspars suspended in solution

NASA Astrophysics Data System (ADS)

Kumar, Anand; Marcolli, Claudia; Kaufmann, Lukas; Krieger, Ulrich; Peter, Thomas

2017-04-01

Freezing of liquid droplets and subsequent ice crystal growth affects optical properties of clouds and precipitation. Field measurements show that ice formation in cumulus and stratiform clouds begins at temperatures much warmer than those associated with homogeneous ice nucleation in pure water, which is ascribed to heterogeneous ice nucleation occurring on the foreign surfaces of ice nuclei (IN). Various insoluble particles such as mineral dust, soot, metallic particles, volcanic ash, or primary biological particles have been suggested as IN. Among these the suitability of mineral dusts is best established. The ice nucleation ability of mineral dust particles may be modified when secondary organic or inorganic substances are accumulating on the dust during atmospheric transport. If the coating is completely wetting the mineral dust particles, heterogeneous ice nucleation occurs in immersion mode also below 100 % RH. A previous study by Zobrist et al. (2008) Arizona test dust, silver iodide, nonadecanol and silicon dioxide suspensions in various solutes showed reduced ice nucleation efficiency (in immersion mode) of the particles. Though it is still quite unclear how surface modifications and coatings influence the ice nucleation activity of the components present in natural dust particles at a microphysical scale. To improve our understanding how solute and mineral dust particle surface interaction, we run freezing experiments using a differential scanning calorimeter (DSC) with microcline, sanidine, plagioclase, kaolinite and quartz particles suspended in pure water and solutions containing ammonia, ammonium bisulfate, ammonium sulfate, ammonium chloride, ammonium nitrate, potassium chloride, potassium sulfate, sodium sulfate and sulfuric acid. Methodology Suspensions of mineral dust samples (2 - 5 wt%) are prepared in water with varying solute concentrations (0 - 15 wt%). 20 vol% of this suspension plus 80 vol% of a mixture of 95 wt% mineral oil (Aldrich Chemical) and 5 wt% lanolin (Fluka Chemical) is emulsified with a rotor-stator homogenizer for 40 s at a rotation frequency of 7000 rpm. 4 - 10 mg of this mixture is pipetted in an aluminum pan (closed hermetically), placed in the DSC and subjected to three freezing cycles. The first and the third freezing cycles are executed at a cooling rate of 10 K/min to control the stability of the sample. The second freezing cycle is executed at a 1 K/min cooling rate and is used for evaluation. Freezing temperatures are obtained by evaluating the onset of the freezing signal in the DSC curve and plotted against water activity. Results Based on Koop et al. (2000), a general decreasing trend in ice nucleation efficiency of the mineral samples with increasing solute concentrations is expected. Interestingly, feldspars (microcline, sanidine, plagioclase) in very dilute solutions of ammonia and ammonium salts (water activity close to one) show an increase in ice nucleation efficiency of 4 to 6 K compared to that in pure water. Similar trends but less pronounced are observed for kaolinite while quartz shows barely any effect. Therefore, there seem to be specific interactions between the feldspar surface and ammonia and/or ammonium ions which result in an increase in freezing temperatures at low solute concentrations. The surface ion exchange seems to be secondary for this effect since it is also present in ammonia solution. We hypothesize that ammonia adsorbs on the aluminol/silanol groups present on feldspar (viz. aluminosilicate surface) surfaces (Nash and Marshall, 1957; Belchinskaya et al., 2013). Hence allowing one of the N-H bonds to stick outwards from the surface, facing towards the bulk water and providing a favorable template for ice to grow. The current study gives an insight into the ice nucleation behavior of aluminosilicate minerals when present in conjunction with chemical species, eg. ammonium/sulfates, which is of high atmospheric relevance. References Koop et al., (2000), doi:10.1038/35020537. Zobrist et al., (2008). J. Phys. Chem., 112:3965-3975. Nash and Marshall (1957). Proceedings Soil Sci. Society, 21:149-153. Belchinskaya et al., (2013). J. Applied Chemistry, doi:10.1155/2013/789410

Impacts of the Air Temperature Rising on the Soil Freezing-thawing Processes and the Surface Fluxes on the Tibetan Plateau

NASA Astrophysics Data System (ADS)

Zheng, G.; Yang, D.

2017-12-01

The Tibetan Plateau (TP) is the highest plateau all over the world and plays an essential role on the global water cycle and the atmospheric circulation, because many large rivers originating there and it acts as a "heat source" to pump the Asian summer monsoon. During the past 50 years, the TP is among the most sensitive regions to the climatic warming. Many previous researches have been delved into the impacts of the permafrost degradation there. But the variations and the impacts of the changes of the seasonally frozen ground, which consists 50 % of the plateau region, have been less discussed. Thus, this study uses the geomorphology-based eco-hydrological model to simulate the long-term land surface processes on 37 after picked China Meteorological Administration stations. And, these stations uniformly locate within the seasonally frozen regions of the TP. The modelled freezing-thawing cycles have successfully reproduced the observations with the correlation squares of 0.8 (significance level p < 0.05) and the mean biases of +0.05 m. The simulated results show that, during the past 50 years, annually maximum frozen depth and the near-surface frozen duration have significantly decreased at the rate of 0.13 m/decade and 4.6 days/decade. The changes of the near-surface freezing-thawing cycles exert large influences on the flux exchanges between the land surface and the atmosphere. The advance (delay) of the freezing ending (starting) time has caused 13 % (p < 0.05) of the reduction of the sensible heat fluxes significantly during the early spring (autumn). And, except for the dry western part of the TP, they contribute little to the variations of the latent heat fluxes which are mainly controlled by the precipitation instead. For the western region, the near-surface thawing increases available liquid moisture significantly (p < 0.05) and so does the evaporation there. Furthermore, the advanced freezing ending time during the early spring has more climatic and biological meanings. The weakened sensible heat would influence the following summer monsoon and redistribute the precipitation over the southeastern Asia. Also, as the incoming radiation and the latent heat keeping stable, less sensible heat fluxes would lead to more ground heat storage which provides a better thermal condition for the vegetation growth.

Animal ice-binding (antifreeze) proteins and glycolipids: an overview with emphasis on physiological function.

PubMed

Duman, John G

2015-06-01

Ice-binding proteins (IBPs) assist in subzero tolerance of multiple cold-tolerant organisms: animals, plants, fungi, bacteria etc. IBPs include: (1) antifreeze proteins (AFPs) with high thermal hysteresis antifreeze activity; (2) low thermal hysteresis IBPs; and (3) ice-nucleating proteins (INPs). Several structurally different IBPs have evolved, even within related taxa. Proteins that produce thermal hysteresis inhibit freezing by a non-colligative mechanism, whereby they adsorb onto ice crystals or ice-nucleating surfaces and prevent further growth. This lowers the so-called hysteretic freezing point below the normal equilibrium freezing/melting point, producing a difference between the two, termed thermal hysteresis. True AFPs with high thermal hysteresis are found in freeze-avoiding animals (those that must prevent freezing, as they die if frozen) especially marine fish, insects and other terrestrial arthropods where they function to prevent freezing at temperatures below those commonly experienced by the organism. Low thermal hysteresis IBPs are found in freeze-tolerant organisms (those able to survive extracellular freezing), and function to inhibit recrystallization - a potentially damaging process whereby larger ice crystals grow at the expense of smaller ones - and in some cases, prevent lethal propagation of extracellular ice into the cytoplasm. Ice-nucleator proteins inhibit supercooling and induce freezing in the extracellular fluid at high subzero temperatures in many freeze-tolerant species, thereby allowing them to control the location and temperature of ice nucleation, and the rate of ice growth. Numerous nuances to these functions have evolved. Antifreeze glycolipids with significant thermal hysteresis activity were recently identified in insects, frogs and plants. © 2015. Published by The Company of Biologists Ltd.

Spray Irrigation Effects on Surface-Layer Stability in an Experimental Citrus Orchard during Winter Freezes.

NASA Astrophysics Data System (ADS)

Cooper, Harry J.; Smith, Eric A.; Martsolf, J. David

1997-02-01

Observations taken by two surface radiation and energy budget stations deployed in the University of Florida/Institute for Food and Agricultural Service experimental citrus orchard in Gainesville, Florida, have been analyzed to identify the effects of sprayer irrigation on thermal stability and circulation processes within the orchard during three 1992 winter freeze episodes. Lapse rates of temperature observed from a micrometeorological tower near the center of the orchard were also recorded during periods of irrigation for incorporation into the analysis. Comparisons of the near-surface temperature lapse rates observed with the two energy budget stations show consistency between the two sites and with the tower-based lapse rates taken over a vertical layer from 1.5 to 15 m above ground level. A theoretical framework was developed that demonstrates that turbulent-scale processes originating within the canopy, driven by latent heat release associated with condensation and freezing processes from water vapor and liquid water released from sprayer nozzles, can destabilize lapse rates and promote warm air mixing above the orchard canopy. The orchard data were then analyzed in the context of the theory for evidence of local overturning and displacement of surface-layer air, with warmer air from aloft driven by locally buoyant plumes generated by water vapor injected into the orchard during the irrigation periods. It was found that surface-layer lapse rates were lower during irrigation periods than under similar conditions when irrigation was not occurring, indicating a greater degree of vertical mixing of surface-layer air with air from above treetops, as a result of local convective overturning induced by the condensation heating of water vapor released at the nozzles of the sprinklers. This provides an additional explanation to the well-accepted heat of fusion release effect, of how undertree irrigation of a citrus orchard during a freeze period helps protect crops against frost damage.

40 CFR Appendix A to Subpart M of... - Interpretive Rule Governing Roof Removal Operations

Code of Federal Regulations, 2010 CFR

2010-07-01

...)). 3.B.3. An exemption from wetting is also allowed when the air or roof surface temperature at the point of wetting is below freezing, as specified in § 61.145(c)(7). If freezing temperatures are indicated as the reason for not wetting, records must be kept of the temperature at the beginning, middle...

How Circulation of Water Affects Freezing in Ponds

ERIC Educational Resources Information Center

Moreau, Theresa; Lamontagne, Robert; Letzring, Daniel

2007-01-01

One means of preventing the top of a pond from freezing involves running a circulating pump near the bottom to agitate the surface and expose it to air throughout the winter months. This phenomenon is similar to that of the flowing of streams in subzero temperatures and to the running of taps to prevent pipe bursts in winter. All of these cases…

Greenland coastal air temperatures linked to Baffin Bay and Greenland Sea ice conditions during autumn through regional blocking patterns

NASA Astrophysics Data System (ADS)

Ballinger, Thomas J.; Hanna, Edward; Hall, Richard J.; Miller, Jeffrey; Ribergaard, Mads H.; Høyer, Jacob L.

2018-01-01

Variations in sea ice freeze onset and regional sea surface temperatures (SSTs) in Baffin Bay and Greenland Sea are linked to autumn surface air temperatures (SATs) around coastal Greenland through 500 hPa blocking patterns, 1979-2014. We find strong, statistically significant correlations between Baffin Bay freeze onset and SSTs and SATs across the western and southernmost coastal areas, while weaker and fewer significant correlations are found between eastern SATs, SSTs, and freeze periods observed in the neighboring Greenland Sea. Autumn Greenland Blocking Index values and the incidence of meridional circulation patterns have increased over the modern sea ice monitoring era. Increased anticyclonic blocking patterns promote poleward transport of warm air from lower latitudes and local warm air advection onshore from ocean-atmosphere sensible heat exchange through ice-free or thin ice-covered seas bordering the coastal stations. Temperature composites by years of extreme late freeze conditions, occurring since 2006 in Baffin Bay, reveal positive monthly SAT departures that often exceed 1 standard deviation from the 1981-2010 climate normal over coastal areas that exhibit a similar spatial pattern as the peak correlations.

Evaluation of Hydrometeor Classification for Winter Mixed-Phase Precipitation Events

NASA Astrophysics Data System (ADS)

Hickman, B.; Troemel, S.; Ryzhkov, A.; Simmer, C.

2016-12-01

Hydrometeor classification algorithms (HCL) typically discriminate radar echoes into several classes including rain (light, medium, heavy), hail, dry snow, wet snow, ice crystals, graupel and rain-hail mixtures. Despite the strength of HCL for precipitation dominated by a single phase - especially warm-season classification - shortcomings exist for mixed-phase precipitation classification. Properly identifying mixed-phase can lead to more accurate precipitation estimates, and better forecasts for aviation weather and ground warnings. Cold season precipitation classification is also highly important due to their potentially high impact on society (e.g. black ice, ice accumulation, snow loads), but due to the varying nature of the hydrometeor - density, dielectric constant, shape - reliable classification via radar alone is not capable. With the addition of thermodynamic information of the atmosphere, either from weather models or sounding data, it has been possible to extend more and more into winter time precipitation events. Yet, inaccuracies still exist in separating more benign (ice pellets) from more the more hazardous (freezing rain) events. We have investigated winter mixed-phase precipitation cases which include freezing rain, ice pellets, and rain-snow transitions from several events in Germany in order to move towards a reliable nowcasting of winter precipitation in hopes to provide faster, more accurate winter time warnings. All events have been confirmed to have the specified precipitation from ground reports. Classification of the events is achieved via a combination of inputs from a bulk microphysics numerical weather prediction model and the German dual-polarimetric C-band radar network, into a 1D spectral bin microphysical model (SBC) which explicitly treats the processes of melting, refreezing, and ice nucleation to predict four near-surface precipitation types: rain, snow, freezing rain, ice pellets, rain/snow mixture, and freezing rain/pellet mixture. Evaluation of the classification is performed by means of disdrometer data, in-situ ground observations, and eye-witness reports from the European Severe Weather Database (ESWD). Additionally, a comparison to an existing radar based HCL is performed as a sanity check and a performance evaluator.

Biochip-based instruments development for space exploration: influence of the antibody immobilization process on the biochip resistance to freeze-drying, temperature shifts and cosmic radiations

NASA Astrophysics Data System (ADS)

Coussot, G.; Moreau, T.; Faye, C.; Vigier, F.; Baqué, M.; Le Postollec, A.; Incerti, S.; Dobrijevic, M.; Vandenabeele-Trambouze, O.

2017-04-01

Due to the diversity of antibody (Ab)-based biochips chemistries available and the little knowledge about biochips resistance to space constraints, immobilization of Abs on the surface of the biochips dedicated to Solar System exploration is challenging. In the present paper, we have developed ten different biochip models including covalent or affinity immobilization with full-length Abs or Ab fragments. Ab immobilizations were carried out in oriented/non-oriented manner using commercial activated surfaces with N-hydroxysuccinic ester (NHS-surfaces) or homemade surfaces using three generations of dendrimers (dendrigraft of poly L-lysine (DGL) surfaces). The performances of the Ab -based surfaces were cross-compared on the following criteria: (i) analytical performances (expressed by both the surface density of immobilized Abs and the amount of antigens initially captured by the surface) and (ii) resistance of surfaces to preparation procedure (freeze-drying, storage) or spatial constraints (irradiation and temperature shifts) encountered during a space mission. The latter results have been expressed as percentage of surface binding capacity losses (or percentage of remaining active Abs). The highest amount of captured antigen was achieved with Ab surfaces having full-length Abs and DGL-surfaces that have much higher surface densities than commercial NHS-surface. After freeze-drying process, thermal shift and storage sample exposition, we found that more than 80% of surface binding sites remained active in this case. In addition, the resistance of Ab surfaces to irradiation with particles such as electron, carbon ions or protons depends not only on the chemistries (covalent/affinity linkages) and strategies (oriented/non-oriented) used to construct the biochip, but also on the type, energy and fluence of incident particles. Our results clearly indicate that full-length Ab immobilization on NHS-surfaces and DGL-surfaces should be preferred for potential use in instruments for planetary exploration.

Changes in the Microenvironment of Nitroxide Radicals around the Glass Transition Temperature.

PubMed

Bordignon, Enrica; Nalepa, Anna I; Savitsky, Anton; Braun, Lukas; Jeschke, Gunnar

2015-10-29

For structural characterization by pulsed EPR methods, spin-labeled macromolecules are routinely studied at cryogenic temperatures. The equilibration of the conformational ensemble during shock-freezing occurs to a good approximation at the glass transition temperature (Tg). In this work, we used X-band power saturation continuous wave (cw) EPR to obtain information on the glass transition temperatures in the microenvironment of nitroxide radicals in solvents or bound to different sites in proteins. The temperature dependence of the saturation curve of nitroxide probes in pure glycerol or ortho-terphenyl showed detectable transitions at the respective Tg values, with the latter solvent characterized by a sharper change of the saturation properties, according to its higher fragility. In contrast, nitroxide probes in a glycerol/water mixture showed a discontinuity in the saturation properties close to the expected glass transition temperature, which made the determination of Tg complicated. Low-temperature W-band cw EPR and W-band ELDOR-detected NMR experiments demonstrated that the discontinuity is due to local rearrangements of H-bonds between water molecules and the nitroxide reporter group. The change in the network of H-bonds formed between the nitroxide and water molecules that occurs around Tg was found to be site-dependent in spin-labeled proteins. This effect can therefore be modulated by neighboring residues with different steric hindrances and/or charge distributions and possibly by the glycerol enrichment on protein surfaces. In conclusion, if the thermal history of the sample is carefully reproduced, the nitroxide probe is extremely sensitive in reporting site-specific changes in the H-bonding to water molecules close to Tg and local glass transition temperatures in spin-labeled macromolecules.

Ammonia photolysis and the greenhouse effect in the primordial atmosphere of the earth

NASA Technical Reports Server (NTRS)

Kuhn, W. R.; Atreya, S. K.

1979-01-01

Photochemical calculations indicate that in the prebiotic atmosphere of earth ammonia would have been irreversibly converted to N2 in less than 40 years if the ammonia surface mixing ratio were no more than 0.0001. However, if a continuous outgassing of ammonia were maintained, radiative-equilibrium calculations indicate that a surface mixing ratio of ammonia of 0.0001 or greater would provide a sufficient greenhouse effect to keep the surface temperature above freezing. With a 0.0001 mixing ratio of ammonia, 60% to 70% of the present-day solar luminosity would be adequate to maintain surface temperatures above freezing. A lower limit to the time constant for accumulation of an amount of nitrogen equivalent to the present day value is 10 my if the outgassing were such as to provide a continuous surface mixing ratio of ammonia of at least 0.00001.

Oligosaccharide-based Surfactant/Citric Acid Buffer System Stabilizes Lactate Dehydrogenase during Freeze-drying and Storage without the Addition of Natural Sugar.

PubMed

Ogawa, Shigesaburo; Kawai, Ryuichiro; Koga, Maito; Asakura, Kouichi; Takahashi, Isao; Osanai, Shuichi

2016-06-01

Experiments were conducted to assess the maintenance effects of oligosaccharide-based surfactants on the enzymatic activity of a model protein, lactate dehydrogenase (LDH), during freeze-drying and room temperature storage using the citric acid buffer system. Oligosaccharide-based surfactants, which exhibit a high glass transition temperature (Tg), promoted the eminent retention of enzymatic activity during these protocols, whereas monosaccharide-based surfactants with a low Tg displayed poor performance at high concentration, albeit much better than that of Tween 80 at middle concentration. The increase in the alkyl chain length did not exert positive effects as observed for the maintenance effect during freeze-thawing, but an amphiphilic nature and a glass forming ability were crucial for the effective stabilization at a low excipient concentration during freeze-drying. Even a low oligosaccharide-based surfactant content (0.1 mg mL(-1)) could maintain LDH activity during freeze-drying, but a high surfactant content (1.0 mg mL(-1)) was required to prevent buffer precipitation and retain high LDH activity on storage. Regarding storage, glass formation restricted molecular mobility in the lyophilized matrix, and LDH activity was effectively retained. The present results describe a strategy based on the glass-forming ability of surfactant-type excipients that affords a natural sugar-free formulation or an alternative use for polysorbate-type surfactants.

Detecting phase separation of freeze-dried binary amorphous systems using pair-wise distribution function and multivariate data analysis.

PubMed

Chieng, Norman; Trnka, Hjalte; Boetker, Johan; Pikal, Michael; Rantanen, Jukka; Grohganz, Holger

2013-09-15

The purpose of this study is to investigate the use of multivariate data analysis for powder X-ray diffraction-pair-wise distribution function (PXRD-PDF) data to detect phase separation in freeze-dried binary amorphous systems. Polymer-polymer and polymer-sugar binary systems at various ratios were freeze-dried. All samples were analyzed by PXRD, transformed to PDF and analyzed by principal component analysis (PCA). These results were validated by differential scanning calorimetry (DSC) through characterization of glass transition of the maximally freeze-concentrate solute (Tg'). Analysis of PXRD-PDF data using PCA provides a more clear 'miscible' or 'phase separated' interpretation through the distribution pattern of samples on a score plot presentation compared to residual plot method. In a phase separated system, samples were found to be evenly distributed around the theoretical PDF profile. For systems that were miscible, a clear deviation of samples away from the theoretical PDF profile was observed. Moreover, PCA analysis allows simultaneous analysis of replicate samples. Comparatively, the phase behavior analysis from PXRD-PDF-PCA method was in agreement with the DSC results. Overall, the combined PXRD-PDF-PCA approach improves the clarity of the PXRD-PDF results and can be used as an alternative explorative data analytical tool in detecting phase separation in freeze-dried binary amorphous systems. Copyright © 2013 Elsevier B.V. All rights reserved.

Fabrication and icing property of superhydrophilic and superhydrophobic aluminum surfaces derived from anodizing aluminum foil in a sodium chloride aqueous solution

NASA Astrophysics Data System (ADS)

Song, Meirong; Liu, Yuru; Cui, Shumin; Liu, Long; Yang, Min

2013-10-01

An aluminum foil with a rough surface was first prepared by anodic treatment in a neutral aqueous solution with the help of pitting corrosion of chlorides. First, the hydrophobic Al surface (contact angle around 79°) became superhydrophilic (contact angle smaller than 5°) after the anodizing process. Secondly, the superhydrophilic Al surface became superhydrophobic (contact angle larger than 150°) after being modified by oleic acid. Finally, the icing property of superhydrophilic, untreated, and superhydrophobic Al foils were investigated in a refrigerated cabinet at -12 °C. The mean total times to freeze a water droplet (6 μL) on the three foils were 17 s, 158 s and 1604 s, respectively. Thus, the superhydrophilic surface accelerates the icing process, while the superhydrophobic surface delays the process. The main reason for this transition might mainly result from the difference of the contact area of the water droplet with Al substrate: the increase in contact area with Al substrate will accelerate the heat conduct process, as well as the icing process; the decrease in contact area with Al substrate will delay the heat conduct process, as well as the icing process. Compared to the untreated Al foil, the contact area of the water droplet with the Al substrate was higher on superhydrophilic surface and smaller on the superhydrophobic surface, which led to the difference of the heat transfer time as well as the icing time.

A sample-freezing drive shoe for a wire line piston core sampler

USGS Publications Warehouse

Murphy, F.; Herkelrath, W.N.

1996-01-01

Loss of fluids and samples during retrieval of cores of saturated, noncohesive sediments results in incorrect measures of fluid distributions and an inaccurate measure of the stratigraphic position of the sample. To reduce these errors, we developed a hollow drive shoe that freezes in place the lowest 3 inches (75 mm) of a 1.88-inch-diameter (48 mm), 5-foot-long (1.5 m) sediment sample taken using a commercial wire line piston core sampler. The end of the core is frozen by piping liquid carbon dioxide at ambient temperature through a steel tube from a bottle at the land surface to the drive shoe where it evaporates and expands, cooling the interior surface of the shoe to about -109??F (-78??C). Freezing a core end takes about 10 minutes. The device was used to collect samples for a study of oil-water-air distributions, and for studies of water chemistry and microbial activity in unconsolidated sediments at the site of an oil spill near Bemidji, Minnesota. Before freezing was employed, samples of sandy sediments from near the water table sometimes flowed out of the core barrel as the sampler was withdrawn. Freezing the bottom of the core allowed for the retention of all material that entered the core barrel and lessened the redistribution of fluids within the core. The device is useful in the unsaturated and shallow saturated zones, but does not freeze cores well at depths greater than about 20 feet (6 m) below water, possibly because the feed tube plugs with dry ice with increased exhaust back-pressure, or because sediment enters the annulus between the core barrel and the core barrel liner and blocks the exhaust.

Design of ice-free nanostructured surfaces based on repulsion of impacting water droplets.

PubMed

Mishchenko, Lidiya; Hatton, Benjamin; Bahadur, Vaibhav; Taylor, J Ashley; Krupenkin, Tom; Aizenberg, Joanna

2010-12-28

Materials that control ice accumulation are important to aircraft efficiency, highway and powerline maintenance, and building construction. Most current deicing systems include either physical or chemical removal of ice, both energy and resource-intensive. A more desirable approach would be to prevent ice formation rather than to fight its build-up. Much attention has been given recently to freezing of static water droplets resting on supercooled surfaces. Ice accretion, however, begins with the droplet/substrate collision followed by freezing. Here we focus on the behavior of dynamic droplets impacting supercooled nano- and microstructured surfaces. Detailed experimental analysis of the temperature-dependent droplet/surface interaction shows that highly ordered superhydrophobic materials can be designed to remain entirely ice-free down to ca. -25 to -30 °C, due to their ability to repel impacting water before ice nucleation occurs. Ice accumulated below these temperatures can be easily removed. Factors contributing to droplet retraction, pinning and freezing are addressed by combining classical nucleation theory with heat transfer and wetting dynamics, forming the foundation for the development of rationally designed ice-preventive materials. In particular, we emphasize the potential of hydrophobic polymeric coatings bearing closed-cell surface microstructures for their improved mechanical and pressure stability, amenability to facile replication and large-scale fabrication, and opportunities for greater tuning of their material and chemical properties.

Melittin liposomes surface modified with poloxamer 188: in vitro characterization and in vivo evaluation.

PubMed

Tian, J L; Ke, X; Chen, Z; Wang, C J; Zhang, Y; Zhong, T C

2011-05-01

Melittin liposomes surface modified with poloxamer 188 were developed, and the effect of poloxamer 188 was investigated with regard to anti-cancer effect and vascular stimulation. Melittin liposomes surface modified with poloxamer 188 at different concentrations (0%, 2%, and 5%) were prepared using the adsorption method, followed by in vitro characterization, including entrapment efficiency, zeta potential, particle size, and morphology. Subsequently, the influence of repeated freeze-thawing on the liposomes was investigated, and the effect of poloxamer 188 on the repeated freeze-thawing process was explored. Vascular stimulation effects of MLT, and MLT liposome that surface coated with or without poloxamer were all studied. Pharmacokinetics of the different MLT preparations were determined and the anticancer activity of the MLT formulations was investigated. The particle size of the liposomes gradually increased with increasing poloxamer 188 content, while the entrapment efficiency did not change significantly. After the first freeze-thaw cycle, size and PDI were both markedly reduced, entrapment efficiency rose, and there was no significant change of zeta potential. The vascular irritation caused by MLT could be reduced to an extent by encapsulation in liposome, but not completely eliminated, while liposomes coated with poloxamer 188 can effectively abolish the phenomenon. Melittin liposomes with surface modified by poloxamer exhibit enhanced bioavailability, effective anticancer activity, and reduced side effects compared with melittin solution. Poloxamer plays an important role in melittin liposomes.

Impact behaviour of freeze-dried and fresh pomelo (Citrus maxima) peel: influence of the hydration state

PubMed Central

Thielen, Marc; Speck, Thomas; Seidel, Robin

2015-01-01

Pomelos (Citrus maxima) are known for their thick peel which—inter alia—serves as energy dissipator when fruits impact on the ground after being shed. It protects the fruit from splitting open and thus enables the contained seeds to stay germinable and to potentially be dispersed by animal vectors. The main part of the peel consists of a parenchymatous tissue that can be interpreted from a materials point of view as open pored foam whose struts are pressurized and filled with liquid. In order to investigate the influence of the water content on the energy dissipation capacity, drop weight tests were conducted with fresh and with freeze-dried peel samples. Based on the coefficient of restitution it was found that freeze-drying markedly reduces the relative energy dissipation capacity of the peel. Measuring the transmitted force during impact furthermore indicated a transition from a uniform collapse of the foam-like tissue to a progressive collapse due to water extraction. Representing the peel by a Maxwell model illustrates that freeze-drying not only drastically reduces the damping function of the dashpots but also stiffens the springs of the model. PMID:26543566

Modelling the impact, spreading and freezing of a water droplet on horizontal and inclined superhydrophobic cooled surfaces

NASA Astrophysics Data System (ADS)

Yao, Yina; Li, Cong; Zhang, Hui; Yang, Rui

2017-10-01

It is quite important to clearly understand the dynamic and freezing process of water droplets impacting a cold substrate for the prevention of ice accretion. In this study, a three-dimensional model including an extended phase change method was developed on OpenFOAM platform to simulate the impact, spreading and freezing of a water droplet on a cooled solid substrate. Both normal and oblique impact conditions were studied numerically. The evolution of the droplet shape and dynamic characteristics such as area ratio and spread factor were compared between numerical and experimental results. Good agreements were obtained. The effects of Weber number and Ohnersorge number on the oblique impact and freezing process were investigated. A regime map which depicts the different responses of droplets as a function of normal Weber number and Ohnesorge number was obtained. Moreover, the impact, spreading and freezing behaviour of water droplets were analyzed in detail from the numerical results.

Cavitation and water fluxes driven by ice water potential in Juglans regia during freeze-thaw cycles.

PubMed

Charra-Vaskou, Katline; Badel, Eric; Charrier, Guillaume; Ponomarenko, Alexandre; Bonhomme, Marc; Foucat, Loïc; Mayr, Stefan; Améglio, Thierry

2016-02-01

Freeze-thaw cycles induce major hydraulic changes due to liquid-to-ice transition within tree stems. The very low water potential at the ice-liquid interface is crucial as it may cause lysis of living cells as well as water fluxes and embolism in sap conduits, which impacts whole tree-water relations. We investigated water fluxes induced by ice formation during freeze-thaw cycles in Juglans regia L. stems using four non-invasive and complementary approaches: a microdendrometer, magnetic resonance imaging, X-ray microtomography, and ultrasonic acoustic emissions analysis. When the temperature dropped, ice nucleation occurred, probably in the cambium or pith areas, inducing high water potential gradients within the stem. The water was therefore redistributed within the stem toward the ice front. We could thus observe dehydration of the bark's living cells leading to drastic shrinkage of this tissue, as well as high tension within wood conduits reaching the cavitation threshold in sap vessels. Ultrasonic emissions, which were strictly emitted only during freezing, indicated cavitation events (i.e. bubble formation) following ice formation in the xylem sap. However, embolism formation (i.e. bubble expansion) in stems was observed only on thawing via X-ray microtomography for the first time on the same sample. Ultrasonic emissions were detected during freezing and were not directly related to embolism formation. These results provide new insights into the complex process and dynamics of water movements and ice formation during freeze-thaw cycles in tree stems. © The Author 2015. Published by Oxford University Press on behalf of the Society for Experimental Biology.

Low-cost rural surface alternatives : demonstration project : [tech transfer summary].

DOT National Transportation Integrated Search

2015-06-01

Identify the most effective and economical methods for preventing or : mitigating freeze-thaw damage to granular surfaced roads in seasonally : cold regions : Construct demonstration test sections using several stabilization : methods recomme...

Geographical Distribution of Thundersnow and their Properties from GPM Ku-band Radar

NASA Astrophysics Data System (ADS)

Adhikari, A.; Liu, C.

2017-12-01

Lightning in snow and freezing rain are relatively uncommon, compared to the warm season thunderstorm. These events can be identified by lightning with the surface temperature colder than 0oC, or named as "cold lightning", A six-years of "cold lightning" characteristics and climatology, including seasonal, diurnal, and surface temperature distribution, are generated after collocating WWLLN and NLDN lightning with ERA-Interim 2 meter temperature. The thundersnow cases are further identified with all vertical temperature profile below 0oC, and the freezing rain cases have temperature warmer than 4oC somewhere in the column above the freezing surface. The statistics of thundersnow events from WWLLN and NLDN are compared over the United States (US). Though with different detection efficiency, WWLLN and NLDN demonstrate almost identical geographical distribution of thundersnow over the US. Taking the full advantage of the Global Precipitation Measuring Mission (GPM) Ku band radar, Thunder Snow Features (TSFs) are defined with contiguous area of non-zero near surface snow precipitation derived from Ku radar along with the collocated WWLLN lightning strikes. Though only a small number of TSFs are identified with three year GPM data, all TSFs have maximum radar reflectivity above 30 dBZ at temperature colder than -10oC, which indicates the importance of non-inductive charging in these events.

Application of Satellite SAR Imagery in Mapping the Active Layer of Arctic Permafrost

NASA Technical Reports Server (NTRS)

Li, Shu-Sun; Romanovsky, V.; Lovick, Joe; Wang, Z.; Peterson, Rorik

2003-01-01

A method of mapping the active layer of Arctic permafrost using a combination of conventional synthetic aperture radar (SAR) backscatter and more sophisticated interferometric SAR (INSAR) techniques is proposed. The proposed research is based on the sensitivity of radar backscatter to the freeze and thaw status of the surface soil, and the sensitivity of INSAR techniques to centimeter- to sub-centimeter-level surface differential deformation. The former capability of SAR is investigated for deriving the timing and duration of the thaw period for surface soil of the active layer over permafrost. The latter is investigated for the feasibility of quantitative measurement of frost heaving and thaw settlement of the active layer during the freezing and thawing processes. The resulting knowledge contributes to remote sensing mapping of the active layer dynamics and Arctic land surface hydrology.

Dynamics of water in LiCl and CaCl 2 aqueous solutions confined in silica matrices: A backscattering neutron spectroscopy study

NASA Astrophysics Data System (ADS)

Mamontov, E.; Cole, D. R.; Dai, S.; Pawel, M. D.; Liang, C. D.; Jenkins, T.; Gasparovic, G.; Kintzel, E.

2008-09-01

Backscattering neutron spectroscopy was used to probe the dynamics of water molecules in LiCl and CaCl 2 aqueous solutions confined in 2.7, 1.9, and 1.4 nm diameter pores of various silica matrices. The pore size of 2.7 nm was found to be sufficiently large for the confined liquids to exhibit characteristic traits of bulk behavior, such as a freezing-melting transition and a phase separation. On the other hand, none of the fluids in the 1.4 nm pores exhibited a clear freezing-melting transition; instead, their dynamics at low temperatures gradually became too slow for the nanosecond resolution of the experiment. The greatest suppression of water mobility was observed in the CaCl 2 solutions, which suggests that cation charge and perhaps the cation hydration environment have a profound influence on the dynamics of the water molecules. Quasielastic neutron scattering measurements of pure H 2O and 1 m LiCl-H 2O solution confined in 1.9 nm pores revealed a dynamic transition in both liquids at practically the same temperature of 225-226 K, even though the dynamics of the solution at room temperature appeared to slow down by more than an order of magnitude compared to the pure water. The observation of the dynamic transition in the solution suggests that this transition may be a universal feature of water governed by processes acting on the local scale, such as a change in the hydrogen bonding.

The UC2-x - Carbon eutectic: A laser heating study

NASA Astrophysics Data System (ADS)

Manara, D.; Boboridis, K.; Morel, S.; De Bruycker, F.

2015-11-01

The UC2-x - carbon eutectic has been studied by laser heating and fast multi-wavelength pyrometry under inert atmosphere. The study has been carried out on three compositions, two of which close to the phase boundary of the UC2-x - C miscibility gap (with C/U atomic ratios 2 and 2.1), and one, more crucial, with a large excess of carbon (C/U = 2.82). The first two compositions were synthesised by arc-melting. This synthesis method could not be applied to the last composition, which was therefore completed directly by laser irradiation. The U - C - O composition of the samples was checked by using a combustion method in an ELTRA® analyser. The eutectic temperature, established to be 2737 K ± 20 K, was used as a radiance reference together with the cubic - tetragonal (α → β) solid state transition, fixed at 2050 K ± 20 K. The normal spectral emissivity of the carbon-richer compounds increases up to 0.7, whereas the value 0.53 was established for pure hypostoichiometric uranium dicarbide at the limit of the eutectic region. This increase is analysed in the light of the demixing of excess carbon, and used for the determination of the liquidus temperature (3220 K ± 50 K for UC2.82). Due to fast solid state diffusion, also fostered by the cubic - tetragonal transition, no obvious signs of a lamellar eutectic structure could be observed after quenching to room temperature. The eutectic surface C/UC2-x composition could be qualitatively, but consistently, followed during the cooling process with the help of the recorded radiance spectra. Whereas the external liquid surface is almost entirely constituted by uranium dicarbide, it gets rapidly enriched in demixed carbon upon freezing. Demixed carbon seems to quickly migrate towards the inner bulk during further cooling. At the α → β transition, uranium dicarbide covers again the almost entire external surface.

Inhibition of Listeria monocytogenes in Hot Dogs by Surface Application of Freeze-Dried Bacteriocin-Containing Powders from Lactic Acid Bacteria.

PubMed

Ünlü, Gülhan; Nielsen, Barbara; Ionita, Claudia

2016-06-01

Six lactic acid bacteria (LAB) strains, Lactococcus lactis BFE 920, L. lactis subsp. lactis ATCC 11454, L. lactis subsp. cremoris ATCC 14365, Lactobacillus curvatus L442, Lact. curvatus LTH 1174, and Lact. bavaricus MN, were grown in cheddar cheese whey supplemented with complex nutrient sources. Cell-free culture supernatants were freeze-dried, and the resulting bacteriocin-containing powders were applied on the surface of hot dogs that were inoculated (~4 log cfu/hot dog) with a five-strain Listeria monocytogenes cocktail. Hot dogs were vacuum-sealed and stored at 4 °C for 4 weeks. L. monocytogenes was enumerated, using both tryptic soy agar (TSA) and oxford listeria agar (OXA), on day 0 and at 1, 2, 3, and 4 weeks of the refrigerated storage. In hot dogs containing only the L. monocytogenes inoculum, L. monocytogenes counts increased from 4 up to 7 log cfu/hot dog. All samples containing freeze-dried bacteriocin-containing powders exhibited significantly lowered (P < 0.05) L. monocytogenes populations on the surface of hot dogs throughout the 4-week study except for bavaricin MN powder. Bacterial counts on hot dogs packed without any powder were statistically equal on day 0 when enumerated on OXA. Freeze-dried bacteriocin-containing powders from Lact. curvatus L442 and L. lactis subsp. cremoris ATCC 14365 decreased L. monocytogenes populations on the surface of hot dogs by greater than 2 log cfu/hot dog throughout the 4-week study. For the powdered bacteriocin preparations from L. lactis BFE 920, L. lactis subsp. lactis ATCC 11454, and Lact. curvatus LTH 1174, L. monocytogenes populations were determined to be approximately 3-log cfu/hot dog after 4 weeks of storage.

THE ACTION OF EXTREME COLD ON LEUKEMIC CELLS OF MICE

PubMed Central

Breedis, Charles

1942-01-01

Suspensions of leukemic cells of mice from three different strains of leukemia were subjected to rapid or slow freezing and rapid or slow thawing. Suspensions rapidly frozen to –196°C. were in all cases innocuous, whereas those frozen slowly were capable of transmitting leukemia. The infectivity of slowly frozen material varied from an estimated 0.0001 per cent to 1 per cent of that of fresh material, and this figure probably represents the percentage of surviving leukemic cells. Particles of spleen and lymph node reacted to slow and rapid freezing in the same manner as suspensions prepared from them. For one of the strains rapid thawing was less injurious than slow thawing; for the other two the rate of thawing seemed to be immaterial. Infectivity was equally well preserved after freezing to –21°C. whether freezing occurred spontaneously after supercooling or was initiated near the freezing point by inoculation with ice, or whether thawing was slow or rapid. Suspensions already slowly frozen at temperatures of –2° or lower, whether spontaneously or by inoculation with ice, could no longer be completely inactivated by subsequent rapid cooling to –196°C. Unfrozen suspensions initially above the freezing point or supercooled to –2°C. or –8°C. and then rapidly cooled to –196°C. were inactivated. This protective action of previous slow freezing was most marked when the initial temperature of the frozen suspension was –15°C. or lower; when it was –2°C. protection was barely detected. These observations indicate that the changes which are peculiar to rapid freezing alone and lead to complete inactivation take place during rapid transition from the liquid to the solid state, in a range of temperature lying between –15°C. and the freezing point. Temperature measurements carried out in this range showed that suspensions were about equally infections whether the temperature at their centers dropped from 0°C. to –15°C. in 30 minutes or in 1 minute; when the drop occurred in 12 seconds or less, the suspensions became innocuous. PMID:19871231

Reduced pressure ice fog technique for controlled ice nucleation during freeze-drying.

PubMed

Patel, Sajal M; Bhugra, Chandan; Pikal, Michael J

2009-01-01

A method to achieve controlled ice nucleation during the freeze-drying process using an ice fog technique was demonstrated in an earlier report. However, the time required for nucleation was about 5 min, even though only one shelf was used, which resulted in Ostwald ripening (annealing) in some of the vials that nucleated earlier than the others. As a result, the ice structure was not optimally uniform in all the vials. The objective of the present study is to introduce a simple variation of the ice fog method whereby a reduced pressure in the chamber is utilized to allow more rapid and uniform freezing which is also potentially easier to scale up. Experiments were conducted on a lab scale freeze dryer with sucrose as model compound at different concentration, product load, and fill volume. Product resistance during primary drying was measured using manometric temperature measurement. Specific surface area of the freeze-dried cake was also determined. No difference was observed either in average product resistance or specific surface area for the different experimental conditions studied, indicating that with use of the reduced pressure ice fog technique, the solutions nucleated at very nearly the same temperature (-10 degrees C). The striking feature of the "Reduced Pressure Ice Fog Technique" is the rapid ice nucleation (less than a minute) under conditions where the earlier procedure required about 5 min; hence, effects of variable Ostwald ripening were not an issue.

Water deficit severity during berry development alters onset of dormancy transitions in wine grape cultivar Malbec

USDA-ARS?s Scientific Manuscript database

Dormancy is a survival strategy for withstanding exposure to adverse environmental conditions. Grapevines (Vitis vinifera L.) are often exposed to water deficits during the growing season and freezing temperatures during winter, yet the influence of water stress on dormancy has received little resea...

A Photographic Study of Freezing of Water Droplets Falling Freely in Air

NASA Technical Reports Server (NTRS)

Dorsch, Robert G.; Levine, Joseph

1952-01-01

A photographic technique for investigating water droplets of diameter less than 200 microns falling freely in air at temperatures between 0 C and -50 C has been devised and used to determine: (i) The shape of frozen droplets (2) The occurrence of collisions of partly frozen or of frozen and liquid droplets (3) The statistics on the freezing temperatures of individual free-falling droplets A considerable number of droplets were found to have a nonspherical shape after freezing because of various protuberances and frost growth, and droplet aggregates formed by collision. The observed frequency of collision of partly frozen droplets showed good order of magnitude agreement with the frequency computed from theoretical collection efficiencies. The freezing temperature statistics indicated a general similarity of the data to those obtained for droplets frozen on a metallic surface in previous experiments.

Kinetics of Water Loss from Cells at Subzero Temperatures and the Likelihood of Intracellular Freezing

PubMed Central

Mazur, Peter

1963-01-01

The survival of various cells subjected to low temperature exposure is higher when they are cooled slowly. This increase is consistent with the view that slow cooling decreases the probability of intracellular freezing by permitting water to leave the cell rapidly enough to keep the protoplasm at its freezing point. The present study derives a quantitative relation between the amount of water in a cell and temperature. The relation is a differential equation involving cooling rate, surface-volume ratio, membrane permeability to water, and the temperature coefficient of the permeability constant. Numerical solutions to this equation give calculated water contents which permit predictions as to the likelihood of intracellular ice formation. Both the calculated water contents and the predictions on internal freezing are consistent with the experimental observations of several investigators. PMID:14085017

DEVELOPMENT OF A MODEL TO INVESTIGATE RED BLOOD CELL SURFACE CHARACTERISTICS AFTER CRYOPRESERVATION.

PubMed

Gordiyenko, O I; Anikieieva, M O; Rozanova, S L; Kovalenko, S Ye; Kovalenkol, I F; Gordiyenko, E O

2015-01-01

Maintaining cell surface properties after freezing and thawing, characterized in particular by the surface potential and associated with it cell ability to intercellular adhesion, could be used as a characteristic of successful cryopreservation. This study was conducted to research applying different erythrocytes freezing modes and analyses the regimes cryopreservation effect on the cell surface charge and adhesion to microorganisms. Human erythrocytes frozen by three modes. In order to determine adhesion index was used dried bacterial cells of S. thermophilus. The surface charge of erythrocytes was evaluated using Alcian blue cationic dye. The results showed the significant decrease in the lactobacillus adhesion to erythrocytes frozen glycerol and 1,2-propanediol. After erythrocytes were freezen with glycerol and 1,2-propanediol, the cationic dye binding to erythrocytes significantly reduced. AB binding to erythrocytes frozen with PEG-1500 does not differ from control data. Erythrocytes frozen with PEG-1500 mantained surface properties after thawing better, compared to erythrocytes cryopreserved by other methods.

Low-cost rural surface alternatives : tech transfer summary.

DOT National Transportation Integrated Search

2013-12-01

Freezing-thawing action induces physical changes to granular surface : roads that can negatively impact public users, reduce emergency : responder access/time, and result in maintenance costs for secondary : road departments. Stabilization can help r...

The WeIzmann Supercooled Droplets Observation on a Microarray (WISDOM) and application for ambient dust

NASA Astrophysics Data System (ADS)

Reicher, Naama; Segev, Lior; Rudich, Yinon

2018-01-01

The WeIzmann Supercooled Droplets Observation on Microarray (WISDOM) is a new setup for studying ice nucleation in an array of monodisperse droplets for atmospheric implications. WISDOM combines microfluidics techniques for droplets production and a cryo-optic stage for observation and characterization of freezing events of individual droplets. This setup is designed to explore heterogeneous ice nucleation in the immersion freezing mode, down to the homogeneous freezing of water (235 K) in various cooling rates (typically 0.1-10 K min-1). It can also be used for studying homogeneous freezing of aqueous solutions in colder temperatures. Frozen fraction, ice nucleation active surface site densities and freezing kinetics can be obtained from WISDOM measurements for hundreds of individual droplets in a single freezing experiment. Calibration experiments using eutectic solutions and previously studied materials are described. WISDOM also allows repeatable cycles of cooling and heating for the same array of droplets. This paper describes the WISDOM setup, its temperature calibration, validation experiments and measurement uncertainties. Finally, application of WISDOM to study the ice nucleating particle (INP) properties of size-selected ambient Saharan dust particles is presented.

Particle size distribution of wheat starch granules in relation to baking properties of frozen dough.

PubMed

Tao, Han; Wang, Pei; Wu, Fengfeng; Jin, Zhengyu; Xu, Xueming

2016-02-10

The impact of freezing on the wheat starches with different particle size was studied using a range of characterization methods including X-ray diffraction, differential scanning calorimetry, the Rapid Visco Analyser and a reconstitution dough system. Wheat starches were fractionated into A- and B-type granules, and then subjected to freezing/thawing treatment for 3 cycles. The freezing treatment did not cause apparent damage on A-type granular surface but induced cracked structure on B-type granules. It facilitated materials such as amylose, proteins, and lipids leaching from starch granule and an increase in gelatinization temperatures, melting enthalpy, and pasting viscosities. A smaller bread specific volume was obtained from freezing-treated B-granules while the crumb firmness significantly increased (p>0.05). No marked differences were observed in the counterparts of A-granules after freezing treatment. It seemed that the B-type granules were more sensitive to the freezing/thawing treatment, thus facilitating structural transformations from dough to bread. Results indicated that the deterioration in frozen bread quality derived from starch could be minimized by increasing the A-granules content. Copyright © 2015 Elsevier Ltd. All rights reserved.

Analysis of isothermal and cooling-rate-dependent immersion freezing by a unifying stochastic ice nucleation model

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alpert, Peter A.; Knopf, Daniel A.

Immersion freezing is an important ice nucleation pathway involved in the formation of cirrus and mixed-phase clouds. Laboratory immersion freezing experiments are necessary to determine the range in temperature, T, and relative humidity, RH, at which ice nucleation occurs and to quantify the associated nucleation kinetics. Typically, isothermal (applying a constant temperature) and cooling-rate-dependent immersion freezing experiments are conducted. In these experiments it is usually assumed that the droplets containing ice nucleating particles (INPs) all have the same INP surface area (ISA); however, the validity of this assumption or the impact it may have on analysis and interpretation of the experimentalmore » data is rarely questioned. Descriptions of ice active sites and variability of contact angles have been successfully formulated to describe ice nucleation experimental data in previous research; however, we consider the ability of a stochastic freezing model founded on classical nucleation theory to reproduce previous results and to explain experimental uncertainties and data scatter. A stochastic immersion freezing model based on first principles of statistics is presented, which accounts for variable ISA per droplet and uses parameters including the total number of droplets, N tot, and the heterogeneous ice nucleation rate coefficient, J het( T). This model is applied to address if (i) a time and ISA-dependent stochastic immersion freezing process can explain laboratory immersion freezing data for different experimental methods and (ii) the assumption that all droplets contain identical ISA is a valid conjecture with subsequent consequences for analysis and interpretation of immersion freezing. The simple stochastic model can reproduce the observed time and surface area dependence in immersion freezing experiments for a variety of methods such as: droplets on a cold-stage exposed to air or surrounded by an oil matrix, wind and acoustically levitated droplets, droplets in a continuous-flow diffusion chamber (CFDC), the Leipzig aerosol cloud interaction simulator (LACIS), and the aerosol interaction and dynamics in the atmosphere (AIDA) cloud chamber. Observed time-dependent isothermal frozen fractions exhibiting non-exponential behavior can be readily explained by this model considering varying ISA. An apparent cooling-rate dependence of J het is explained by assuming identical ISA in each droplet. When accounting for ISA variability, the cooling-rate dependence of ice nucleation kinetics vanishes as expected from classical nucleation theory. Finally, the model simulations allow for a quantitative experimental uncertainty analysis for parameters N tot, T, RH, and the ISA variability. We discuss the implications of our results for experimental analysis and interpretation of the immersion freezing process.« less

Analysis of isothermal and cooling-rate-dependent immersion freezing by a unifying stochastic ice nucleation model

DOE PAGES

Alpert, Peter A.; Knopf, Daniel A.

2016-02-24

Immersion freezing is an important ice nucleation pathway involved in the formation of cirrus and mixed-phase clouds. Laboratory immersion freezing experiments are necessary to determine the range in temperature, T, and relative humidity, RH, at which ice nucleation occurs and to quantify the associated nucleation kinetics. Typically, isothermal (applying a constant temperature) and cooling-rate-dependent immersion freezing experiments are conducted. In these experiments it is usually assumed that the droplets containing ice nucleating particles (INPs) all have the same INP surface area (ISA); however, the validity of this assumption or the impact it may have on analysis and interpretation of the experimentalmore » data is rarely questioned. Descriptions of ice active sites and variability of contact angles have been successfully formulated to describe ice nucleation experimental data in previous research; however, we consider the ability of a stochastic freezing model founded on classical nucleation theory to reproduce previous results and to explain experimental uncertainties and data scatter. A stochastic immersion freezing model based on first principles of statistics is presented, which accounts for variable ISA per droplet and uses parameters including the total number of droplets, N tot, and the heterogeneous ice nucleation rate coefficient, J het( T). This model is applied to address if (i) a time and ISA-dependent stochastic immersion freezing process can explain laboratory immersion freezing data for different experimental methods and (ii) the assumption that all droplets contain identical ISA is a valid conjecture with subsequent consequences for analysis and interpretation of immersion freezing. The simple stochastic model can reproduce the observed time and surface area dependence in immersion freezing experiments for a variety of methods such as: droplets on a cold-stage exposed to air or surrounded by an oil matrix, wind and acoustically levitated droplets, droplets in a continuous-flow diffusion chamber (CFDC), the Leipzig aerosol cloud interaction simulator (LACIS), and the aerosol interaction and dynamics in the atmosphere (AIDA) cloud chamber. Observed time-dependent isothermal frozen fractions exhibiting non-exponential behavior can be readily explained by this model considering varying ISA. An apparent cooling-rate dependence of J het is explained by assuming identical ISA in each droplet. When accounting for ISA variability, the cooling-rate dependence of ice nucleation kinetics vanishes as expected from classical nucleation theory. Finally, the model simulations allow for a quantitative experimental uncertainty analysis for parameters N tot, T, RH, and the ISA variability. We discuss the implications of our results for experimental analysis and interpretation of the immersion freezing process.« less

Numerical simulation of phase transition problems with explicit interface tracking

DOE PAGES

Hu, Yijing; Shi, Qiangqiang; de Almeida, Valmor F.; ...

2015-12-19

Phase change is ubiquitous in nature and industrial processes. Started from the Stefan problem, it is a topic with a long history in applied mathematics and sciences and continues to generate outstanding mathematical problems. For instance, the explicit tracking of the Gibbs dividing surface between phases is still a grand challenge. Our work has been motivated by such challenge and here we report on progress made in solving the governing equations of continuum transport in the presence of a moving interface by the front tracking method. The most pressing issue is the accounting of topological changes suffered by the interfacemore » between phases wherein break up and/or merge takes place. The underlying physics of topological changes require the incorporation of space-time subscales not at reach at the moment. Therefore we use heuristic geometrical arguments to reconnect phases in space. This heuristic approach provides new insight in various applications and it is extensible to include subscale physics and chemistry in the future. We demonstrate the method on applications such as simulating freezing, melting, dissolution, and precipitation. The later examples also include the coupling of the phase transition solution with the Navier-Stokes equations for the effect of flow convection.« less

Competing magnetic interactions and low temperature magnetic phase transitions in composite multiferroics

NASA Astrophysics Data System (ADS)

Borkar, Hitesh; Choudhary, R. J.; Singh, V. N.; Tomar, M.; Gupta, Vinay; Kumar, Ashok

2015-08-01

Novel magnetic properties and magnetic interactions in composite multiferroic oxides Pb[(Zr0.52Ti0.48)0.60(Fe0.67W0.33).40]O3]0.80-[CoFe2O4]0.20 (PZTFW-CFO) have been studied from 50 to 1000 Oe field cooled (FC) and zero field cooled (ZFC) probing conditions, and over a wide range of temperatures (4-350 K). Crystal structure analysis, surface morphology, and high resolution transmission electron microscopy images revealed the presence of two distinct phases, where micro- and nano-size spinel CFO were embedded in tetragonal PZTFW matrix and applied a significant built-in compressive strain (˜0.4-0.8%). Three distinct magnetic phase transitions were observed with the subtle effect of CFO magnetic phase on PZTFW magnetic phase transitions below the blocking temperature (TB). Temperature dependence magnetic property m(T) shows a clear evidence of spin freezing in magnetic order with lowering in thermal vibration. Chemical inhomogeneity and confinement of nanoscale ferrimagnetic phase in paramagnetic/antiferromagnetic matrix restrict the long range interaction of spin which in turn develop a giant spin frustration. A large divergence in the FC and ZFC data and broad hump in ZFC data near 200 (±10) K were observed which suggests that large magnetic anisotropy and short range order magnetic dipoles lead to the development of superparamagnetic states in composite.

A comprehensive laboratory study on the immersion freezing behavior of illite NX particles: a comparison of 17 ice nucleation measurement techniques

NASA Astrophysics Data System (ADS)

Hiranuma, N.; Augustin-Bauditz, S.; Bingemer, H.; Budke, C.; Curtius, J.; Danielczok, A.; Diehl, K.; Dreischmeier, K.; Ebert, M.; Frank, F.; Hoffmann, N.; Kandler, K.; Kiselev, A.; Koop, T.; Leisner, T.; Möhler, O.; Nillius, B.; Peckhaus, A.; Rose, D.; Weinbruch, S.; Wex, H.; Boose, Y.; DeMott, P. J.; Hader, J. D.; Hill, T. C. J.; Kanji, Z. A.; Kulkarni, G.; Levin, E. J. T.; McCluskey, C. S.; Murakami, M.; Murray, B. J.; Niedermeier, D.; Petters, M. D.; O'Sullivan, D.; Saito, A.; Schill, G. P.; Tajiri, T.; Tolbert, M. A.; Welti, A.; Whale, T. F.; Wright, T. P.; Yamashita, K.

2015-03-01

Immersion freezing is the most relevant heterogeneous ice nucleation mechanism through which ice crystals are formed in mixed-phase clouds. In recent years, an increasing number of laboratory experiments utilizing a variety of instruments have examined immersion freezing activity of atmospherically relevant ice-nucleating particles. However, an intercomparison of these laboratory results is a difficult task because investigators have used different ice nucleation (IN) measurement methods to produce these results. A remaining challenge is to explore the sensitivity and accuracy of these techniques and to understand how the IN results are potentially influenced or biased by experimental parameters associated with these techniques. Within the framework of INUIT (Ice Nuclei Research Unit), we distributed an illite-rich sample (illite NX) as a representative surrogate for atmospheric mineral dust particles to investigators to perform immersion freezing experiments using different IN measurement methods and to obtain IN data as a function of particle concentration, temperature (T), cooling rate and nucleation time. A total of 17 measurement methods were involved in the data intercomparison. Experiments with seven instruments started with the test sample pre-suspended in water before cooling, while 10 other instruments employed water vapor condensation onto dry-dispersed particles followed by immersion freezing. The resulting comprehensive immersion freezing data set was evaluated using the ice nucleation active surface-site density, ns, to develop a representative ns(T) spectrum that spans a wide temperature range (-37 °C < T < -11 °C) and covers 9 orders of magnitude in ns. In general, the 17 immersion freezing measurement techniques deviate, within a range of about 8 °C in terms of temperature, by 3 orders of magnitude with respect to ns. In addition, we show evidence that the immersion freezing efficiency expressed in ns of illite NX particles is relatively independent of droplet size, particle mass in suspension, particle size and cooling rate during freezing. A strong temperature dependence and weak time and size dependence of the immersion freezing efficiency of illite-rich clay mineral particles enabled the ns parameterization solely as a function of temperature. We also characterized the ns(T) spectra and identified a section with a steep slope between -20 and -27 °C, where a large fraction of active sites of our test dust may trigger immersion freezing. This slope was followed by a region with a gentler slope at temperatures below -27 °C. While the agreement between different instruments was reasonable below ~ -27 °C, there seemed to be a different trend in the temperature-dependent ice nucleation activity from the suspension and dry-dispersed particle measurements for this mineral dust, in particular at higher temperatures. For instance, the ice nucleation activity expressed in ns was smaller for the average of the wet suspended samples and higher for the average of the dry-dispersed aerosol samples between about -27 and -18 °C. Only instruments making measurements with wet suspended samples were able to measure ice nucleation above -18 °C. A possible explanation for the deviation between -27 and -18 °C is discussed. Multiple exponential distribution fits in both linear and log space for both specific surface area-based ns(T) and geometric surface area-based ns(T) are provided. These new fits, constrained by using identical reference samples, will help to compare IN measurement methods that are not included in the present study and IN data from future IN instruments.

Synergistic method for boreal soil moisture and soil freeze retrievals using active and passive microwave instruments

NASA Astrophysics Data System (ADS)

Smolander, Tuomo; Lemmetyinen, Juha; Rautiainen, Kimmo; Schwank, Mike; Pulliainen, Jouni

2017-04-01

Soil moisture and soil freezing are important for diverse hydrological, biogeochemical, and climatological applications. They affect surface energy balance, surface and subsurface water flow, and exchange rates of carbon with the atmosphere. Soil freezing controls important biogeochemical processes, like photosynthetic activity of plants and microbial activity within soils. Permafrost covers approximately 24% of the land surface in the Northern Hemisphere and seasonal freezing occurs on approximately 51% of the area. The retrieval method presented is based on an inversion technique and applies a semiempirical backscattering model that describes the dependence of radar backscattering of forest as a function of stem volume, soil permittivity, the extinction coefficient of forest canopy, surface roughness, incidence angle, and radar frequency. It gives an estimate of soil permittivity using active microwave measurements. Applying a Bayesian assimilation scheme, it is also possible to use other soil permittivity retrievals to regulate this estimate to combine for example low resolution passive observations with high resolution active observations for a synergistic retrieval. This way the higher variance in the active retrieval can be constricted with the passive retrieval when at the same time the spatial resolution of the product is improved compared to the passive-only retrieval. The retrieved soil permittivity estimate can be used to detect soil freeze/thaw state by considering the soil to be frozen when the estimate is below a threshold value. The permittivity retrieval can also be used to estimate the relative moisture of the soil. The method was tested using SAR (Synthetic Aperture Radar) measurements from ENVISAT ASAR instrument for the years 2010-2012 and from Sentinel-1 satellite for the years 2015-2016 in Sodankylä area in Northern Finland. The synergistic method was tested combining the SAR measurements with a SMOS (Soil Moisture Ocean Salinity) radiometer based retrieval. The results were validated using in situ measurements from automatic soil state observation stations in Sodankylä calibration and validation (CAL-VAL) site, which is a reference site for several EO (Earth Observation) data products.

A novel particle engineering technology to enhance dissolution of poorly water soluble drugs: spray-freezing into liquid.

PubMed

Rogers, True L; Nelsen, Andrew C; Hu, Jiahui; Brown, Judith N; Sarkari, Marazban; Young, Timothy J; Johnston, Keith P; Williams, Robert O

2002-11-01

A novel cryogenic spray-freezing into liquid (SFL) process was developed to produce microparticulate powders consisting of an active pharmaceutical ingredient (API) molecularly embedded within a pharmaceutical excipient matrix. In the SFL process, a feed solution containing the API was atomized beneath the surface of a cryogenic liquid such that the liquid-liquid impingement between the feed and cryogenic liquids resulted in intense atomization into microdroplets, which were frozen instantaneously into microparticles. The SFL micronized powder was obtained following lyophilization of the frozen microparticles. The objective of this study was to develop a particle engineering technology to produce micronized powders of the hydrophobic drug, danazol, complexed with hydroxypropyl-beta-cyclodextrin (HPbetaCD) and to compare these SFL micronized powders to inclusion complex powders produced from other techniques, such as co-grinding of dry powder mixtures and lyophilization of bulk solutions. Danazol and HPbetaCD were dissolved in a water/tetrahydrofuran cosolvent mixture prior to SFL processing or slow freezing. Identical quantities of the API and HPbetaCD used in the solutions were co-ground in a mortar and pestle and blended to produce a co-ground physical mixture for comparison. The powder samples were characterized by differential scanning calorimetry (DSC), powder X-ray diffraction (XRD), Fourier transform infrared spectrometry (FTIR), scanning electron microscopy, surface area analysis, and dissolution testing. The results provided by DSC, XRD, and FTIR suggested the formation of inclusion complexes by both slow-freezing and SFL. However, the specific surface area was significantly higher for the latter. Dissolution results suggested that equilibration of the danazol/HPbetaCD solution prior to SFL processing was required to produce the most soluble conformation of the resulting inclusion complex following SFL. SFL micronized powders exhibited better dissolution profiles than the slowly frozen aggregate powder. Results indicated that micronized SFL inclusion complex powders dissolved faster in aqueous dissolution media than inclusion complexes formed by conventional techniques due to higher surface areas and stabilized inclusion complexes obtained by ultra-rapid freezing.

Negligible carrier freeze-out facilitated by impurity band conduction in highly p-type GaN

NASA Astrophysics Data System (ADS)

Gunning, Brendan; Lowder, Jonathan; Moseley, Michael; Alan Doolittle, W.

2012-08-01

Highly p-type GaN films with hole concentrations exceeding 6 × 1019 cm-3 grown by metal-modulated epitaxy are electrically characterized. Temperature-dependent Hall effect measurements at cryogenic temperatures reveal minimal carrier freeze-out in highly doped samples, while less heavily doped samples exhibited high resistivity and donor-compensated conductivity as is traditionally observed. Effective activation energies as low as 43 meV were extracted, and a maximum Mg activation efficiency of 52% was found. In addition, the effective activation energy was found to be negatively correlated to the hole concentration. These results indicate the onset of the Mott-Insulator transition leading to impurity band conduction.

Applicability of Satellite Freeze Forecasting and Cold Climate Mapping to the Other Parts of the United States

NASA Technical Reports Server (NTRS)

1981-01-01

Tasks performed to determine the value of using GOES satellite thermal imagery to enhance fruit crop production in Michigan are described. An overview is presented of the system developed for image processing and thermal image and surface environmental data bases prepared to assess the physical models developed in Florida. These data bases were used to identify correlations between satellite apparent temperatures patterns and Earth surface factors. Significant freeze events in 1981 and the physical models used to provide a perspective on how Florida models can be applied in the context of the Michigan environment are discussed.

Determination of Intracellular Vitrification Temperatures for Unicellular Micro Organisms under Conditions Relevant for Cryopreservation.

PubMed

Fonseca, Fernanda; Meneghel, Julie; Cenard, Stéphanie; Passot, Stéphanie; Morris, G John

2016-01-01

During cryopreservation ice nucleation and crystal growth may occur within cells or the intracellular compartment may vitrify. Whilst previous literature describes intracellular vitrification in a qualitative manner, here we measure the intracellular vitrification temperature of bacteria and yeasts under conditions relevant to cryopreservation, including the addition of high levels of permeating and nonpermeating additives and the application of rapid rates of cooling. The effects of growth conditions that are known to modify cellular freezing resistance on the intracellular vitrification temperature are also examined. For bacteria a plot of the activity on thawing against intracellular glass transition of the maximally freeze-concentrated matrix (Tg') shows that cells with the lowest value of intracellular Tg' survive the freezing process better than cells with a higher intracellular Tg'. This paper demonstrates the role of the physical state of the intracellular environment in determining the response of microbial cells to preservation and could be a powerful tool to be manipulated to allow the optimization of methods for the preservation of microorganisms.

Freezing and melting water in lamellar structures.

PubMed Central

Gleeson, J T; Erramilli, S; Gruner, S M

1994-01-01

The manner in which ice forms in lamellar suspensions of dielaidoylphosphatidylethanolamine, dielaidoylphosphatidylcholine, and dioleoylphosphatidylcholine in water depends strongly on the water fraction. For weight fractions between 15 and 9%, the freezing and melting temperatures are significantly depressed below 0 degree C. The ice exhibits a continuous melting transition spanning as much as 20 degrees C. When the water weight fraction is below 9%, ice never forms at temperatures as low as -40 degrees C. We show that when water contained in a lamellar lipid suspension freezes, the ice is not found between the bilayers; it exists as pools of crystalline ice in equilibrium with the bound water associated with the polar lipid headgroups. We have used this effect, together with the known chemical potential of ice, to measure hydration forces between lipid bilayers. We find exponentially decaying hydration repulsion when the bilayers are less than about 7 A apart. For larger separations, we find significant deviations from single exponential decay. PMID:7948683

Influence of Emulsified Asphalt on the Mechanical Property and Microstructure of Cement-Stabilized Gravel under Freezing and Thawing Cycle Conditions.

PubMed

Wang, Yiqi; Tan, Yiqiu; Guo, Meng; Wang, Xinglong

2017-05-06

Properties of cement-stabilized gravel modified by emulsified asphalt under freezing and thawing cycle conditions were investigated by adjusting the dosage of cement. Mercury intrusion porosimetry (MIP) and Scanning electron microscopy (SEM) were introduced to analyze the influential mechanism. The results indicate that cement emulsified asphalt stabilized gravel with 5 wt % of cement performed well in both mechanics and frost-resistance. Although the addition of emulsified asphalt would lead to a partial decrease of strength, it can extend the process of strength loss and improve the freezing resistance. The main reason for this is that the permeability can be improved by the filling effects of emulsified asphalt. The frost-heave stress caused by the phase transition of water can also be remitted by emulsified asphalt, the elasticity modulus of which is much lower than the matrix. The generating speed of the micro crack can also be slowed down by emulsified asphalt.

Improvement of fish freshness determination method by the application of amorphous freeze-dried enzymes.

PubMed

Srirangsan, Paveena; Hamada-Sato, Naoko; Kawai, Kiyoshi; Watanabe, Manabu; Suzuki, Toru

2010-12-08

Alkaline phosphatase (ALP), nucleoside phosphorylase (NP), and xanthine oxidase (XOD) were used in a colorimetric method for evaluation of fish freshness based on the Ki value. Two enzyme mixtures, NP-XOD and ALP-NP-XOD, were prepared with a color developing agent, and stabilities of the enzymes were improved by freeze-drying with glass-forming additives, i.e., sucrose and sucrose-gelatin. As a result, a linear relationship was obtained between the Ki values determined by the developed colorimetric method and a conventional high-performance liquid chromatography with a high correlation coefficient of 0.997. All enzyme samples containing the additive(s) were amorphous, and higher enzymes activities were maintained compared to those freeze-dried without an additive. Sucrose-gelatin/enzyme mixtures showed higher glass transition temperature; consequently, the enzymes were better stabilized than the sucrose/enzyme formulations. Using the sucrose-gelatin/enzyme mixture, Ki values of fish meat could be accurately determined even after 6-month storage of the dried enzymes at 40 °C.

Computational thermo-hydro-mechanics for freezing and thawing multiphase geological media in the finite deformation range

NASA Astrophysics Data System (ADS)

Sun, W.; Na, S.

2017-12-01

A stabilized thermo-hydro-mechanical (THM) finite element model is introduced to investigate the freeze-thaw action of frozen porous media in the finite deformation range. By applying the mixture theory, frozen soil is idealized as a composite consisting of three phases, i.e., solid grain, unfrozen water and ice crystal. A generalized hardening rule at finite strain is adopted to replicate how the elasto-plastic responses and critical state evolve under the influence of phase transitions and heat transfer. The enhanced particle interlocking and ice strengthening during the freezing processes and the thawing-induced consolidation at the geometrical nonlinear regimes are both replicated in numerical examples. The numerical issues due to lack of two-fold inf-sup condition and ill-conditioning of the system of equations are addressed. Numerical examples for engineering applications at cold region are analyzed via the proposed model to predict the impacts of changing climate on infrastructure at cold regions.

Surface crystallization of supercooled water in clouds

PubMed Central

Tabazadeh, A.; Djikaev, Y. S.; Reiss, H.

2002-01-01

The process by which liquid cloud droplets homogeneously crystallize into ice is still not well understood. The ice nucleation process based on the standard and classical theory of homogeneous freezing initiates within the interior volume of a cloud droplet. Current experimental data on homogeneous freezing rates of ice in droplets of supercooled water, both in air and emulsion oil samples, show considerable scatter. For example, at −33°C, the reported volume-based freezing rates of ice in supercooled water vary by as many as 5 orders of magnitude, which is well outside the range of measurement uncertainties. Here, we show that the process of ice nucleus formation at the air (or oil)-liquid water interface may help to explain why experimental results on ice nucleation rates yield different results in different ambient phases. Our results also suggest that surface crystallization of ice in cloud droplets can explain why low amounts of supercooled water have been observed in the atmosphere near −40°C. PMID:12456877

Methods and apparatus for producing cryogenic inertially driven fusion targets

DOEpatents

Miller, John R.

1981-01-01

A new technique for producing uniform layers of solid DT on microballoon surfaces. Local heating of the target, typically by means of a focused laser, within an isothermal freezing cell containing a low pressure cryogenic exchange gas such as helium, vaporizes the DT fuel. Removal of the laser heating source causes the DT gas to rapidly condense and freeze in a layer which exhibits a good degree of uniformity.

Fluid insulation to prevent ice formation in heat exchangers

NASA Technical Reports Server (NTRS)

Coffinberry, G. A.

1973-01-01

Heat transfer surfaces were insulated to maintain air side surface temperature above freezing. Double wall tubes, with annular space between tubes, were filled with static liquid hydrogen. Low thermal conductivity of this hydrogen provided thermal resistance.

Low-cost rural surface alternatives : demonstration project.

DOT National Transportation Integrated Search

2015-06-01

The goals of this project were to implement several stabilization methods for preventing or mitigating freeze-thaw damage to : granular surfaced roads and identify the most effective and economical methods for the soil and climate conditions of Iowa....

Temperature measurement of supercooled droplet in icing phenomenon by means of dual-luminescent imaging

NASA Astrophysics Data System (ADS)

Tanaka, M.; Morita, K.; Mamori, H.; Fukushima, N.; Yamamoto, M.

2017-08-01

The collision of a supercooled water droplet with a surface result an object creates ice accretion on the surface. The icing problem in any cold environments leads to severe damages on aircrafts, and a lot of studies on prevention and prediction techniques for icing have been conducted so far. Therefore, it is very important to know the detail of freezing mechanism of supercooled water droplets to improve the anti-and de-icing devices and icing simulation codes. The icing mechanism of a single supercooled water droplet impacting on an object surface would give us great insights for the purpose. In the present study, we develop a dual-luminescent imaging technique to measure the time-resolved temperature of a supercooled water droplet impacting on the surface under different temperature conditions. We apply this technique to measure the exact temperature of a water droplet, and to discuss the detail of the freezing process.

Optimization of a protective medium for freeze-dried Pichia membranifaciens and application of this biocontrol agent on citrus fruit.

PubMed

Niu, X; Deng, L; Zhou, Y; Wang, W; Yao, S; Zeng, K

2016-07-01

To optimize a protective medium for freeze-dried Pichia membranifaciens and to evaluate biocontrol efficacies of agents against blue and green mould and anthracnose in citrus fruit. Based on the screening assays of saccharides and antioxidants, response surface methodology was used to optimize sucrose, sodium glutamate and skim milk to improve viability of freeze-dried Pi. membranifaciens. Biocontrol assays were conducted between fresh and freeze-dried Pi. membranifaciens against Penicillium italicum, Penicillium digitatum and Colletotrichum gloeosporioides in citrus fruit. Solving the regression equation indicated that the optimal protective medium was 6·06% (w/v) sucrose combined with 3·40% (w/v) sodium glutamate and 5·43% (w/v) skim milk. Pi. membranifaciens freeze-dried in the optimal protective medium showed 76·80% viability, and retained biocontrol efficacy against Pe. italicum, Pe. digitatum and Co. gloeosporioides in citrus fruit. The optimal protective medium showed more effective protective properties than each of the three protectants used alone. The viability of freeze-dried Pi. membranifaciens finally reached 76·80%. Meanwhile, the biocontrol efficacies showed no significant difference between fresh and freeze-dried yeast against Pe. italicum, Pe. digitatum and Co. gloeosporioides in citrus fruit. The results showed the potential value of Pi. membranifaciens CICC 32259 for commercialization. © 2016 The Society for Applied Microbiology.

Numerical Simulation of the Freeze-Thaw Behavior of Mortar Containing Deicing Salt Solution

PubMed Central

Esmaeeli, Hadi S.; Farnam, Yaghoob; Bentz, Dale P.; Zavattieri, Pablo D.; Weiss, Jason

2016-01-01

This paper presents a one-dimensional finite difference model that is developed to describe the freeze-thaw behavior of an air-entrained mortar containing deicing salt solution. A phenomenological model is used to predict the temperature and the heat flow for mortar specimens during cooling and heating. Phase transformations associated with the freezing/melting of water/ice or transition of the eutectic solution from liquid to solid are included in this phenomenological model. The lever rule is used to calculate the quantity of solution that undergoes the phase transformation, thereby simulating the energy released/absorbed during phase transformation. Undercooling and pore size effects are considered in the numerical model. To investigate the effect of pore size distribution, this distribution is considered using the Gibbs-Thomson equation in a saturated mortar specimen. For an air-entrained mortar, the impact of considering pore size (and curvature) on freezing was relatively insignificant; however the impact of pore size is much more significant during melting. The fluid inside pores smaller than 5 nm (i.e., gel pores) has a relatively small contribution in the macroscopic freeze-thaw behavior of mortar specimens within the temperature range used in this study (i.e., +24 °C to −35 °C), and can therefore be neglected for the macroscopic freeze-thaw simulations. A heat sink term is utilized to simulate the heat dissipation during phase transformations. Data from experiments performed using a low-temperature longitudinal guarded comparative calorimeter (LGCC) on mortar specimens fully saturated with various concentration NaCl solutions or partially saturated with water is compared to the numerical results and a promising agreement is generally obtained. PMID:28082830

Cryopreservation of lipid bilayers by LEA proteins from Artemia franciscana and trehalose.

PubMed

Moore, Daniel S; Hand, Steven C

2016-10-01

The capacity of Late Embryogenesis Abundant (LEA) proteins and trehalose to protect liposomes against freezing-induced damage was examined by measuring the leakage of 5(6)-carboxyfluorescein (CF). Liposomes were prepared to simulate the lipid compositions of the inner leaflet of the plasma membrane, outer mitochondrial membrane (OMM), and inner mitochondrial membrane (IMM). Two recombinant LEA proteins belonging to Group 3 (AfrLEA2 and AfrLEA3m) were expressed and purified from embryos of Artemia franciscana. Only OMM-like liposomes were significantly protected by AfrLEA2 and AfrLEA3m against freeze-thaw damage; at the highest protein:lipid mass ratio tested, leakage of CF was 56.3% of control with AfrLEA3m and 29.3% with AfrLEA2. By comparison, trehalose provided protection to all compositional types. The greatest stabilization during freezing occurred when trehalose was present on both sides of the bilayer. When mitochondria isolated from rat liver were freeze-thawed in trehalose solution, the OMM remained intact based on the absence of increased oxygen consumption when cytochrome c was added during oxidative phosphorylation (OXPHOS). Respiratory control ratios (OXPHOS/LEAK) were depressed by only 30% after freeze-thawing in trehalose compared to non-frozen controls, which indicated some retention of OXPHOS capacity by the IMM. Trehalose then was loaded into the matrix (0.24 μmol/mg mitochondrial protein) by transient opening of the permeability transition pore, a procedure optimized for retention of OMM integrity. Surprisingly, respiratory control ratios were not improved after freeze-thawing with external plus matrix trehalose, when compared to external trehalose alone. This result could perhaps be explained by insufficient accumulation of matrix trehalose. Copyright © 2016 Elsevier Inc. All rights reserved.

Numerical Simulation of the Freeze-Thaw Behavior of Mortar Containing Deicing Salt Solution.

PubMed

Esmaeeli, Hadi S; Farnam, Yaghoob; Bentz, Dale P; Zavattieri, Pablo D; Weiss, Jason

2017-02-01

This paper presents a one-dimensional finite difference model that is developed to describe the freeze-thaw behavior of an air-entrained mortar containing deicing salt solution. A phenomenological model is used to predict the temperature and the heat flow for mortar specimens during cooling and heating. Phase transformations associated with the freezing/melting of water/ice or transition of the eutectic solution from liquid to solid are included in this phenomenological model. The lever rule is used to calculate the quantity of solution that undergoes the phase transformation, thereby simulating the energy released/absorbed during phase transformation. Undercooling and pore size effects are considered in the numerical model. To investigate the effect of pore size distribution, this distribution is considered using the Gibbs-Thomson equation in a saturated mortar specimen. For an air-entrained mortar, the impact of considering pore size (and curvature) on freezing was relatively insignificant; however the impact of pore size is much more significant during melting. The fluid inside pores smaller than 5 nm (i.e., gel pores) has a relatively small contribution in the macroscopic freeze-thaw behavior of mortar specimens within the temperature range used in this study (i.e., +24 °C to -35 °C), and can therefore be neglected for the macroscopic freeze-thaw simulations. A heat sink term is utilized to simulate the heat dissipation during phase transformations. Data from experiments performed using a low-temperature longitudinal guarded comparative calorimeter (LGCC) on mortar specimens fully saturated with various concentration NaCl solutions or partially saturated with water is compared to the numerical results and a promising agreement is generally obtained.

Monitoring Freeze-Thaw States in the Pan-Arctic: Application of Microwave Remote Sensing to Monitoring Hydrologic and Ecological Processes

NASA Astrophysics Data System (ADS)

McDonald, K. C.; Kimball, J. S.

2004-12-01

The transition of the landscape between predominantly frozen and non-frozen conditions in seasonally frozen environments impacts climate, hydrological, ecological and biogeochemical processes profoundly. Satellite microwave remote sensing is uniquely capable of detecting and monitoring a range of related biophysical processes associated with the measurement of landscape freeze/thaw status. We present the development, physical basis, current techniques and selected hydrological applications of satellite-borne microwave remote sensing of landscape freeze/thaw states for the terrestrial cryosphere. Major landscape hydrological processes embracing the remotely-sensed freeze/thaw signal include timing and spatial dynamics of seasonal snowmelt and associated soil thaw, runoff generation and flooding, ice breakup in large rivers and lakes, and timing and length of vegetation growing seasons and associated productivity and trace gas exchange. Employing both active and passive microwave sensors, we apply a selection of temporal change classification algorithms to examine a variety of hydrologic processes. We investigate contemporaneous and retrospective applications of the QuikSCAT scatterometer, and the SSM/I and SMMR radiometers to this end. Results illustrate the strong correspondence between regional thawing, seasonal ice break up for rivers, and the springtime pulse in river flow. We present the physical principles of microwave sensitivity to landscape freeze/thaw state, recent progress in applying these principles toward satellite remote sensing of freeze/thaw processes over broad regions, and potential for future global monitoring of this significant phenomenon of the global cryosphere. This work was carried out at the Jet Propulsion Laboratory, California Institute of Technology, and at the University of Montana, Missoula, under contract to the National Aeronautics and Space Administration.

Adaptive and freeze-tolerant heteronetwork organohydrogels with enhanced mechanical stability over a wide temperature range

NASA Astrophysics Data System (ADS)

Gao, Hainan; Zhao, Ziguang; Cai, Yudong; Zhou, Jiajia; Hua, Wenda; Chen, Lie; Wang, Li; Zhang, Jianqi; Han, Dong; Liu, Mingjie; Jiang, Lei

2017-06-01

Many biological organisms with exceptional freezing tolerance can resist the damages to cells from extra-/intracellular ice crystals and thus maintain their mechanical stability at subzero temperatures. Inspired by the freezing tolerance mechanisms found in nature, here we report a strategy of combining hydrophilic/oleophilic heteronetworks to produce self-adaptive, freeze-tolerant and mechanically stable organohydrogels. The organohydrogels can simultaneously use water and oil as a dispersion medium, and quickly switch between hydrogel- and organogel-like behaviours in response to the nature of the surrounding phase. Accordingly, their surfaces display unusual adaptive dual superlyophobic in oil/water system (that is, they are superhydrophobic under oil and superoleophobic under water). Moreover, the organogel component can inhibit the ice crystallization of the hydrogel component, thus enhancing the mechanical stability of organohydrogel over a wide temperature range (-78 to 80 °C). The organohydrogels may have promising applications in complex and harsh environments.

Influence of surface morphology on the immersion mode ice nucleation efficiency of hematite particles

NASA Astrophysics Data System (ADS)

Hiranuma, N.; Hoffmann, N.; Kiselev, A.; Dreyer, A.; Zhang, K.; Kulkarni, G.; Koop, T.; Möhler, O.

2014-03-01

In this paper, the effect of the morphological modification of aerosol particles with respect to heterogeneous ice nucleation is comprehensively investigated for laboratory-generated hematite particles as a model substrate for atmospheric dust particles. The surface-area-scaled ice nucleation efficiencies of monodisperse cubic hematite particles and milled hematite particles were measured with a series of expansion cooling experiments using the Aerosol Interaction and Dynamics in the Atmosphere (AIDA) cloud simulation chamber. Complementary offline characterization of physico-chemical properties of both hematite subsets were also carried out with scanning electron microscopy (SEM), energy dispersive X-ray (EDX) spectroscopy, dynamic light scattering (DLS), and an electro-kinetic particle charge detector to further constrain droplet-freezing measurements of hematite particles. Additionally, an empirical parameterization derived from our laboratory measurements was implemented in the single-column version of the Community Atmospheric Model version 5 (CAM5) to investigate the model sensitivity in simulated ice crystal number concentration on different ice nucleation efficiencies. From an experimental perspective, our results show that the immersion mode ice nucleation efficiency of milled hematite particles is almost an order of magnitude higher at -35.2 °C < T < -33.5 °C than that of the cubic hematite particles, indicating a substantial effect of morphological irregularities on immersion mode freezing. Our modeling results similarly show that the increased droplet-freezing rates of milled hematite particles lead to about one order magnitude higher ice crystal number in the upper troposphere than cubic hematite particles. Overall, our results suggest that the surface irregularities and associated active sites lead to greater ice activation through droplet freezing.

Chemistry and Spectroscopy of Frozen Chloride Salts on Icy Bodies

NASA Astrophysics Data System (ADS)

Johnson, P. V.; Thomas, E. C.; Hodyss, R. P.; Vu, T. H.; Choukroun, M.

2016-12-01

Understanding the habitability of Europa's ocean is of great interest to astrobiology and is the focus of missions currently being considered to explore Europa. Currently, our best means of constraining the subsurface ocean composition and its subsequent habitability is by further study of Europa's surface chemical composition. Analysis of existing (and future) remote sensing data is limited by the availability of spectral libraries of candidate materials under relevant conditions (temperature, thermal/radiation history, etc.). Geochemical predictions of Europa's ocean composition suggest that chloride salts are likely to exist on the surface of Europa as well as other ocean worlds. We have conducted a study of frozen chloride-salt brines prepared at temperatures, pressures and radiation conditions (UV) in order to simulate conditions on the surface of Europa and other airless bodies. Hydration states of various chloride salts as a function of temperature were determined using Raman spectroscopy. Near IR reflectance spectra of identically prepared samples were measured to provide reference spectra of the identified hydrated salts. We find that the freezing of NaCl at temperatures ranging from 80 K to 233 K forms hydrohalite. In contrast, KCl hydrates are not formed from the freezing of KCl brines. In addition, a stable hexahydrate forms from the freezing of MgCl2 solutions, while a hexahydrate, a tetrahydrate, and a dihydrate, form upon freezing of CaCl2 solutions. Salts were observed to dehydrated with increasing temperatures, leading to a succession of hydration states in the case of CaCl2. Irradiation with vacuum ultraviolet light was observed to lead to dehydration as well.

Comparative analysis of the cold acclimation and freezing tolerance capacities of seven diploid Brachypodium distachyon accessions

PubMed Central

Colton-Gagnon, Katia; Ali-Benali, Mohamed Ali; Mayer, Boris F.; Dionne, Rachel; Bertrand, Annick; Do Carmo, Sonia; Charron, Jean-Benoit

2014-01-01

Background and Aims Cold is a major constraint for cereal cultivation under temperate climates. Winter-hardy plants interpret seasonal changes and can acquire the ability to resist sub-zero temperatures. This cold acclimation process is associated with physiological, biochemical and molecular alterations in cereals. Brachypodium distachyon is considered a powerful model system to study the response of temperate cereals to adverse environmental conditions. To date, little is known about the cold acclimation and freezing tolerance capacities of Brachypodium. The main objective of this study was to evaluate the cold hardiness of seven diploid Brachypodium accessions. Methods An integrated approach, involving monitoring of phenological indicators along with expression profiling of the major vernalization regulator VRN1 orthologue, was followed. In parallel, soluble sugars and proline contents were determined along with expression profiles of two COR genes in plants exposed to low temperatures. Finally, whole-plant freezing tests were performed to evaluate the freezing tolerance capacity of Brachypodium. Key Results Cold treatment accelerated the transition from the vegetative to the reproductive phase in all diploid Brachypodium accessions tested. In addition, low temperature exposure triggered the gradual accumulation of BradiVRN1 transcripts in all accessions tested. These accessions exhibited a clear cold acclimation response by progressively accumulating proline, sugars and COR gene transcripts. However, whole-plant freezing tests revealed that these seven diploid accessions only have a limited capacity to develop freezing tolerance when compared with winter varieties of temperate cereals such as wheat and barley. Furthermore, little difference in terms of survival was observed among the accessions tested despite their previous classification as either spring or winter genotypes. Conclusions This study is the first to characterize the freezing tolerance capacities of B. distachyon and provides strong evidence that some diploid accessions such as Bd21 have a facultative growth habit. PMID:24323247

Investigation of PEG crystallization in frozen and freeze-dried PEGylated recombinant human growth hormone-sucrose systems: implications on storage stability.

PubMed

Bhatnagar, Bakul S; Martin, Susan W H; Hodge, Tamara S; Das, Tapan K; Joseph, Liji; Teagarden, Dirk L; Shalaev, Evgenyi Y; Suryanarayanan, Raj

2011-08-01

The objectives of the current study were to investigate (i) the phase behavior of a PEGylated recombinant human growth hormone (PEG-rhGH, ∼60 kDa) during freeze-drying and (ii) its storage stability. The phase transitions during freeze-thawing of an aqueous solution containing PEG-rhGH and sucrose were characterized by differential scanning calorimetry. Finally, PEG-rhGH and sucrose formulations containing low, medium, and high polyethylene glycol (PEG) to sucrose ratios were freeze-dried in dual-chamber syringes and stored at 4°C and 25°C. Chemical decomposition (methionine oxidation and deamidation) and irreversible aggregation were characterized by size-exclusion and ion-exchange chromatography, and tryptic mapping. PEG crystallization was facilitated when it was covalently linked with rhGH. When the solutions were frozen, phase separation into PEG-rich and sucrose-rich phases facilitated PEG crystallization and the freeze-dried cake contained crystalline PEG. Annealing caused PEG crystallization and when coupled with higher drying temperatures, the primary drying time decreased by up to 51%. When the freeze-dried cakes were stored at 4°C, while there was no change in the purity of the PEG-rhGH monomer, deamidation was highest in the formulations with the lowest PEG to sucrose ratio. When stored at 25°C, this composition also showed the most pronounced decrease in monomer purity, the highest level of aggregation, and deamidation. Furthermore, an increase in PEG crystallinity during storage was accompanied by a decrease in PEG-rhGH stability. Interestingly, during storage, there was no change in PEG crystallinity in formulations with medium and high PEG to sucrose ratios. Although PEG crystallization during freeze-drying did not cause protein degradation, crystallization during storage might have influenced protein stability. Copyright © 2011 Wiley-Liss, Inc.

Crystallization, melting, and structure of water nanoparticles at atmospherically relevant temperatures.

PubMed

Johnston, Jessica C; Molinero, Valeria

2012-04-18

Water nanoparticles play an important role in atmospheric processes, yet their equilibrium and nonequilibrium liquid-ice phase transitions and the structures they form on freezing are not yet fully elucidated. Here we use molecular dynamics simulations with the mW water model to investigate the nonequilibrium freezing and equilibrium melting of water nanoparticles with radii R between 1 and 4.7 nm and the structure of the ice formed by crystallization at temperatures between 150 and 200 K. The ice crystallized in the particles is a hybrid form of ice I with stacked layers of the cubic and hexagonal ice polymorphs in a ratio approximately 2:1. The ratio of cubic ice to hexagonal ice is insensitive to the radius of the water particle and is comparable to that found in simulations of bulk water around the same temperature. Heating frozen particles that contain multiple crystallites leads to Ostwald ripening and annealing of the ice structures, accompanied by an increase in the amount of ice at the expense of the liquid water, before the particles finally melt from the hybrid ice I to liquid, without a transition to hexagonal ice. The melting temperatures T(m) of the nanoparticles are not affected by the ratio of cubic to hexagonal layers in the crystal. T(m) of the ice particles decreases from 255 to 170 K with the particle size and is well described by the Gibbs-Thomson equation, T(m)(R) = T(m)(bulk) - K(GT)/(R - d), with constant K(GT) = 82 ± 5 K·nm and a premelted liquid of width d = 0.26 ± 0.05 nm, about one monolayer. The freezing temperatures also decrease with the particles' radii. These results are important for understanding the composition, freezing, and melting properties of ice and liquid water particles under atmospheric conditions. © 2012 American Chemical Society

Effect of whey protein isolate and β-cyclodextrin wall systems on stability of microencapsulated vanillin by spray-freeze drying method.

PubMed

Hundre, Swetank Y; Karthik, P; Anandharamakrishnan, C

2015-05-01

Vanillin flavour is highly volatile in nature and due to that application in food incorporation is limited; hence microencapsulation of vanillin is an ideal technique to increase its stability and functionality. In this study, vanillin was microencapsulated for the first time by non-thermal spray-freeze-drying (SFD) technique and its stability was compared with other conventional techniques such as spray drying (SD) and freeze-drying (FD). Different wall materials like β-cyclodextrin (β-cyd), whey protein isolate (WPI) and combinations of these wall materials (β-cyd + WPI) were used to encapsulate vanillin. SFD microencapsulated vanillin with WPI showed spherical shape with numerous fine pores on the surface, which in turn exhibited good rehydration ability. On the other hand, SD powder depicted spherical shape without pores and FD encapsulated powder yielded larger particle sizes with flaky structure. FTIR analysis confirmed that there was no interaction between vanillin and wall materials. Moreover, spray-freeze-dried vanillin + WPI sample exhibited better thermal stability than spray dried and freeze-dried microencapsulated samples. Copyright © 2014 Elsevier Ltd. All rights reserved.

Freeze-out conditions in proton-proton collisions at the highest energies available at the BNL Relativistic Heavy Ion Collider and the CERN Large Hadron Collider

NASA Astrophysics Data System (ADS)

Das, Sabita; Mishra, Debadeepti; Chatterjee, Sandeep; Mohanty, Bedangadas

2017-01-01

The freeze-out conditions in proton-proton collisions at √{sNN}=200 , 900, and 7000 GeV have been extracted by fits to the mean hadron yields at midrapidity within the framework of the statistical model of an ideal gas of hadrons and resonances in the grand canonical ensemble. The variation of the extracted freeze-out thermal parameters and the goodness of the fits with √{sN N} are discussed. We find the extracted temperature and baryon chemical potential of the freeze-out surface to be similar in p +p and heavy-ion collisions. On the other hand, the thermal behavior of the strange hadrons is qualitatively different in p +p as compared to A +A collisions. We find an additional parameter accounting for nonequilibrium strangeness production is essential for describing the p +p data. This is in contrast to A +A where the nonequilibrium framework could be successfully replaced by a sequential and complete equilibrium model with an early freeze-out of the strange hadrons.

The Soil Moisture Active and Passive (SMAP) Mission

NASA Technical Reports Server (NTRS)

Entekhabi, Dara; Nijoku, Eni G.; ONeill, Peggy E.; Kellogg, Kent H.; Crow, Wade T.; Edelstein, Wendy N.; Entin, Jared K.; Goodman, Shawn D.; Jackson, Thomas J.; Johnson, Joel;

Research on Heat Exchange Process in Aircraft Air Conditioning System

NASA Astrophysics Data System (ADS)

Chichindaev, A. V.

2017-11-01

Using of heat-exchanger-condenser in the air conditioning system of the airplane Tu-204 (Boeing, Airbus, Superjet 100, MS-21, etc.) for cooling the compressed air by the cold air with negative temperature exiting the turbine results in a number of operational problems. Mainly it’s frosting of the heat exchange surface, which is the cause of live-section channels frosting, resistance increasing and airflow in the system decreasing. The purpose of this work is to analyse the known freeze-up-fighting methods for heat-exchanger-condenser, description of the features of anti-icing protection and offering solutions to this problem. For the problem of optimizing the design of heat exchangers in this work used generalized criterion that describes the ratio of thermal resistances of cold and hot sections, which include: the ratio of the initial values of heat transfer agents flow state; heat exchange surface finning coefficients; factors which describes the ratio of operating parameters and finning area. By controlling the ratio of the thermal resistances can be obtained the desired temperature of the heat exchange surface, which would prevent freezing. The work presents the results of a numerical study of the effect of different combinations of regime and geometrical factors changes on reduction of the heat-exchanger-condenser freezing surface area, including using of variable ratio of thermal resistances.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Semenov, A. N.

We propose a new spin-glass model with no positional quenched disorder which is regarded as a coarse-grained model of a structural glass-former. The model is analyzed in the 1D case when the number N of states of a primary cell is large. For N → ∞, the model exhibits a sharp freezing transition of the thermodynamic origin. It is shown both analytically and numerically that the glass transition is accompanied by a significant growth of a static length scale ξ pointing to the structural (equilibrium) nature of dynamical slowdown effects in supercooled liquids.

The Chemistry and Excitation of Water in Molecular Clouds

NASA Technical Reports Server (NTRS)

Hollenbach, David

2003-01-01

We model the chemistry and thermal balance of opaque molecular clouds exposed to an external flux of ultraviolet photons. We include the processes of gas phase and grain surface chemical reactions; in particular we examine closely the freezing of atoms and molecules onto grain surfaces and the desorption of molecules from grain surfaces as a function of depth into a molecular cloud. We find that on the surface of a molecular cloud the gas phase water abundances are low because of photodissociation, and the grain phase water (ice) abundance is low because of photodesorption of water from the grain surfaces. Deeper into the cloud, at A(sub v) less than or approximately 2-8 depending on the strength of the external ultraviolet flux, the gas phase water abundance increases with depth as the photodissociation rates decline due to dust attenuation of the ultraviolet field. However, beyond A(sub v) less than or approximately 2-8 the gas phase water abundance declines because the water freezes as water ice on the grains, and photodesorption is no longer effective in clearing the ice. A peak water abundance of about 10(exp -6) to 10(exp -7) occurs at about A(sub v) approximately 2-8, relatively independent of the gas density and the ultraviolet field. We show that such a model matches very closely the observations of the Submillimeter Wave Astronomical Satellite (SWAS), a NASA Small Explorer Mission. The model elucidates several mechanisms that have been recently invoked to understand gas phase chemistry in clouds, including-the freeze-out of molecules onto grain surface, the desorption of these molecules from the surfaces, and the abundance gradients of molecules as functions of depth into molecular clouds.

Controlling the physical form of mannitol in freeze-dried systems.

PubMed

Mehta, Mehak; Bhardwaj, Sunny P; Suryanarayanan, Raj

2013-10-01

A potential drawback with the use of mannitol as a bulking agent is its existence as mannitol hemihydrate (MHH; C₆H₁₄O₆·0.5H₂O) in the lyophile. Once formed during freeze-drying, MHH dehydration may require secondary drying under aggressive conditions which can be detrimental to the stability of thermolabile components. If MHH is retained in the lyophile, the water released by MHH dehydration during storage has the potential to cause product instability. We systematically identified the conditions under which anhydrous mannitol and MHH crystallized in frozen systems with the goal of preventing MHH formation during freeze-drying. When mannitol solutions were cooled, the temperature of solute crystallization was the determinant of the physical form of mannitol. Based on low temperature X-ray diffractometry (using both laboratory and synchrotron sources), MHH formation was observed when solute crystallization occurred at temperatures ≤ -20 °C, while anhydrous mannitol crystallized at temperatures ≤ -10 °C. The transition temperature (anhydrate - MHH) appears to be ∼-15 °C. The use of a freeze-dryer with controlled ice nucleation technology enabled anhydrous mannitol crystallization at ∼-5 °C. Thus, ice crystallization followed by annealing at temperatures ≤ -10 °C can be an effective strategy to prevent MHH formation. Copyright © 2013 Elsevier B.V. All rights reserved.

Nature and morphology of fumed oxides and features of interfacial phenomena

NASA Astrophysics Data System (ADS)

Gun'ko, V. M.; Zarko, V. I.; Goncharuk, O. V.; Matkovsky, A. K.; Remez, O. S.; Skubiszewska-Zięba, J.; Wojcik, G.; Walusiak, B.; Blitz, J. P.

2016-03-01

Individual and complex fumed nanooxides were studied using high-resolution transmission electron microscopy, X-ray diffraction, ultraviolet-visible (UV-vis) spectroscopy, differential scanning calorimetry, nuclear magnetic resonance spectroscopy, adsorption, desorption (evaporation), and quantum chemical methods. For mixed nanooxides in contrast to simple and small nanoparticles of individual silica or titania, complex core-shell nanoparticles (50-200 nm in size) with titania or alumina cores and silica or alumina shells can be destroyed under high-pressure cryogelation (HPCG), mechnochemical activation (MCA) that also affect the structure of aggregates of nanoparticles and agglomerates of aggregates becoming more compacted. This is accompanied by changes in color from white to beige of different tints and changes in the UV-vis spectra in the 300-600 nm range, as well as changes in crystalline structure of alumina. Any treatment of 'soft' nanooxides affects the interfacial behavior of polar and nonpolar adsorbates. For some of them, the hysteresis loops become strongly open. Rearrangement of secondary particles affects the freezing-melting point depression. Clusterization of adsorbates bound in pores causes diminution of heat effects during phase transition (freezing, fusion). Freezing point depression and increasing melting point cause significant hysteresis freezing-melting effects for adsorbates bound to oxide nanoparticles. The study shows that complex nanooxides can be more sensitive to external actions than simple nanooxides such as silica.

Development of SMAP Mission Cal/Val Activities

NASA Technical Reports Server (NTRS)

Colliander, A.; Jackson, T.; Kimball, J.; Cosh, M.; Spencer, M.; Entekhabi, D.; Njoku, E.; ONeill, P.

2010-01-01

The Soil Moisture Active Passive (SMAP) mission is a NASA directed mission to map global land surface soil moisture and freeze-thaw state. Instrument and mission details are shown. The key SMAP soil moisture product is provided at 10 km resolution with 0.04cubic cm/cubic cm accuracy. The freeze/thaw product is provided at 3 km resolution and 80% frozen-thawed classification accuracy. The full list of SMAP data products is shown.

Apparatus for producing cryogenic inertially driven fusion targets

DOEpatents

Miller, John R.

1981-01-01

A new technique for producing uniform layers of solid DT on microballoon surfaces. Local heating of the target, typically by means of a focused laser, within an isothermal freezing cell containing a low pressure cryogenic exchange gas such as helium, vaporizes the DT fuel contained within the microballoon. Removal of the laser heating source causes the DT gas to rapidly condense and freeze in a layer which exhibits a good degree of uniformity.

Evaluation of anti-freeze viscosity modifier for potential external tank applications

NASA Technical Reports Server (NTRS)

Lynn, R. O. L.

1981-01-01

Viscosity modifiers and gelling agents were evaluated in combination with ethylene glycol and dimethyl sulfoxide water eutectics. Pectin and agarose are found to gel these eutectics effectively in low concentration, but the anti-freeze protection afforded by these compositions is found to be marginal in simulations of the intended applications. Oxygen vent shutters and vertical metallic surfaces were simulated, with water supplied as a spray, dropwise, and by condensation from the air.

The immersion freezing behavior of size-segregated soot and kaolinite particles

NASA Astrophysics Data System (ADS)

Hartmann, S.; Augustin, S.; Clauss, T.; Niedermeier, D.; Raddatz, M.; Wex, H.; Shaw, R. A.; Stratmann, F.

2011-12-01

Heterogeneous ice nucleation plays a crucial role for ice formation in mixed-phase and cirrus clouds and has an important impact on precipitation formation, global radiation balances, and therefore Earth's climate (Cantrell and Heymsfield, 2005). Mineral dust and soot particles are found to be a major component of ice crystal residues (e.g., Pratt et al., 2009) so these substances are potential sources of atmospheric ice nuclei (IN). Experimental studies investigating the immersion freezing behavior of size-segregated soot and kaolinite particles conducted at the Leipzig Aerosol Cloud Interaction Simulator (LACIS) are presented. In our measurements only one aerosol particle is immersed in an air suspended water droplet which can trigger ice nucleation. The method facilitates very precise examinations with respect to temperature, ice nucleation time and ice nucleus size. Considering laboratory studies, the picture of the IN ability of soot particles is quite heterogeneous. Our studies show that submicron flame, spark soot particles and optionally coated with sulfuric acid to simulate chemically aging do not act as IN at temperatures higher than homogeneous freezing taking place. Therefore soot particles might not be an important source of IN for immersion freezing in the atmosphere. In contrast, kaolinite being representative for natural mineral dust with a well known composition and structure is found to be very active in forming ice for all freezing modes (e.g., Mason and Maybank, 1958). Analyzing the immersion freezing behavior of different sized kaolinite particles (300, 500 and 700 nm in diameter) the size effect was clearly observed, i.e. the ice fraction (number of frozen droplets per total number) scales with particle surface, i.e. the larger the ice nucleus surface the higher the ice fraction. The slope of the logarithm of the ice fraction as function of temperature is similar for all particle sizes investigated and fits very well with the results of Lüönd et al. (2010) and Murray et al. (2011). Heterogeneous ice nucleation rate coefficients are derived which can be used to describe the immersion freezing process size-segregated in cloud microphysical models.

The role of natural mineral particles collected at one site in Patagonia as immersion freezing ice nuclei

NASA Astrophysics Data System (ADS)

López, María Laura; Borgnino, Laura; Ávila, Eldo E.

2018-05-01

This work studies the role of mineral particles collected in the region of Patagonia (Neuquén, Argentina) as ice nuclei particles (INPs) by immersion freezing mode. The particle immersion-freezing ability was analyzed under laboratory conditions by using an established drop-freezing technique. Mineralogical composition was characterized by using X-ray diffraction and electron micro probe analysis. Dynamic light scattering was used to determine the grain size distribution of particles, while the N2 adsorption and methylene blue adsorption methods were applied to determine their specific surface area. Water droplets of different volumes containing different concentrations of particles were cooled until droplets were frozen. For all the analyzed drop volumes, an increase in the freezing temperature of the drops was observed with increasing dust concentration. In the same way, the freezing temperature increased when the drop volume was increased at constant dust concentration. Both behaviors were linked to the availability of active sites in the particles. A plateau in the freezing temperature was observed at high suspension concentration for all the drop volumes. This plateau was related to the aggregation of the particles when the suspension concentration was increased and to the consequent decrease in the number of active sites. The active sites per unit of surface area were calculated and reported. For the studied range of temperature, results are in agreement with those reported for different sites and particles. From the chemical and morphological analysis of the particle components and the results obtained from the literature, it was concluded that even though montmorillonite was the main mineral in the collected sample, the accessory minerals deserve to be analyzed in detail in order to know if they could be responsible for the ability of the collected soil particles to act as INPs. Considering that the region of Patagonia has been identified as an important source of natural mineral particles in the atmosphere, it is important to analyze the ability of these particles to act as INP. As far as we know, this is the first study carrying out this investigation.

A tissue snap-freezing apparatus without sacrificial cryogens

NASA Astrophysics Data System (ADS)

Vanapalli, Srinivas; Jagga, Sahil; Holland, Harry; ter Brake, Marcel

2017-12-01

Molecular technologies in cancer diagnosis require a fresh and frozen tissue, which is obtained by means of snap-freezing. Currently, coolants such as solid carbon dioxide and liquid nitrogen are used to preserve good morphology of the tissue. Using these coolants, snap freezing of tissues for diagnostic and research purposes is often time consuming, laborious, even hazardous and not user friendly. For that reason snap-freezing is not routinely applied at the location of biopsy acquisition. Furthermore, the influence of optimal cooling rate and cold sink temperature on the viability of the cells is not well known. In this paper, a snap-freezing apparatus powered by a small cryocooler is presented that will allow bio-medical research of tissue freezing methods and is safe to use in a hospital. To benchmark this apparatus, cooldown of a standard aluminum cryo-vial in liquid nitrogen is measured and the cooling rate is about -25 K/s between 295 K and 120 K. Sufficient cooling rate is obtained by a forced convective helium gas flow through a gap formed between the cryo-vial and a cold surface and is therefore chosen as the preferred cooling method. A conceptual design of the snap-apparatus with forced flow is discussed in this paper.

Binder of Sperm Proteins protect ram spermatozoa from freeze-thaw damage.

PubMed

Pini, Taylor; Farmer, Kiri; Druart, Xavier; Teixeira-Gomes, Ana Paula; Tsikis, Guillaume; Labas, Valerie; Leahy, Tamara; de Graaf, Simon P

2018-06-01

Cryopreservation causes sub-lethal damage which limits the fertility of frozen thawed spermatozoa. Seminal plasma has been investigated as a cryoprotectant, but has yielded inconsistent results due to considerable variation in its constituents. Individual seminal plasma proteins offer an ideal alternative to whole seminal plasma, and several have been correlated with freezing success. Binder of Sperm Proteins (BSPs) are abundant ram seminal plasma proteins which have been suggested to have significant protective effects on ram spermatozoa during cold shock. This is in direct opposition to bull spermatozoa, where BSPs cause sperm deterioration during in vitro handling. We investigated the potential of BSP1 and BSP5 to prevent freezing associated damage to important functional parameters of ram spermatozoa. BSPs purified by size exclusion chromatography improved post thaw motility and penetration through artificial mucus. Highly purified BSP1 and BSP5, isolated by gelatin affinity and RP-HPLC, improved motility and membrane integrity, and reduced post thaw protein tyrosine phosphorylation. Exposure to BSP5 before freezing increased the amount of phosphatidylethanolamine on the sperm surface after thawing. Neither BSP1 nor BSP5 prevented freezing associated changes in membrane lipid disorder. These results suggest that BSPs may significantly improve freezing outcomes of ram spermatozoa. Copyright © 2018 Elsevier Inc. All rights reserved.

Inactivation of avirulent Yersinia pestis on food and food contact surfaces by ultraviolet light and freezing.

PubMed

Sommers, Christopher H; Sheen, Shiowshuh

2015-09-01

Yersinia pestis, the causative agent of plague, can occasionally be contracted as a naso-pharyngeal or gastrointestinal illness through consumption of contaminated meat. In this study, the use of 254 nm ultraviolet light (UV-C) to inactivate a multi-isolate cocktail of avirulent Y. pestis on food and food contact surfaces was investigated. When a commercial UV-C conveyor was used (5 mW/cm(2)/s) 0.5 J/cm(2) inactivated >7 log of the Y. pestis cocktail on agar plates. At 0.5 J/cm(2), UV-C inactivated ca. 4 log of Y. pestis in beef, chicken, and catfish, exudates inoculated onto high density polypropylene or polyethylene, and stainless steel coupons, and >6 log was eliminated at 1 J/cm(2). Approximately 1 log was inactivated on chicken breast, beef steak, and catfish fillet surfaces at a UV-C dose of 1 J/cm(2). UV-C treatment prior to freezing of the foods did not increase the inactivation of Y. pestis over freezing alone. These results indicate that routine use of UV-C during food processing would provide workers and consumers some protection against Y. pestis. Published by Elsevier Ltd.

Simulation of Soil Frost and Thaw Fronts Dynamics with Community Land Model 4.5

NASA Astrophysics Data System (ADS)

Gao, J.; Xie, Z.

2016-12-01

Freeze-thaw processes in soils, including changes in frost and thaw fronts (FTFs) , are important physical processes. The movement of FTFs affects soil water and thermal characteristics, as well as energy and water exchanges between land surface and the atmosphere, and then the land surface hydrothermal process. In this study, a two-directional freeze and thaw algorithm for simulating FTFs is incorporated into the community land surface model CLM4.5, which is called CLM4.5-FTF. The simulated FTFs depth and soil temperature of CLM4.5-FTF compared well with the observed data both in D66 station (permafrost) and Hulugou station (seasonally frozen soil). Because the soil temperature profile within a soil layer can be estimated according to the position of FTFs, CLM4.5 performed better in soil temperature simulation. Permafrost and seasonally frozen ground conditions in China from 1980 to 2010 were simulated using the CLM4.5-FTF. Numerical experiments show that the spatial distribution of simulated maximum frost depth by CLM4.5-FTF has seasonal variation obviously. Significant positive active-layer depth trends for permafrost regions and negative maximum freezing depth trends for seasonal frozen soil regions are simulated in response to positive air temperature trends except west of Black Sea.

Computational study of the melting-freezing transition in the quantum hard-sphere system for intermediate densities. II. Structural features.

PubMed

Sesé, Luis M; Bailey, Lorna E

2007-04-28

The structural features of the quantum hard-sphere system in the region of the fluid-face-centered-cubic-solid transition, for reduced number densities 0.45

Roles of Terminology, Experience, and Energy Concepts in Student Conceptions of "Freezing" and "Boiling"

ERIC Educational Resources Information Center

Jasien, Paul G.

2013-01-01

A discussion of some student conceptions of the solid-liquid and liquid-vapor phase transitions is presented. Data from open-ended, short-answer questions were collected from first-semester general chemistry students and then discussed in the context of previous studies. The responses gave insight into the various student conceptions about these…

Determination of the season-acclimation of photosynthetic apparatus by heat-induced changes in chlorophyll fluorescence

Treesearch

Nicolay Alexandrovich Gaevsky

2002-01-01

Resistance to damage from freezing temperatures is one of the most adaptive properties of "evergreen" (shoot bark, felloderma, needles) woody and bush plant tissues. Species-specific processes accompanying transition of chloroplasts to a frost resistant state (reduction of photochemical activity, the change of chemical structure and structural organization of...

Glassy behavior and dynamic tweed in defect-free multiferroics

NASA Astrophysics Data System (ADS)

Wang, Xiaofei; Salje, Ekhard K. H.; Sun, Jun; Ding, Xiangdong

2018-01-01

Multiferroics often show significant elastic fluctuations even when the transition is strongly stepwise. Molecular dynamics simulations of a generic toy model show the appearance of tweed nanostructures (cross hatched patterns) in the paraelastic phase just above the transition point. This tweed lowers the elastic modulus C12 when approaching the transition temperature. The spatial and temporal correlations of the tweed structure follow the Vogel-Fulcher relationship, and the Vogel-Fulcher temperature is slightly below the transition temperature Ttrans, preventing this glassy state to freeze completely. Spatial correlations of shear strain show that the size of tweed patches reaches about eight lattice spacings near Ttrans. Cross- and rod-shaped diffuse scattering, similar to that in relaxors, emerges around {hh0}* and {h00}* Bragg reflections. The viscosity of the sample increases dramatically at the transition point with a significant precursor increase in the tweed regime.

Short- and long-term stability of lyophilised melatonin-loaded lecithin/chitosan nanoparticles.

PubMed

Hafner, Anita; Dürrigl, Marjana; Pepić, Ivan; Filipović-Grčić, Jelena

2011-01-01

The aim of this study was to establish a freeze-drying process for melatonin-loaded lecithin/chitosan nanoparticles (NPs) to preserve their chemical and physical stability for a longer time period that what is possible in an aqueous suspension. Glucose and trehalose were investigated as potential excipients during freeze-drying of NP suspensions. Lecithin/chitosan NPs were characterised by mean diameter and zeta potential, ranging between 117.4 and 328.5 nm and 6.7 and 30.2 mV, respectively, depending on the lecithin type and chitosan content in the preparation. Melatonin loadings were up to 7.1%. For all lecithin/chitosan NPs, no notable differences in the mean particle size, size distribution, zeta potential or melatonin content were observed before or immediately after the lyophilisation process or after 7 months of storage at 4 °C. The residual moisture contents of lyophilisates with glucose and trehalose immediately after the lyophilisation process varied between 4.0-4.8% and 2.4-3.0%, respectively. All lecithin/chitosan NPs had a fully amorphous nature after the freeze-drying process, as indicated by modulated differential scanning calorimetry. NP lyophilisates with glucose had a low glass transition temperature (ca. 5 °C), confirming that lyophilisation with glucose as a cryoprotectant was not appropriate. All lyophilisates with trehalose had a glass transition temperature above the room temperature, allowing formation of the cake without a collapse of the structure, which was capable of preserving its characteristics and appearance following 7 months of storage at 4 °C.

Cryo-planing of frozen-hydrated samples using cryo triple ion gun milling (CryoTIGM™).

PubMed

Chang, Irene Y T; Joester, Derk

2015-12-01

Cryo-SEM is a high throughput technique for imaging biological ultrastructure in its most pristine state, i.e. without chemical fixation, embedding, or drying. Freeze fracture is routinely used to prepare internal surfaces for cryo-SEM imaging. However, the propagation of the fracture plane is highly dependent on sample properties, and the resulting surface frequently shows substantial topography, which can complicate image analysis and interpretation. We have developed a broad ion beam milling technique, called cryogenic triple ion gun milling (CryoTIGM™ ['krī-ə-,tīm]), for cryo-planing frozen-hydrated biological specimens. Comparing sample preparation by CryoTIGM™ and freeze fracture in three model systems, Baker's yeast, mouse liver tissue, and whole sea urchin embryos, we find that CryoTIGM™ yields very large (∼700,000 μm(2)) and smooth sections that present ultrastructural details at similar or better quality than freeze-fractured samples. A particular strength of CryoTIGM™ is the ability to section samples with hard-soft contrast such as brittle calcite (CaCO3) spicules in the sea urchin embryo. Copyright © 2015 Elsevier Inc. All rights reserved.

Ice nucleation triggered by negative pressure.

PubMed

Marcolli, Claudia

2017-11-30

Homogeneous ice nucleation needs supercooling of more than 35 K to become effective. When pressure is applied to water, the melting and the freezing points both decrease. Conversely, melting and freezing temperatures increase under negative pressure, i.e. when water is stretched. This study presents an extrapolation of homogeneous ice nucleation temperatures from positive to negative pressures as a basis for further exploration of ice nucleation under negative pressure. It predicts that increasing negative pressure at temperatures below about 262 K eventually results in homogeneous ice nucleation while at warmer temperature homogeneous cavitation, i. e. bubble nucleation, dominates. Negative pressure occurs locally and briefly when water is stretched due to mechanical shock, sonic waves, or fragmentation. The occurrence of such transient negative pressure should suffice to trigger homogeneous ice nucleation at large supercooling in the absence of ice-nucleating surfaces. In addition, negative pressure can act together with ice-inducing surfaces to enhance their intrinsic ice nucleation efficiency. Dynamic ice nucleation can be used to improve properties and uniformity of frozen products by applying ultrasonic fields and might also be relevant for the freezing of large drops in rainclouds.

Melting/freezing behavior of a fluid confined in porous glasses and MCM-41: Dielectric spectroscopy and molecular simulation

NASA Astrophysics Data System (ADS)

Sliwinska-Bartkowiak, Malgorzata; Dudziak, Grazyna; Sikorski, Roman; Gras, Roman; Radhakrishnan, Ravi; Gubbins, Keith E.

2001-01-01

We report both experimental measurements and molecular simulations of the melting and freezing behavior of fluids in nanoporous media. The experimental studies are for nitrobenzene in the silica-based pores of controlled pore glass, Vycor, and MCM-41. Dielectric relaxation spectroscopy is used to determine melting points and the orientational relaxation times of the nitrobenzene molecules in the bulk and the confined phase. Monte Carlo simulations, together with a bond orientational order parameter method, are used to determine the melting point and fluid structure inside cylindrical pores modeled on silica. Qualitative comparison between experiment and simulation are made for the shift in the freezing temperatures and the structure of confined phases. From both the experiments and the simulations, it is found that the confined fluid freezes into a single crystalline structure for average pore diameters greater than 20σ, where σ is the diameter of the fluid molecule. For average pore sizes between 20σ and 15σ, part of the confined fluid freezes into a frustrated crystal structure with the rest forming an amorphous region. For pore sizes smaller than 15σ, even the partial crystallization did not occur. Our measurements and calculations show clear evidence of a novel intermediate "contact layer" phase lying between liquid and crystal; the contact layer is the confined molecular layer adjacent to the pore wall and experiences a deeper fluid-wall potential energy compared to the inner layers. We also find evidence of a liquid to "hexatic" transition in the quasi-two-dimensional contact layer at high temperatures.

Conventional freezing plus high pressure-low temperature treatment: Physical properties, microbial quality and storage stability of beef meat.

PubMed

Fernández, Pedro P; Sanz, Pedro D; Molina-García, Antonio D; Otero, Laura; Guignon, Bérengère; Vaudagna, Sergio R

2007-12-01

Meat high-hydrostatic pressure treatment causes severe decolouration, preventing its commercialisation due to consumer rejection. Novel procedures involving product freezing plus low-temperature pressure processing are here investigated. Room temperature (20°C) pressurisation (650MPa/10min) and air blast freezing (-30°C) are compared to air blast freezing plus high pressure at subzero temperature (-35°C) in terms of drip loss, expressible moisture, shear force, colour, microbial quality and storage stability of fresh and salt-added beef samples (Longissimus dorsi muscle). The latter treatment induced solid water transitions among ice phases. Fresh beef high pressure treatment (650MPa/20°C/10min) increased significantly expressible moisture while it decreased in pressurised (650MPa/-35°C/10min) frozen beef. Salt addition reduced high pressure-induced water loss. Treatments studied did not change fresh or salt-added samples shear force. Frozen beef pressurised at low temperature showed L, a and b values after thawing close to fresh samples. However, these samples in frozen state, presented chromatic parameters similar to unfrozen beef pressurised at room temperature. Apparently, freezing protects meat against pressure colour deterioration, fresh colour being recovered after thawing. High pressure processing (20°C or -35°C) was very effective reducing aerobic total (2-log(10) cycles) and lactic acid bacteria counts (2.4-log(10) cycles), in fresh and salt-added samples. Frozen+pressurised beef stored at -18°C during 45 days recovered its original colour after thawing, similarly to just-treated samples while their counts remain below detection limits during storage.

Formation of highly porous aerosol particles by atmospheric freeze-drying in ice clouds

PubMed Central

Adler, Gabriela; Koop, Thomas; Haspel, Carynelisa; Taraniuk, Ilya; Moise, Tamar; Koren, Ilan; Heiblum, Reuven H.; Rudich, Yinon

2013-01-01

The cycling of atmospheric aerosols through clouds can change their chemical and physical properties and thus modify how aerosols affect cloud microphysics and, subsequently, precipitation and climate. Current knowledge about aerosol processing by clouds is rather limited to chemical reactions within water droplets in warm low-altitude clouds. However, in cold high-altitude cirrus clouds and anvils of high convective clouds in the tropics and midlatitudes, humidified aerosols freeze to form ice, which upon exposure to subsaturation conditions with respect to ice can sublimate, leaving behind residual modified aerosols. This freeze-drying process can occur in various types of clouds. Here we simulate an atmospheric freeze-drying cycle of aerosols in laboratory experiments using proxies for atmospheric aerosols. We find that aerosols that contain organic material that undergo such a process can form highly porous aerosol particles with a larger diameter and a lower density than the initial homogeneous aerosol. We attribute this morphology change to phase separation upon freezing followed by a glass transition of the organic material that can preserve a porous structure after ice sublimation. A porous structure may explain the previously observed enhancement in ice nucleation efficiency of glassy organic particles. We find that highly porous aerosol particles scatter solar light less efficiently than nonporous aerosol particles. Using a combination of satellite and radiosonde data, we show that highly porous aerosol formation can readily occur in highly convective clouds, which are widespread in the tropics and midlatitudes. These observations may have implications for subsequent cloud formation cycles and aerosol albedo near cloud edges. PMID:24297908

Formation of highly porous aerosol particles by atmospheric freeze-drying in ice clouds.

PubMed

Adler, Gabriela; Koop, Thomas; Haspel, Carynelisa; Taraniuk, Ilya; Moise, Tamar; Koren, Ilan; Heiblum, Reuven H; Rudich, Yinon

2013-12-17

The cycling of atmospheric aerosols through clouds can change their chemical and physical properties and thus modify how aerosols affect cloud microphysics and, subsequently, precipitation and climate. Current knowledge about aerosol processing by clouds is rather limited to chemical reactions within water droplets in warm low-altitude clouds. However, in cold high-altitude cirrus clouds and anvils of high convective clouds in the tropics and midlatitudes, humidified aerosols freeze to form ice, which upon exposure to subsaturation conditions with respect to ice can sublimate, leaving behind residual modified aerosols. This freeze-drying process can occur in various types of clouds. Here we simulate an atmospheric freeze-drying cycle of aerosols in laboratory experiments using proxies for atmospheric aerosols. We find that aerosols that contain organic material that undergo such a process can form highly porous aerosol particles with a larger diameter and a lower density than the initial homogeneous aerosol. We attribute this morphology change to phase separation upon freezing followed by a glass transition of the organic material that can preserve a porous structure after ice sublimation. A porous structure may explain the previously observed enhancement in ice nucleation efficiency of glassy organic particles. We find that highly porous aerosol particles scatter solar light less efficiently than nonporous aerosol particles. Using a combination of satellite and radiosonde data, we show that highly porous aerosol formation can readily occur in highly convective clouds, which are widespread in the tropics and midlatitudes. These observations may have implications for subsequent cloud formation cycles and aerosol albedo near cloud edges.

Methods for characterizing convective cryoprobe heat transfer in ultrasound gel phantoms.

PubMed

Etheridge, Michael L; Choi, Jeunghwan; Ramadhyani, Satish; Bischof, John C

2013-02-01

While cryosurgery has proven capable in treating of a variety of conditions, it has met with some resistance among physicians, in part due to shortcomings in the ability to predict treatment outcomes. Here we attempt to address several key issues related to predictive modeling by demonstrating methods for accurately characterizing heat transfer from cryoprobes, report temperature dependent thermal properties for ultrasound gel (a convenient tissue phantom) down to cryogenic temperatures, and demonstrate the ability of convective exchange heat transfer boundary conditions to accurately describe freezing in the case of single and multiple interacting cryoprobe(s). Temperature dependent changes in the specific heat and thermal conductivity for ultrasound gel are reported down to -150 °C for the first time here and these data were used to accurately describe freezing in ultrasound gel in subsequent modeling. Freezing around a single and two interacting cryoprobe(s) was characterized in the ultrasound gel phantom by mapping the temperature in and around the "iceball" with carefully placed thermocouple arrays. These experimental data were fit with finite-element modeling in COMSOL Multiphysics, which was used to investigate the sensitivity and effectiveness of convective boundary conditions in describing heat transfer from the cryoprobes. Heat transfer at the probe tip was described in terms of a convective coefficient and the cryogen temperature. While model accuracy depended strongly on spatial (i.e., along the exchange surface) variation in the convective coefficient, it was much less sensitive to spatial and transient variations in the cryogen temperature parameter. The optimized fit, convective exchange conditions for the single-probe case also provided close agreement with the experimental data for the case of two interacting cryoprobes, suggesting that this basic characterization and modeling approach can be extended to accurately describe more complicated, multiprobe freezing geometries. Accurately characterizing cryoprobe behavior in phantoms requires detailed knowledge of the freezing medium's properties throughout the range of expected temperatures and an appropriate description of the heat transfer across the probe's exchange surfaces. Here we demonstrate that convective exchange boundary conditions provide an accurate and versatile description of heat transfer from cryoprobes, offering potential advantages over the traditional constant surface heat flux and constant surface temperature descriptions. In addition, although this study was conducted on Joule-Thomson type cryoprobes, the general methodologies should extend to any probe that is based on convective exchange with a cryogenic fluid.

CRYOPRESERVATION STRATEGY FOR TISSUE ENGINEERING CONSTRUCTS CONSISTING OF HUMAN MESENHYMAL STEM CELLS AND HYDROGEL BIOMATERIALS.

PubMed

Wu, Y; Wen, F; Gouk, S S; Lee, E H; Kuleshova, L

2015-01-01

The development of vitrification strategy for cell-biomaterial constructs, particularly biologically inspired nanoscale materials and hydrogels mimicking the in vivo environment is an active area. A cryopreservation strategy mimicking the in vivo environment for cell-hydrogel constructs may enhance cell proliferation and biological function. To demonstrate the efficacy of vitrification as a platform technology involving tissue engineering and human mesenchymal stem cells (hMSCs). Microcarriers made from alginate coated with chitosan and collagen are used. Conventional freezing and vitrification were compared. The vitrification strategy includes 10 min step-wise exposure to a vitrification solution (40% v/v EG, 0.6M sucrose) and immersion into liquid nitrogen. Confocal imaging of live/dead staining of hMSCs cultured on the surface of microcarriers demonstrated that vitrified cells had excellent appearance and prolonged spindle shape morphology. The proliferation ability of post-vitrified cells arbitrated to protein Ki-67 gene expression was not significantly different in comparison to untreated control, while that of post-freezing cells was almost lost. The ability of hMSCs cultured on the surface of microcarriers to proliferate has been not affected by vitrification and it was significantly better after vitrification than after conventional freezing during continuous culture. Collagen II related mRNA expression by 4 weeks post-vitrification and post-freezing showed that ability to differentiate into cartilage was sustained during vitrification and reduced during conventional freezing. No significant difference was found between control and vitrification groups only. Vitrification strategy coupled with advances in hMSC-expansion platform that completely preserves the ability of stem cells to proliferate and subsequently differentiate allows not only to reach a critical cell number, but also demonstrate prospects for effective utilization and transportation of cells with their support system, creating demand for novel biodegradable materials.

Initiation of the ice phase by marine biogenic surfaces in supersaturated gas and supercooled aqueous phases.

PubMed

Alpert, Peter A; Aller, Josephine Y; Knopf, Daniel A

2011-11-28

Biogenic particles have the potential to affect the formation of ice crystals in the atmosphere with subsequent consequences for the hydrological cycle and climate. We present laboratory observations of heterogeneous ice nucleation in immersion and deposition modes under atmospherically relevant conditions initiated by Nannochloris atomus and Emiliania huxleyi, marine phytoplankton with structurally and chemically distinct cell walls. Temperatures at which freezing, melting, and water uptake occur are observed using optical microscopy. The intact and fragmented unarmoured cells of N. atomus in aqueous NaCl droplets enhance ice nucleation by 10-20 K over the homogeneous freezing limit and can be described by a modified water activity based ice nucleation approach. E. huxleyi cells covered by calcite plates do not enhance droplet freezing temperatures. Both species nucleate ice in the deposition mode at an ice saturation ratio, S(ice), as low as ~1.2 and below 240 K, however, for each, different nucleation modes occur at warmer temperatures. These observations show that markedly different biogenic surfaces have both comparable and contrasting effects on ice nucleation behaviour depending on the presence of the aqueous phase and the extent of supercooling and water vapour supersaturation. We derive heterogeneous ice nucleation rate coefficients, J(het), and cumulative ice nuclei spectra, K, for quantification and analysis using time-dependent and time-independent approaches, respectively. Contact angles, α, derived from J(het)via immersion freezing depend on T, a(w), and S(ice). For deposition freezing, α can be described as a function of S(ice) only. The different approaches yield different predictions of atmospheric ice crystal numbers primarily due to the time evolution allowed for the time-dependent approach with implications for the evolution of mixed-phase and ice clouds.

Development of a Soluplus budesonide freeze-dried powder for nasal drug delivery.

PubMed

Pozzoli, Michele; Traini, Daniela; Young, Paul M; Sukkar, Maria B; Sonvico, Fabio

2017-09-01

The aim of this work was to develop an amorphous solid dispersions/solutions (ASD) of a poorly soluble drug, budesonide (BUD) with a novel polymer Soluplus ® (BASF, Germany) using a freeze-drying technique, in order to improve dissolution and absorption through the nasal route. The small volume of fluid present in the nasal cavity limits the absorption of a poorly soluble drug. Budesonide is a corticosteroid, practically insoluble and normally administered as a suspension-based nasal spray. The formulation was prepared through freeze-drying of polymer-drug solution. The formulation was assessed for its physicochemical (specific surface area, calorimetric analysis and X-ray powder diffraction), release properties and aerodynamic properties as well as transport in vitro using RPMI 2650 nasal cells, in order to elucidate the efficacy of the Soluplus-BUD formulation. The freeze-dried Soluplus-BUD formulation (LYO) showed a porous structure with a specific surface area of 1.4334 ± 0.0178 m 2 /g. The calorimetric analysis confirmed an interaction between BUD and Soluplus and X-ray powder diffraction the amorphous status of the drug. The freeze-dried formulation (LYO) showed faster release compared to both water-based suspension and dry powder commercial products. Furthermore, a LYO formulation, bulked with calcium carbonate (LYO-Ca), showed suitable aerodynamic characteristics for nasal drug delivery. The permeation across RPMI 2650 nasal cell model was higher compared to a commercial water-based BUD suspension. Soluplus has been shown to be a promising polymer for the formulation of BUD amorphous solid suspension/solution. This opens up opportunities to develop new formulations of poorly soluble drug for nasal delivery.

Immersion and contact freezing experiments in the Mainz wind tunnel laboratory

NASA Astrophysics Data System (ADS)

Eppers, Oliver; Mayer, Amelie; Diehl, Karoline; Mitra, Subir; Borrmann, Stephan; Szakáll, Miklós

2016-04-01

Immersion and contact freezing are of outmost important ice nucleation processes in mixed phase clouds. Experimental studies are carried out in the Mainz vertical wind tunnel laboratory in order to characterize these nucleation processes for different ice nucleating particles (INP), such as for mineral dust or biological particles. Immersion freezing is investigated in our laboratory with two different experimental techniques, both attaining contact-free levitation of liquid droplets and cooling of the surrounding air down to about -25 °C. In an acoustic levitator placed in the cold room of our laboratory, drops with diameters of 2 mm are investigated. In the vertical air stream of the wind tunnel droplets with diameter of 700 micron are freely floated at their terminal velocities, simulating the flow conditions of the free atmosphere. Furthermore, the wind tunnel offers a unique platform for contact freezing experiments. Supercooled water droplets are floated in the vertical air stream at their terminal velocities and INP are injected into the tunnel air stream upstream of them. As soon as INP collides with the supercooled droplet the contact freezing is initiated. The first results of immersion and contact freezing experiments with cellulose particles both in the acoustic levitator and in the wind tunnel will be presented. Cellulose is considered as typical INP of biological origin and a macrotracer for plant debris. Nucleating properties of cellulose will be provided, mainly focusing on the temperature, INP concentration, and specific surface area dependences of the freezing processes. Direct comparison between the different experimental techniques (acoustic levitator and wind tunnel), as well as between nucleation modes (immersion and contact freezing) will be presented. The work is carried out within the framework of the German research unit INUIT.

Antifreeze proteins govern the precipitation of trehalose in a freezing-avoiding insect at low temperature.

PubMed

Wen, Xin; Wang, Sen; Duman, John G; Arifin, Josh Fnu; Juwita, Vonny; Goddard, William A; Rios, Alejandra; Liu, Fan; Kim, Soo-Kyung; Abrol, Ravinder; DeVries, Arthur L; Henling, Lawrence M

2016-06-14

The remarkable adaptive strategies of insects to extreme environments are linked to the biochemical compounds in their body fluids. Trehalose, a versatile sugar molecule, can accumulate to high levels in freeze-tolerant and freeze-avoiding insects, functioning as a cryoprotectant and a supercooling agent. Antifreeze proteins (AFPs), known to protect organisms from freezing by lowering the freezing temperature and deferring the growth of ice, are present at high levels in some freeze-avoiding insects in winter, and yet, paradoxically are found in some freeze-tolerant insects. Here, we report a previously unidentified role for AFPs in effectively inhibiting trehalose precipitation in the hemolymph (or blood) of overwintering beetle larvae. We determine the trehalose level (29.6 ± 0.6 mg/mL) in the larval hemolymph of a beetle, Dendroides canadensis, and demonstrate that the hemolymph AFPs are crucial for inhibiting trehalose crystallization, whereas the presence of trehalose also enhances the antifreeze activity of AFPs. To dissect the molecular mechanism, we examine the molecular recognition between AFP and trehalose crystal interfaces using molecular dynamics simulations. The theory corroborates the experiments and shows preferential strong binding of the AFP to the fast growing surfaces of the sugar crystal. This newly uncovered role for AFPs may help explain the long-speculated role of AFPs in freeze-tolerant species. We propose that the presence of high levels of molecules important for survival but prone to precipitation in poikilotherms (their body temperature can vary considerably) needs a companion mechanism to prevent the precipitation and here present, to our knowledge, the first example. Such a combination of trehalose and AFPs also provides a novel approach for cold protection and for trehalose crystallization inhibition in industrial applications.

Antifreeze proteins govern the precipitation of trehalose in a freezing-avoiding insect at low temperature

PubMed Central

Wen, Xin; Wang, Sen; Duman, John G.; Arifin, Josh Fnu; Juwita, Vonny; Goddard, William A.; Rios, Alejandra; Liu, Fan; Kim, Soo-Kyung; Abrol, Ravinder; DeVries, Arthur L.; Henling, Lawrence M.

2016-01-01

The remarkable adaptive strategies of insects to extreme environments are linked to the biochemical compounds in their body fluids. Trehalose, a versatile sugar molecule, can accumulate to high levels in freeze-tolerant and freeze-avoiding insects, functioning as a cryoprotectant and a supercooling agent. Antifreeze proteins (AFPs), known to protect organisms from freezing by lowering the freezing temperature and deferring the growth of ice, are present at high levels in some freeze-avoiding insects in winter, and yet, paradoxically are found in some freeze-tolerant insects. Here, we report a previously unidentified role for AFPs in effectively inhibiting trehalose precipitation in the hemolymph (or blood) of overwintering beetle larvae. We determine the trehalose level (29.6 ± 0.6 mg/mL) in the larval hemolymph of a beetle, Dendroides canadensis, and demonstrate that the hemolymph AFPs are crucial for inhibiting trehalose crystallization, whereas the presence of trehalose also enhances the antifreeze activity of AFPs. To dissect the molecular mechanism, we examine the molecular recognition between AFP and trehalose crystal interfaces using molecular dynamics simulations. The theory corroborates the experiments and shows preferential strong binding of the AFP to the fast growing surfaces of the sugar crystal. This newly uncovered role for AFPs may help explain the long-speculated role of AFPs in freeze-tolerant species. We propose that the presence of high levels of molecules important for survival but prone to precipitation in poikilotherms (their body temperature can vary considerably) needs a companion mechanism to prevent the precipitation and here present, to our knowledge, the first example. Such a combination of trehalose and AFPs also provides a novel approach for cold protection and for trehalose crystallization inhibition in industrial applications. PMID:27226297

Microencapsulation of grape (Vitis labrusca var. Bordo) skin phenolic extract using gum Arabic, polydextrose, and partially hydrolyzed guar gum as encapsulating agents.

PubMed

Kuck, Luiza Siede; Noreña, Caciano Pelayo Zapata

2016-03-01

Bordo grape skin extract was microencapsulated by spray-drying and freeze-drying, using gum arabic (GA), partially hydrolyzed guar gum (PHGG), and polydextrose (PD) as encapsulating agents. Total phenolics and total monomeric anthocyanin, antioxidant activity, color, moisture, water activity (aw), solubility, hygroscopicity, glass transition temperature (Tg), particle size, and microstructure of the powders were evaluated. The retention of phenolics and anthocyanins ranged from 81.4% to 95.3%, and 80.8% to 99.6%, respectively, while the retention of antioxidant activity ranged from 45.4% to 83.7%. Treatments subjected to spray-drying had lower moisture, aw, and particle size, and greater solubility, while the freeze-dried samples were less hygroscopic. Tg values ranged from 10.1 to 52.2°C, and the highest values corresponded to the spray-dried microparticles. The spray-dried particles had spherical shape, while the freeze-dried powders showed irregular structures. The spray drying technique and the use of 5% PHGG and 5% PD has proven to be the best treatment. Copyright © 2015 Elsevier Ltd. All rights reserved.

Thermodynamic properties of Heusler Fe2VSi

NASA Astrophysics Data System (ADS)

Ito, Masakazu; Kai, Keita; Furuta, Tatsuya; Manaka, Hirotaka; Terada, Norio; Hiroi, Masahiko; Kondo, Akihiro; Kindo, Koichi

2018-05-01

We investigated temperature, T, dependence of magnetization, M(T), electrical resistivity, ρ(T), and specific heat, Cp(T), for the Heusler compound Fe2VSi. M(T) shows anomalies at TN1 ˜ 115 K and at TN2 ˜ 35 K. The anomaly at TN1 is caused by the magnetic transition with a crystal structural change. On the other hand, ρ(T) and Cp(T) show only anomaly at TN1, and no trace of anomaly at TN2 is observed. Because of the irreversibility of M(T), which is the characteristic of spin-glass freezing, appears below TN2, a spin-glass freezing may occur at TN2. From the analogy of the Heusler compound (Fe1-xVx ) 3Si with the cubic D03 crystal structure, (0 ≤ x ≤ 0.2), we suggested that the atomic disorder of V site by the Fe atoms gives rise to the magnetic frustration. This could be cause for the spin-glass freezing. By the Clausius-Clapeyron relation, pressure, P, derivative of TN1, (d/TN 1 d P ), is estimated to be ˜-10 K/Gpa.

Predictive model for ice formation on superhydrophobic surfaces.

PubMed

Bahadur, Vaibhav; Mishchenko, Lidiya; Hatton, Benjamin; Taylor, J Ashley; Aizenberg, Joanna; Krupenkin, Tom

2011-12-06

The prevention and control of ice accumulation has important applications in aviation, building construction, and energy conversion devices. One area of active research concerns the use of superhydrophobic surfaces for preventing ice formation. The present work develops a physics-based modeling framework to predict ice formation on cooled superhydrophobic surfaces resulting from the impact of supercooled water droplets. This modeling approach analyzes the multiple phenomena influencing ice formation on superhydrophobic surfaces through the development of submodels describing droplet impact dynamics, heat transfer, and heterogeneous ice nucleation. These models are then integrated together to achieve a comprehensive understanding of ice formation upon impact of liquid droplets at freezing conditions. The accuracy of this model is validated by its successful prediction of the experimental findings that demonstrate that superhydrophobic surfaces can fully prevent the freezing of impacting water droplets down to surface temperatures of as low as -20 to -25 °C. The model can be used to study the influence of surface morphology, surface chemistry, and fluid and thermal properties on dynamic ice formation and identify parameters critical to achieving icephobic surfaces. The framework of the present work is the first detailed modeling tool developed for the design and analysis of surfaces for various ice prevention/reduction strategies. © 2011 American Chemical Society

Regional and seasonal limitations for Mars intrinsic ecopoiesis.

PubMed

Badescu, Viorel

2005-04-01

Mars ecopoiesis is a human controlled process consisting in changes needed for anaerobic life to be established on planet surface. The daily minimum temperature on present day Mars is well below the water freezing point, due to the low thermal inertia of the surface. A simple time-dependent model to evaluate the ground temperature is developed here. It takes into account the incident solar radiation, the greenhouse effect and surface thermal inertia. The model is applied to two modified Martian atmospheres. Increasing surface thermal inertia seems to be necessary for Mars intrinsic ecopoiesis. This can be done either by removing the regolith layer covering the bedrock or by regolith compression. The Northern hemisphere of the terraformed Mars appears to be more hospitable than the Southern hemisphere, because the amplitude of the daily temperature excursion there is lower and the freezing temperature appears at higher latitudes. A regional (and seasonal) terraforming of Mars is suggested. c2005 Elsevier Ltd. All rights reserved.

Can we define an asymptotic value for the ice active surface site density for heterogeneous ice nucleation?

NASA Astrophysics Data System (ADS)

Niedermeier, Dennis; Augustin-Bauditz, Stefanie; Hartmann, Susan; Wex, Heike; Ignatius, Karoliina; Stratmann, Frank

2015-05-01

The immersion freezing behavior of droplets containing size-segregated, monodisperse feldspar particles was investigated. For all particle sizes investigated, a leveling off of the frozen droplet fraction was observed reaching a plateau within the heterogeneous freezing temperature regime (T >- 38°C). The frozen fraction in the plateau region was proportional to the particle surface area. Based on these findings, an asymptotic value for ice active surface site density ns, which we named ns⋆, could be determined for the investigated feldspar sample. The comparison of these results with those of other studies not only elucidates the general feasibility of determining such an asymptotic value but also shows that the value of ns⋆ strongly depends on the method of the particle surface area determination. However, such an asymptotic value might be an important input parameter for atmospheric modeling applications. At least it shows that care should be taken when ns is extrapolated to lower or higher temperature.

Preservation of EDTA-expanded grid-mounted chromosomes and nuclei for electron microscopy using a specially designed freeze-dryer.

PubMed

Woods, P S; Ledbetter, M C; Tempel, N

1991-06-01

We describe methods for freezing and drying EDTA-expanded, fixed metaphase chromosomes and nuclei, attached to grids as whole-mounts, for transmission electron microscopy. These methods use a special apparatus that is simple to construct. While separate freezers and dryers are commercially available, one for freezing blocks of tissue by slamming them against a cold metal surface, and the other for vacuum drying the frozen tissue, our apparatus is designed for gentler, cryogenic liquid plunge freezing and drying, sequentially, in the same apparatus, thus avoiding any compression or damage to the specimen. Use of a cryoprotectant is not essential; however, good results are obtained more often when 20% ethanol is used. Freezing is accomplished by rapid propulsion of the grid, with specimens attached, into slushy N2 (-210 degrees C) within the drying chamber; drying is automatic, by either sublimation under vacuum or by solvent substitution using absolute ethanol followed by acetone, which, in turn, is removed with a critical-point dryer. The apparatus offers a means of drying chromosomes and nuclei in an expanded state, and avoids the shrinkage of these structures that occurs during stepwise passage through increasing concentrations of ethanol or acetone.

Optimization of Freeze Drying Conditions for Purified Pectinase from Mango (Mangifera indica cv. Chokanan) Peel

PubMed Central

Mehrnoush, Amid; Mustafa, Shuhaimi; Yazid, Abdul Manap Mohd

2012-01-01

Response surface methodology (RSM) along with central composite design (CCD) was applied to optimize the freeze drying conditions for purified pectinase from mango (Mangifera indica cv. Chokanan) peel. The effect of pectinase content (−2.66, 62.66 mg/mL), Arabic gum (−1.21, 10.21%, w/v), and maltodextrin (0.73, 7.26%, w/v) as independent variables on activity, yield, and storage stability of freeze-dried enzyme was evaluated. Storage stability of pectinase was investigated after one week at 4 °C and yield percentage of the enzyme after encapsulation was also determined. The independent variables had the most significant (p < 0.05) effect on pectinase activity and yield of the enzyme. It was observed that the interaction effect of Arabic gum and maltodextrin improved the enzymatic properties of freeze-dried pectinase. The optimal conditions for freeze-dried pectinase from mango peel were obtained using 30 mg/mL of pectinase content, 4.5 (%, w/v) of Arabic gum, and 4 (%, w/v) of maltodextrin. Under these conditions, the maximum activity (11.12 U/mL), yield (86.4%) and storage stability (84.2%) of encapsulated pectinase were achieved. PMID:22489134

The innovation of cryo-SEM freeze-fracturing methodology demonstrated on high pressure frozen biofilm.

PubMed

Hrubanova, Kamila; Nebesarova, Jana; Ruzicka, Filip; Krzyzanek, Vladislav

2018-07-01

In this study we present an innovative method for the preparation of fully hydrated samples of microbial biofilms of cultures Staphylococcus epidermidis, Candida parapsilosis and Candida albicans. Cryo-scanning electron microscopy (cryo-SEM) and high-pressure freezing (HPF) rank among cutting edge techniques in the electron microscopy of hydrated samples such as biofilms. However, the combination of these techniques is not always easily applicable. Therefore, we present a method of combining high-pressure freezing using EM PACT2 (Leica Microsystems), which fixes hydrated samples on small sapphire discs, with a high resolution SEM equipped with the widely used cryo-preparation system ALTO 2500 (Gatan). Using a holder developed in house, a freeze-fracturing technique was applied to image and investigate microbial cultures cultivated on the sapphire discs. In our experiments, we focused on the ultrastructure of the extracellular matrix produced during cultivation and the relationships among microbial cells in the biofilm. The main goal of our investigations was the detailed visualization of areas of the biofilm where the microbial cells adhere to the substrate/surface. We show the feasibility of this technique, which is clearly demonstrated in experiments with various freeze-etching times. Copyright © 2018 Elsevier Ltd. All rights reserved.

Optimization of freeze drying conditions for purified pectinase from mango (Mangifera indica cv. Chokanan) peel.

PubMed

Mehrnoush, Amid; Mustafa, Shuhaimi; Yazid, Abdul Manap Mohd

2012-01-01

Response surface methodology (RSM) along with central composite design (CCD) was applied to optimize the freeze drying conditions for purified pectinase from mango (Mangifera indica cv. Chokanan) peel. The effect of pectinase content (-2.66, 62.66 mg/mL), Arabic gum (-1.21, 10.21%, w/v), and maltodextrin (0.73, 7.26%, w/v) as independent variables on activity, yield, and storage stability of freeze-dried enzyme was evaluated. Storage stability of pectinase was investigated after one week at 4 °C and yield percentage of the enzyme after encapsulation was also determined. The independent variables had the most significant (p < 0.05) effect on pectinase activity and yield of the enzyme. It was observed that the interaction effect of Arabic gum and maltodextrin improved the enzymatic properties of freeze-dried pectinase. The optimal conditions for freeze-dried pectinase from mango peel were obtained using 30 mg/mL of pectinase content, 4.5 (%, w/v) of Arabic gum, and 4 (%, w/v) of maltodextrin. Under these conditions, the maximum activity (11.12 U/mL), yield (86.4%) and storage stability (84.2%) of encapsulated pectinase were achieved.

Ice nucleation activity of silicates and aluminosilicates in pure water and aqueous solutions - Part 1: The K-feldspar microcline

NASA Astrophysics Data System (ADS)

Kumar, Anand; Marcolli, Claudia; Luo, Beiping; Peter, Thomas

2018-05-01

Potassium-containing feldspars (K-feldspars) have been considered as key mineral dusts for ice nucleation (IN) in mixed-phase clouds. To investigate the effect of solutes on their IN efficiency, we performed immersion freezing experiments with the K-feldspar microcline, which is highly IN active. Freezing of emulsified droplets with microcline suspended in aqueous solutions of NH3, (NH4)2SO4, NH4HSO4, NH4NO3, NH4Cl, Na2SO4, H2SO4, K2SO4 and KCl, with solute concentrations corresponding to water activities aw = 0.9-1.0, were investigated by means of a differential scanning calorimeter (DSC). The measured heterogeneous IN onset temperatures, Thet(aw), deviate strongly from ThetΔawhet(aw), the values calculated from the water-activity-based approach (where ThetΔawhet(aw) = Tmelt(aw + Δawhet) with a constant offset Δawhet with respect to the ice melting point curve). Surprisingly, for very dilute solutions of NH3 and NH4+ salts (molalities ≲1 mol kg-1 corresponding to aw ≳ 0.96), we find IN temperatures raised by up to 4.5 K above the onset freezing temperature of microcline in pure water (Thet(aw = 1)) and 5.5 K above ThetΔawhet(aw), revealing NH3 and NH4+ to significantly enhance the IN of the microcline surface. Conversely, more concentrated NH3 and NH4+ solutions show a depression of the onset temperature below ThetΔawhet(aw) by as much as 13.5 K caused by a decline in IN ability accompanied with a reduction in the volume fraction of water frozen heterogeneously. All salt solutions not containing NH4+ as cation exhibit nucleation temperatures Thet(aw) < ThetΔawhet(aw) even at very small solute concentrations. In all these cases, the heterogeneous freezing peak displays a decrease as solute concentration increases. This deviation from Δawhet = const. indicates specific chemical interactions between particular solutes and the microcline surface not captured by the water-activity-based approach. One such interaction is the exchange of K+ available on the microcline surface with externally added cations (e.g., NH4+). However, the presence of a similar increase in IN efficiency in dilute ammonia solutions indicates that the cation exchange cannot explain the increase in IN temperatures. Instead, we hypothesize that NH3 molecules hydrogen bonded on the microcline surface form an ice-like overlayer, which provides hydrogen bonding favorable for ice to nucleate on, thus enhancing both the freezing temperatures and the heterogeneously frozen fraction in dilute NH3 and NH4+ solutions. Moreover, we show that aging of microcline in concentrated solutions over several days does not impair IN efficiency permanently in case of near-neutral solutions since most of it recovers when aged particles are resuspended in pure water. In contrast, exposure to severe acidity (pH ≲1.2) or alkalinity (pH ≳11.7) damages the microcline surface, hampering or even destroying the IN efficiency irreversibly. Implications for IN in airborne dust containing microcline might be multifold, ranging from a reduction of immersion freezing when exposed to dry, cold and acidic conditions to a 5 K enhancement during condensation freezing when microcline particles experience high humidity (aw≳0.96) at warm (252-257 K) and NH3/NH4+-rich conditions.

The role of land use and environmental factors on microbial pollution of mountainous limestone aquifers

NASA Astrophysics Data System (ADS)

Allocca, V.; Celico, F.; Petrella, E.; Marzullo, G.; Naclerio, G.

2008-07-01

Limestone aquifers in Southern Italy are often affected by bacterial contamination produced by pasture and agriculture. The main goals of this study were (1) to analyze the role of land use and environmental factors on microbial contamination and, (2) to identify, at field scale, the most suitable indicator of fecal pollution, by comparing fecal coliforms and fecal enterococci. Analyzing surface and spring water, it was noted that both fecal indicators showed a significant decrease during the period characterized by freezing and/or freeze-thaw intervals. The data analysis shows that fecal coliforms are characterized by a significant decrease in population (3 orders of magnitude, at least) during the freezing period, while fecal enterococci are temporarily inhibited. A taxonomic classification of fecal enterococci detected in spring water samples was performed by the API 20 Strep system and by sequencing of the ribosomal 16S DNA genes. The results showed that freezing conditions did not cause any significant change on the set of enterococcal species.

Water-Hydrogel Binding Affinity Modulates Freeze-Drying-Induced Micropore Architecture and Skeletal Myotube Formation.

PubMed

Rich, Max H; Lee, Min Kyung; Marshall, Nicholas; Clay, Nicholas; Chen, Jinrong; Mahmassani, Ziad; Boppart, Marni; Kong, Hyunjoon

2015-08-10

Freeze-dried hydrogels are increasingly used to create 3D interconnected micropores that facilitate biomolecular and cellular transports. However, freeze-drying is often plagued by variance in micropore architecture based on polymer choice. We hypothesized that water-polymer binding affinity plays a significant role in sizes and numbers of micropores formed through freeze-drying, influencing cell-derived tissue quality. Poly(ethylene glycol)diacrylate (PEGDA) hydrogels with alginate methacrylate (AM) were used due to AM's higher binding affinity for water than PEGDA. PEGDA-AM hydrogels with larger AM concentrations resulted in larger sizes and numbers of micropores than pure PEGDA hydrogels, attributed to the increased mass of water binding to the PEGDA-AM gel. Skeletal myoblasts loaded in microporous PEGDA-AM hydrogels were active to produce 3D muscle-like tissue, while those loaded in pure PEGDA gels were localized on the gel surface. We propose that this study will be broadly useful in designing and improving the performance of various microporous gels.

Analysis of a space emergency ammonia dump using the FLOW-NET two-phase flow program

NASA Technical Reports Server (NTRS)

Navickas, J.; Rivard, W. C.

1992-01-01

Venting of cryogenic and non-cryogenic fluids to a vacuum or a very low pressure will take place in many space-based systems that are currently being designed. This may cause liquid freezing either internally within the flow circuit or on external spacecraft surfaces. Typical ammonia flow circuits were investigated to determine the effect of the geometric configuration and initial temperature, pressure, and void fraction on the freezing characteristics of the system. The analysis was conducted also to investigate the ranges of applicability of the FLOW-NET program. It was shown that a typical system can be vented to very low liquid fractions before freezing occurs. However, very small restrictions in the flow circuit can hasten the inception of freezing. The FLOW-NET program provided solutions over broad ranges of system conditions, such as venting of an ammonia tank, initially completely filled with liquid, through a series of contracting and expanding line cross sections to near-vacuum conditions.

Impacts of the thawing-freezing process on runoff generation in the Sources Area of the Yellow River on the northeastern Qinghai-Tibet Plateau

NASA Astrophysics Data System (ADS)

Wu, Xiaoling; Xiang, Xiaohua; Qiu, Chao; Li, Li

2018-06-01

In cold regions, precipitation, air temperature and snow cover significantly influence soil water, heat transfer, the freezing-thawing processes of the active soil layer, and runoff generation. Hydrological regimes of the world's major rivers in cold regions have changed remarkably since the 1960s, but the mechanisms underlying the changes have not yet been fully understood. Using the basic physical processes for water and heat balances and transfers in snow covered soil, a water-heat coupling model for snow cover and its underlying soil layers was established. We found that freezing-thawing processes can affect the thickness of the active layer, storage capacity for liquid water, and subsequent surface runoffs. Based on calculations of thawing-freezing processes, we investigated hydrological processes at Qumalai. The results show that the water-heat coupling model can be used in this region to provide an understanding of the local movement of hydrological regimes.

The Effect of Surface Chemical Functionality Upon Ice Adhesion

NASA Technical Reports Server (NTRS)

Smith, Joseph G., Jr.; Wohl, Christopher J.; Doss, Jereme; Spence, Destiny; Kreeger, Richard E.; Palacios, Jose; Knuth, Taylor; Hadley, Kevin R.; McDougal, Nicholas D.

2015-01-01

In nature, anti-freeze proteins present in fish utilize specific organic functionalities to disrupt ice crystal formation and propagation. Based on these structures, surfaces with controlled chemical functionality and chain length were evaluated both experimentally and computationally to assess the effect of both parameters in mitigating ice formation. Linear aliphatic dimethylethoxysilanes terminated with methyl or hydroxyl groups were prepared, characterized, and used to coat aluminum. The effect upon icing using a microdroplet freezing apparatus and the Adverse Environment Rotor Test Stand found hydroxyl-terminated materials exhibited a greater propensity for ice formation and adhesion. Molecular dynamics simulations of a silica substrate bearing functionalized species of similar composition were brought into contact with a pre-equilibrated ice crystal. Several parameters including chain mobility were monitored to ascertain the size of a quasi-liquid layer. The studies suggested that chain mobility affected the interface between ice and the surface more than terminal group chemical composition.

Segregation effects during solidification in weightless melts

NASA Technical Reports Server (NTRS)

Li, C.

1973-01-01

Two types of melt segregation effects were studied: (1) evaporative segregation, or segregation due to surface evaporation; and (2) freezing segregation, or segregation due to liquid-solid phase transformation. These segregation effects are closely related. In fact, evaporative segregation always precedes freezing segregation to some degree and must often be studied prior to performing meaningful solidification experiments. This is particularly true since evaporation may cause the melt composition, at least at the critical surface regions or layers to be affected manyfold within seconds so that the surface region or layer melting point and other thermophysical properties, nucleation characteristics, base for undercooling, and critical velocity to avoid constitutional supercooling, may be completely unexpected. An important objective was, therefore, to develop the necessary normal evaporation equations for predicting the compositional changes within specified times at temperature and to correlate these equations with actual experimental data collected from the literature.

Freezing Behavior of a Supercooled Water Droplet Impacting on Surface Using Dual-Luminescent Imaging Technique

NASA Astrophysics Data System (ADS)

Tanaka, Mio; Morita, Katsuaki; Yamamoto, Makoto; Sakaue, Hirotaka

2015-11-01

A collision of a supercooled-water droplet on an object creates ice accretion on its surface. These icing problems can be seen in any cold environments and may lead to severe damages on aircrafts, ships, power cables, trees, road signs, and architectures. To solve these problems, various studies on ice-prevention and ice-prediction techniques have been conducted. It is very important to know the detail freezing mechanism of supercooled water droplets to propose or improve those techniques. The icing mechanism of a single supercooled-water droplet impacting on object surface would give us great insights for constructing those techniques. In the present study, we use a dual-luminescent imaging technique to measure the time-resolved temperatures of a supercooled water droplet impacting with different speed. The technique we applied consists of high-speed color camera and two luminescent probes. We will report the current status of this experiment in the presentation.

Coordinated Mapping of Sea Ice Deformation Features with Autonomous Vehicles

NASA Astrophysics Data System (ADS)

Maksym, T.; Williams, G. D.; Singh, H.; Weissling, B.; Anderson, J.; Maki, T.; Ackley, S. F.

2016-12-01

Decreases in summer sea ice extent in the Beaufort and Chukchi Seas has lead to a transition from a largely perennial ice cover, to a seasonal ice cover. This drives shifts in sea ice production, dynamics, ice types, and thickness distribution. To examine how the processes driving ice advance might also impact the morphology of the ice cover, a coordinated ice mapping effort was undertaken during a field campaign in the Beaufort Sea in October, 2015. Here, we present observations of sea ice draft topography from six missions of an Autonomous Underwater Vehicle run under different ice types and deformation features observed during autumn freeze-up. Ice surface features were also mapped during coordinated drone photogrammetric missions over each site. We present preliminary results of a comparison between sea ice surface topography and ice underside morphology for a range of sample ice types, including hummocked multiyear ice, rubble fields, young ice ridges and rafts, and consolidated pancake ice. These data are compared to prior observations of ice morphological features from deformed Antarctic sea ice. Such data will be useful for improving parameterizations of sea ice redistribution during deformation, and for better constraining estimates of airborne or satellite sea ice thickness.

Fundamental differences between glassy dynamics in two and three dimensions.

PubMed

Flenner, Elijah; Szamel, Grzegorz

2015-06-12

The two-dimensional freezing transition is very different from its three-dimensional counterpart. In contrast, the glass transition is usually assumed to have similar characteristics in two and three dimensions. Using computer simulations, here we show that glassy dynamics in supercooled two- and three-dimensional fluids are fundamentally different. Specifically, transient localization of particles on approaching the glass transition is absent in two dimensions, whereas it is very pronounced in three dimensions. Moreover, the temperature dependence of the relaxation time of orientational correlations is decoupled from that of the translational relaxation time in two dimensions but not in three dimensions. Last, the relationships between the characteristic size of dynamically heterogeneous regions and the relaxation time are very different in two and three dimensions. These results strongly suggest that the glass transition in two dimensions is different than in three dimensions.

A Theory of Immersion Freezing

NASA Technical Reports Server (NTRS)

Barahona, Donifan

2017-01-01

Immersion freezing is likely involved in the initiation of precipitation and determines to large extent the phase partitioning in convective clouds. Theoretical models commonly used to describe immersion freezing in atmospheric models are based on the classical nucleation theory which however neglects important interactions near the immersed particle that may affect nucleation rates. This work introduces a new theory of immersion freezing based on two premises. First, immersion ice nucleation is mediated by the modification of the properties of water near the particle-liquid interface, rather than by the geometry of the ice germ. Second, the same mechanism that leads to the decrease in the work of germ formation also decreases the mobility of water molecules near the immersed particle. These two premises allow establishing general thermodynamic constraints to the ice nucleation rate. Analysis of the new theory shows that active sites likely trigger ice nucleation, but they do not control the overall nucleation rate nor the probability of freezing. It also suggests that materials with different ice nucleation efficiency may exhibit similar freezing temperatures under similar conditions but differ in their sensitivity to particle surface area and cooling rate. Predicted nucleation rates show good agreement with observations for a diverse set of materials including dust, black carbon and bacterial ice nucleating particles. The application of the new theory within the NASA Global Earth System Model (GEOS-5) is also discussed.

Effect of Controlled Ice Nucleation on Stability of Lactate Dehydrogenase During Freeze-Drying.

PubMed

Fang, Rui; Tanaka, Kazunari; Mudhivarthi, Vamsi; Bogner, Robin H; Pikal, Michael J

2018-03-01

Several controlled ice nucleation techniques have been developed to increase the efficiency of the freeze-drying process as well as to improve the quality of pharmaceutical products. Owing to the reduction in ice surface area, these techniques have the potential to reduce the degradation of proteins labile during freezing. The objective of this study was to evaluate the effect of ice nucleation temperature on the in-process stability of lactate dehydrogenase (LDH). LDH in potassium phosphate buffer was nucleated at -4°C, -8°C, and -12°C using ControLyo™ or allowed to nucleate spontaneously. Both the enzymatic activity and tetramer recovery after freeze-thawing linearly correlated with product ice nucleation temperature (n = 24). Controlled nucleation also significantly improved batch homogeneity as reflected by reduced inter-vial variation in activity and tetramer recovery. With the correlation established in the laboratory, the degradation of protein in manufacturing arising from ice nucleation temperature differences can be quantitatively predicted. The results show that controlled nucleation reduced the degradation of LDH during the freezing process, but this does not necessarily translate to vastly superior stability during the entire freeze-drying process. The capability of improving batch homogeneity provides potential advantages in scaling-up from lab to manufacturing scale. Copyright © 2018 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

Effect of chlorine, blanching, freezing, and microwave heating on Cryptosporidium parvum viability inoculated on green peppers.

PubMed

Duhain, G L M C; Minnaar, A; Buys, E M

2012-05-01

Cryptosporidium parvum oocysts have been found on the surface of vegetables in both developed and developing countries. C. parvum can contaminate vegetables via various routes, including irrigation water. This study investigated the effect of individual treatments of chlorine, blanching, blast freezing, and microwave heating, as well as combined treatments of chlorine and freezing, and chlorine and microwave heating on the viability of C. parvum oocysts inoculated on green peppers. The viability of the oocysts after the treatments was assessed using propidium iodide and a flow cytometer. Based on the propidium iodide staining, the chlorine treatments did not affect the viability of the oocysts. Blast freezing significantly inactivated 20% of the oocysts. Microwave heating and blanching significantly inactivated 93% of oocysts. Treatment with chlorine followed by blast freezing did not affect the viability of the oocysts significantly. Treatment with chlorine and microwave heating was significantly more effective than microwave heating alone and inactivated 98% of the oocysts. The study indicates that C. parvum oocysts are sensitive to heat and, to some extent, to blast freezing, but are resistant to chlorine. Therefore, the use of chlorine during vegetable processing is not a critical control point for C. parvum oocysts, and the consumption of raw or minimally processed vegetables may constitute a health risk as C. parvum oocysts can still be found viable on ready-to-eat, minimally processed vegetables.

A comprehensive laboratory study on the immersion freezing behavior of illite NX particles. A comparison of 17 ice nucleation measurement techniques

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hiranuma, Naruki; Augustin-Bauditz, Stefanie; Bingemer, Heinz

Immersion freezing is the most relevant heterogeneous ice nucleation mechanism through which ice crystals are formed in mixed-phase clouds. In recent years, an increasing number of laboratory experiments utilizing a variety of instruments have examined immersion freezing activity of atmospherically relevant ice-nucleating particles. However, an intercomparison of these laboratory results is a difficult task because investigators have used different ice nucleation (IN) measurement methods to produce these results. A remaining challenge is to explore the sensitivity and accuracy of these techniques and to understand how the IN results are potentially influenced or biased by experimental parameters associated with these techniques.more » Within the framework of INUIT (Ice Nuclei Research Unit), we distributed an illite-rich sample (illite NX) as a representative surrogate for atmospheric mineral dust particles to investigators to perform immersion freezing experiments using different IN measurement methods and to obtain IN data as a function of particle concentration, temperature ( T), cooling rate and nucleation time. A total of 17 measurement methods were involved in the data intercomparison. Experiments with seven instruments started with the test sample pre-suspended in water before cooling, while 10 other instruments employed water vapor condensation onto dry-dispersed particles followed by immersion freezing. The resulting comprehensive immersion freezing data set was evaluated using the ice nucleation active surface-site density, n s, to develop a representative n s( T) spectrum that spans a wide temperature range (-37 °C < T < -11 °C) and covers 9 orders of magnitude in n s. In general, the 17 immersion freezing measurement techniques deviate, within a range of about 8 °C in terms of temperature, by 3 orders of magnitude with respect to n s. In addition, we show evidence that the immersion freezing efficiency expressed in n s of illite NX particles is relatively independent of droplet size, particle mass in suspension, particle size and cooling rate during freezing. A strong temperature dependence and weak time and size dependence of the immersion freezing efficiency of illite-rich clay mineral particles enabled the n s parameterization solely as a function of temperature. We also characterized the n s( T) spectra and identified a section with a steep slope between -20 and -27 °C, where a large fraction of active sites of our test dust may trigger immersion freezing. This slope was followed by a region with a gentler slope at temperatures below -27 °C. While the agreement between different instruments was reasonable below ~ -27 °C, there seemed to be a different trend in the temperature-dependent ice nucleation activity from the suspension and dry-dispersed particle measurements for this mineral dust, in particular at higher temperatures. For instance, the ice nucleation activity expressed in n s was smaller for the average of the wet suspended samples and higher for the average of the dry-dispersed aerosol samples between about -27 and -18 °C. Only instruments making measurements with wet suspended samples were able to measure ice nucleation above -18 °C. A possible explanation for the deviation between -27 and -18 °C is discussed. Multiple exponential distribution fits in both linear and log space for both specific surface area-based n s( T) and geometric surface area-based n s( T) are provided. These new fits, constrained by using identical reference samples, will help to compare IN measurement methods that are not included in the present study and IN data from future IN instruments.« less

A comprehensive laboratory study on the immersion freezing behavior of illite NX particles. A comparison of 17 ice nucleation measurement techniques

DOE PAGES

Hiranuma, Naruki; Augustin-Bauditz, Stefanie; Bingemer, Heinz; ...

2015-03-06

Immersion freezing is the most relevant heterogeneous ice nucleation mechanism through which ice crystals are formed in mixed-phase clouds. In recent years, an increasing number of laboratory experiments utilizing a variety of instruments have examined immersion freezing activity of atmospherically relevant ice-nucleating particles. However, an intercomparison of these laboratory results is a difficult task because investigators have used different ice nucleation (IN) measurement methods to produce these results. A remaining challenge is to explore the sensitivity and accuracy of these techniques and to understand how the IN results are potentially influenced or biased by experimental parameters associated with these techniques.more » Within the framework of INUIT (Ice Nuclei Research Unit), we distributed an illite-rich sample (illite NX) as a representative surrogate for atmospheric mineral dust particles to investigators to perform immersion freezing experiments using different IN measurement methods and to obtain IN data as a function of particle concentration, temperature ( T), cooling rate and nucleation time. A total of 17 measurement methods were involved in the data intercomparison. Experiments with seven instruments started with the test sample pre-suspended in water before cooling, while 10 other instruments employed water vapor condensation onto dry-dispersed particles followed by immersion freezing. The resulting comprehensive immersion freezing data set was evaluated using the ice nucleation active surface-site density, n s, to develop a representative n s( T) spectrum that spans a wide temperature range (-37 °C < T < -11 °C) and covers 9 orders of magnitude in n s. In general, the 17 immersion freezing measurement techniques deviate, within a range of about 8 °C in terms of temperature, by 3 orders of magnitude with respect to n s. In addition, we show evidence that the immersion freezing efficiency expressed in n s of illite NX particles is relatively independent of droplet size, particle mass in suspension, particle size and cooling rate during freezing. A strong temperature dependence and weak time and size dependence of the immersion freezing efficiency of illite-rich clay mineral particles enabled the n s parameterization solely as a function of temperature. We also characterized the n s( T) spectra and identified a section with a steep slope between -20 and -27 °C, where a large fraction of active sites of our test dust may trigger immersion freezing. This slope was followed by a region with a gentler slope at temperatures below -27 °C. While the agreement between different instruments was reasonable below ~ -27 °C, there seemed to be a different trend in the temperature-dependent ice nucleation activity from the suspension and dry-dispersed particle measurements for this mineral dust, in particular at higher temperatures. For instance, the ice nucleation activity expressed in n s was smaller for the average of the wet suspended samples and higher for the average of the dry-dispersed aerosol samples between about -27 and -18 °C. Only instruments making measurements with wet suspended samples were able to measure ice nucleation above -18 °C. A possible explanation for the deviation between -27 and -18 °C is discussed. Multiple exponential distribution fits in both linear and log space for both specific surface area-based n s( T) and geometric surface area-based n s( T) are provided. These new fits, constrained by using identical reference samples, will help to compare IN measurement methods that are not included in the present study and IN data from future IN instruments.« less

Paraelectric-antiferroelectric phase transition in achiral liquid crystals

NASA Astrophysics Data System (ADS)

Pociecha, Damian; Gorecka, Ewa; Čepič, Mojca; Vaupotič, Nataša; Gomola, Kinga; Mieczkowski, Jozef

2005-12-01

Critical freezing of molecular rotation in an achiral smectic phase, which leads to polar ordering through the second order paraelectric-antiferroelectric (Sm-A→Sm-APA) phase transition is studied theoretically and experimentally. Strong softening of the polar mode in the Sm-A phase and highly intensive dielectric mode in the Sm-APA phase are observed due to weak antiferroelectric interactions in the system. In the Sm-APA phase the dielectric response behaves critically upon biasing by a dc electric field. Such a behavior is found general for the antiferroelectric smectic phase with significant quadrupolar interlayer coupling.

Seismic evidence for silicate melt atop the 410-km mantle discontinuity

USGS Publications Warehouse

Revenaugh, Justin; Sipkin, S.A.

1994-01-01

LABORATORY results demonstrating that basic to ultrabasic melts become denser than olivine-rich mantle at pressures above 6 GPa (refs 1-3) have important implications for basalt petrogenesis, mantle differentiation and the storage of volatiles deep in the Earth. A density cross-over between melt and solid in the extensively molten Archaean mantle has been inferred from komatiitic volcanism and major-element mass balances, but present-day evidence of dense melt below the seismic low-velocity zone is lacking. Here we present mantle shear-wave impedance profiles obtained from multiple-ScS reverberation mapping for corridors connecting western Pacific subduction zone earthquakes with digital seismograph stations in eastern China, imaging a ~5.8% impedance decrease roughly 330 km beneath the Sea of Japan, Yellow Sea and easternmost Asia. We propose that this represents the upper surface of a layer of negatively buoyant melt lying on top of the olivine ??? ??- phase transition (the 410-km seismic discontinuity). Volatile-rich fluids expelled from the partial melt zone as it freezes may migrate upwards, acting as metasomatic agents and perhaps as the deep 'proto-source' of kimberlites. The remaining, dense, crystalline fraction would then concentrate above 410 km, producing a garnet-rich layer that may flush into the transition zone.

Liquid-solid phase transition of hydrogen and deuterium in silica aerogel

NASA Astrophysics Data System (ADS)

Van Cleve, E.; Worsley, M. A.; Kucheyev, S. O.

2014-10-01

Behavior of hydrogen isotopes confined in disordered low-density nanoporous solids remains essentially unknown. Here, we use relaxation calorimetry to study freezing and melting of H2 and D2 in an ˜85%-porous base-catalyzed silica aerogel. We find that liquid-solid transition temperatures of both isotopes inside the aerogel are depressed. The phase transition takes place over a wide temperature range of ˜4 K and non-trivially depends on the liquid filling fraction, reflecting the broad pore size distribution in the aerogel. Undercooling is observed for both H2 and D2 confined inside the aerogel monolith. Results for H2 and D2 are extrapolated to tritium-containing hydrogens with the quantum law of corresponding states.

Methane emission from high-latitude (>50N) lakes: Annual cycle of climatological emissions using satellite-derived lake-ice phenology and freeze-thaw dynamics

NASA Astrophysics Data System (ADS)

Matthews, E.; Romanski, J.; Du, J.; Watts, J. D.

2017-12-01

Lakes are increasingly recognized as potentially important contributors to global methane emissions despite occupying only a few percent of Earth's ice-free land surface. More than 40% of the global lake area lies in regions of amplified warming north of 50˚N. As with wetlands, lake emissions are sensitive to interannual fluctuations in, e.g., temperature and duration of thaw season. Several estimates of CH4emission from high-latitude lakes have been published but none relies on geospatial lake distributions and satellite-based duration and timing of thaw seasons. We report on a climatology of weekly, spatially-explicit methane emissions from high-latitude lakes. Lake break-up and freeze-up dates for lakes >50km^2 were determined from a lake-ice phenology data set derived from brightness temperature (Tb) observations of space-borne Advanced Microwave Scanning Radiometer (AMSR-E/2) sensors. The lake-ice conditions for smaller lakes were estimated using an Earth System Data Record for Land Surface Freeze-Thaw State derived from Tb observations of Scanning Multichannel Microwave Radiometer (SMMR), Special Sensor Microwave Imager (SSM/I), and SSM/I Sounder (SSMIS). Climatologies encompass 2002-2015 for lake ice phenology and 1979 to 2010 for the land surface freeze-thaw state. Climatologies encompass 2003-2014 for ice phenology and 1979 to 2010 for freeze-thaw dynamics. Length and timing of typical methane-emission periods, derived from the satellite data, were integrated with daily diffusive and ebulliative methane fluxes for lake types following the work of Wik et al. (Nature, 2016) to estimate a full annual cycle of emissions from lakes >50˚N. We explored several approaches to estimate the large bursts of emissions observed over short periods during lake-ice breakup immediately prior to full lake thaw since several studies suggest that a substantial fraction of total annual emissions may occur at this time. While highly uncertain, we plan to investigate whether the modest, short-lived but annual uptick in atmospheric methane concentrations in late winter/early spring may be associated with these bursts of methane from lakes.

Stochastic Flux-Freezing in MHD Turbulence and Reconnection in the Heliosheath

NASA Astrophysics Data System (ADS)

Eyink, G. L.; Lalescu, C.; Vishniac, E.

2012-12-01

Fast reconnection of the sectored magnetic field in the heliosheath created by flapping of the heliospheric current sheet has been conjectured to accelerate anomalous cosmic rays and to create other signatures observed by the Voyager probes. The reconnecting flux structures could have sizes up to ˜100 AU, much larger than the ion cyclotron radius ˜10^3 km. Hence MHD should be valid at those scales. To account for rapid reconnection of such large-scale structures, we note that the high Reynolds numbers in the heliosheath for motions perpendicular to the magnetic field (Re ˜10^{14}) suggest transition to turbulence. The Lazarian-Vishnian theory of turbulent reconnection can account for the fast rates, but it implies a puzzling breakdown of magnetic flux-freezing in high-conductivity MHD plasmas. We address this paradox with a novel stochastic formulation of flux-freezing for resistive MHD and a numerical Lagrangian study with a spacetime database of MHD turbulence. We report the first observation of Richardson diffusion in MHD turbulence, which leads to "spontaneous stochasticity" of the Lagrangian trajectories and a violation of standard flux-freezing by many orders of magnitude. The work supports a prediction by Lazarian-Opher (2009) of extended thick reconnection zones within the heliosheath, perhaps up to an AU across, although the microscale reconnection events within these zones would have thickness of order the ion cyclotron radius and be described by kinetic Vlasov theory.

Stochastic Flux-Freezing in MHD Turbulence and Reconnection in the Heliosheath (Invited)

NASA Astrophysics Data System (ADS)

Eyink, G. L.; Lalescu, C. C.; Vishniac, E. T.

2013-12-01

Fast reconnection of the sectored magnetic field in the heliosheath created by flapping of the heliospheric current sheet has been conjectured to accelerate anomalous cosmic rays and to create other signatures observed by the Voyager probes. The reconnecting flux structures could have sizes up to ˜100 AU, much larger than the ion cyclotron radius ˜103 km. Hence MHD should be valid at those scales. To account for rapid reconnection of such large-scale structures, we note that the high Reynolds numbers in the heliosheath for motions perpendicular to the magnetic field (Re ˜1014) suggest transition to turbulence. The Lazarian-Vishnian theory of turbulent reconnection can account for the fast rates, but it implies a puzzling breakdown of magnetic flux-freezing in high-conductivity MHD plasmas. We address this paradox with a novel stochastic formulation of flux-freezing for resistive MHD and a numerical Lagrangian study with a spacetime database of MHD turbulence. We report the first observation of Richardson diffusion in MHD turbulence, which leads to 'spontaneous stochasticity' of the Lagrangian trajectories and a violation of standard flux- freezing by many orders of magnitude. The work supports a prediction by Lazarian-Opher (2009) of extended thick reconnection zones within the heliosheath, perhaps up to an AU across, although the microscale reconnection events within these zones would have thickness of order the ion cyclotron radius and be described by kinetic Vlasov theory.

Response of changes in seasonal soil freeze/thaw state to climate change from 1950 to 2010 across china

NASA Astrophysics Data System (ADS)

Peng, Xiaoqing; Frauenfeld, Oliver W.; Cao, Bin; Wang, Kang; Wang, Huijuan; Su, Hang; Huang, Zhe; Yue, Dongxia; Zhang, Tingjun

2016-11-01

Variations in seasonal soil freeze/thaw state are important indicators of climate change and influence ground temperature, hydrological processes, surface energy, and the moisture balance. Previous studies mainly focused on the active layer and permafrost, while seasonally frozen ground research in nonpermafrost regions has received less attention. In this study, we investigate the response of changes in seasonal soil freeze/thaw state to changes in air temperatures by combining observations from more than 800 stations with gridded mean monthly air temperature data across China. The results show that mean annual air temperature (MAAT) increased statistically significantly by 0.29 ± 0.03°C/decade from 1967 to 2013, with greater warming on the Qinghai-Tibetan Plateau. There is a statistically significant decrease in the freeze/thaw cycle (FTC) at 0.39 ± 0.05 cycles/decade. In addition, there are strong negative correlations between FTC and MAAT. Estimating the soil freeze/thaw state classification based on the number of days in the month, we find that changes of mean annual area extent of seasonal soil freeze/thaw state decreased significantly for completely frozen (CF) ground, while the area extent of partially frozen (PF) and unfrozen (UF) ground both increased. Changes in mean monthly area extent of seasonal soil freeze/thaw state indicate that the extent of CF and UF area was decreasing and increasing, respectively. But for the extent of PF areas, both increasing and decreasing trends were observed. Quantifying the spatial pattern of the seasonal soil freeze/thaw, we find that CF and PF areas are located in northern China and the Tibetan Plateau from December to March, and UF areas are located in southern China. The variations of mean annual area extent departure of soil freeze/thaw states are consistent with MAAT changes in different land cover types across China.

Deposition nucleation viewed as homogeneous or immersion freezing in pores and cavities

NASA Astrophysics Data System (ADS)

Marcolli, C.

2013-06-01

Heterogeneous ice nucleation is an important mechanism for the glaciation of mixed phase clouds and may also be relevant for cloud formation and dehydration at the cirrus cloud level. It is thought to proceed through different mechanisms, namely contact, condensation, immersion and deposition nucleation. Supposedly, deposition nucleation is the only pathway which does not involve liquid water but occurs by direct water vapor deposition on a surface. This study challenges this classical view by putting forward the hypothesis that what is called deposition nucleation is in fact homogeneous or immersion nucleation occurring in pores and cavities that may form between aggregated primary particles and fill with water at relative humidity RHw < 100% because of the inverse Kelvin effect. Evidence for this hypothesis of pore condensation and freezing (PCF) originates from a number of only loosely connected scientific areas. The prime example for PCF is ice nucleation in clay minerals and mineral dusts, for which the data base is best. Studies on freezing in confinement carried out on mesoporous silica materials such as SBA-15, SBA-16, MCM-41, zeolites and KIT have shown that homogeneous ice nucleation occurs abruptly at T=230-235 K in pores with diameters (D) of 3.5-4 nm or larger but only gradually at T=210-230 K in pores with D=2.5-3.5 nm. Melting temperatures in pores are depressed by an amount that can be described by the Gibbs-Thomson equation. Water adsorption isotherms of MCM-41 show that pores with D=3.5-4 nm fill with water at RHw = 56-60% in accordance with an inverse Kelvin effect. Water in such pores should freeze homogeneously for T < 235 K even before relative humidity with respect to ice (RHi) reaches ice saturation. Ice crystal growth by water vapor deposition from the gas phase is therefore expected to set in as soon as RHw > 100%. Pores with D > 7.5 nm fill with water at RHi > 100% for T < 235 K and are likely to freeze homogeneously as soon as they are filled with water. Water in pores can freeze in immersion mode at T > 235 K if the pore walls contain an active site. Pore analysis of clay minerals shows that kaolinites exhibit pore structures with pore diameters of 20-50 nm. The mesoporosity of illites and montmorillonites is characterized by pores with T = 2-5 nm. The number and size of pores is distinctly increased in acid treated montmorillonites like K10. Many clay minerals and mineral dusts show a strong increase in ice nucleation efficiency when temperature is decreased below 235 K. Such an increase is difficult to explain when ice nucleation is supposed to occur by a deposition mechanism, but evident when assuming freezing in pores, because for homogeneous ice nucleation only small pore volumes are needed, while heterogeneous ice nucleation requires larger pore structures to contain at least one active site for immersion nucleation. Together, these pieces of evidence strongly suggest that ice nucleation within pores should be the prevailing freezing mechanism of clay minerals for RHw below water saturation. Extending the analysis to other types of ice nuclei shows that freezing in pores and cracks is probably the prevailing ice nucleation mechanism for glassy and volcanic ash aerosols at RHw below water saturation. Freezing of water in carbon nanotubes might be of significance for ice nucleation by soot aerosols. No case could be identified that gives clear evidence of ice nucleation by water vapor deposition on a solid surface. Inspection of ice nuclei with a close lattice match to ice, such as silver iodide or SnomaxTM, show that for high ice nucleation efficiency below water saturation the presence of impurities or cracks on the surface may be essential. Soluble impurities promote the formation of a liquid phase below water saturation in patches on the surface or as a complete surface layer that offers an environment for immersion freezing. If porous aerosol particles come in contact with semivolatile vapors, these will condense preferentially in pores before a coating on the surface of the particles is formed. A pore partially filled with condensed species attracts water at lower RHw than an empty pore, but the aqueous solution that forms in the pore will freeze at a higher RHi than pure water. The ice nucleation ability of pores completely filled with condensed organic species might be totally impeded. Pores might also be important for preactivation, the capability of a particle to nucleate ice at lower RHi in subsequent experiments when compared to the first initial ice nucleation event. Preactivation has often been explained by persistence of ice embryos at specific sites like dislocations, steps, kinks or pores. However, it is not clear how such features can preserve an ice embryo at RHi < 100%. Rather, ice embryos could be preserved when embedded in water. To keep liquid water at RHw well below 100%, narrow pores are needed but to avoid a strong melting point depression large pores are favorable. A narrow pore opening and a large inner volume are combined in "ink bottle" pores. Such "ink bottle" pores would be suited to preserve ice at RHi < 100% and can arise e.g. in spaces between aggregated particles.

Heterogeneous freezing of droplets with immersed surface modified mineral dust particles

NASA Astrophysics Data System (ADS)

Hartmann, Susan

2010-05-01

In the framework of the international measurement campaign FROST II (FReezing Of duST), the heterogeneous freezing of droplets with an immersed surface modified size-segregated mineral dust particles was investigated at LACIS (Leipzig Aerosol Cloud Interaction Simulator, Stratmann et al. 2004). The following measurements were done: LACIS, CFDC (Continuous Flow thermal gradient Diffusion Chamber, Rogers (1988)) and FINCH (Fast Ice Nucleus Chamber Counter, Bundke et al (2008)) were used to analyze the immersion freezing behavior of the treated Arizona Test Dust (ATD) particles at different temperature regimes. The ability to act as IN (Ice Nucleus) in the deposition nucleation mode was quantified by the PINC (Portable Ice Nucleation Chamber) and the CFDC instrument. AMS (Aerosol Mass Spectrometers, e.g. Schneider et al. (2005)) and ATOFMS (Aerosol Time-Of-Flight Mass Spectrometer) measurements were applied to determine particle composition. The hygroscopic growth and the critical super-saturations needed for droplet activation were determined by means of an H-TDMA (Humidity-Tandem Differential Mobility Analyzer) and CCN counter (Cloud Condensation Nucleus counter, Droplet Measurement Technologies, Roberts and Nenes (2005)). The 300 nm ATD particles were chemically and physically treated by coating with sulphuric acid (H2SO4, three different coating thicknesses) and ammonium sulphate ((NH4)2SO4) or by thermal treatment with a thermodenuder operating at 250°C. The H2SO4 coating modified the particles by reacting with particle material, forming soluble sulfates and therefore changing surface properties. AMS showed free H2SO4 only for thick H2SO4 coatings. In the heated section of the thermodenuder coating materials were evaporated partly and the surface properties of the particles were additionally altered. Uncoated particles and those coated with thin coatings of H2SO4, showed almost no hygroscopic growth. Particles coated with thicker coatings of H2SO4 and of (NH4)2SO4 grew noticeably above 95% relative humidity. All investigated particles were found to activate at atmospherically relevant super-saturations. All kinds of treatment lower the IN-ability, whereas the deposition nucleation was more sensitive to treatments than the immersion freezing mode. Considering the immersion freezing behavior, pure ATD particles and particles coated with thin coatings of H2SO4 were more efficient IN, than particles with thick H2SO4 or (NH4)2SO4 coatings. Thermal treatments of the particles led to further decrease of the IN capability except for particles coated with (NH4)2SO4, where the heating did not effect the immersion freezing behavior likely due to their already reduced IN ability. In order to specify the temperature-dependent immersion freezing, two parameterization based on either stochastic or singular hypothesis were performed. From both theoretical approaches it can be concluded that the treatments lead to particle surface modifications lowering the nucleation efficiency. References: Bundke, U., B. Nillius, et al. (2008), The fast Ice Nucleus chamber FINCH, Atmospheric Research 90(2-4): 180-186. Rader, D. J. and P. H. McMurry (1986), Application of the Tandem Differential Mobility Analyzer to studies of droplet growth or evaporation, J. Aerosol Sci., Vol. 17, No. 5, pp. 771-787. Roberts, G., and A. Nenes (2005), A continuous-flow streamwise thermal-gradient CCN chamber for atmospheric measurements, Aerosol Sci. Technol., 39, 206-221. Schneider, J., N. Hock, S. Weimer, S. Borrmann, U. Kirchner, R. Vogt, and V. Scheer (2005), Nucleation particles in Diesel exhaust: Composition inferred from in situ mass spectrometric analysis, Environ. Sci. Technol., 39, 6153-6161. Rogers,D .C. (1988), Developmenot f a continuousflow thermal gradient diffusion chamber for ice nucleation studies. Atmospheric Research, 22, 149-181. Stratmann, F., A. Kiselev, S. Wurzler, M. Wendisch, J. Heintzenberg, R. J. Charlson, K. Diehl, H. Wex, and S. Schmidt (2004), Laboratory studies and numerical simulations of cloud droplet formation under realistic super-saturation conditions, J. Atmos. Oceanic Technol., 21, 876-887.

Automated Discovery of Elementary Chemical Reaction Steps Using Freezing String and Berny Optimization Methods.

PubMed

Suleimanov, Yury V; Green, William H

2015-09-08

We present a simple protocol which allows fully automated discovery of elementary chemical reaction steps using in cooperation double- and single-ended transition-state optimization algorithms--the freezing string and Berny optimization methods, respectively. To demonstrate the utility of the proposed approach, the reactivity of several single-molecule systems of combustion and atmospheric chemistry importance is investigated. The proposed algorithm allowed us to detect without any human intervention not only "known" reaction pathways, manually detected in the previous studies, but also new, previously "unknown", reaction pathways which involve significant atom rearrangements. We believe that applying such a systematic approach to elementary reaction path finding will greatly accelerate the discovery of new chemistry and will lead to more accurate computer simulations of various chemical processes.

Lithium Circuit Test Section Design and Fabrication

NASA Technical Reports Server (NTRS)

Godfroy, Thomas; Garber, Anne

2006-01-01

The Early Flight Fission - Test Facilities (EFF-TF) team has designed and built an actively pumped lithium flow circuit. Modifications were made to a circuit originally designed for NaK to enable the use of lithium that included application specific instrumentation and hardware. Component scale freeze/thaw tests were conducted to both gain experience with handling and behavior of lithium in solid and liquid form and to supply anchor data for a Generalized Fluid System Simulation Program (GFSSP) model that was modified to include the physics for freeze/thaw transitions. Void formation was investigated. The basic circuit components include: reactor segment, lithium to gas heat exchanger, electromagnetic (EM) liquid metal pump, load/drain reservoir, expansion reservoir, instrumentation, and trace heaters. This paper will discuss the overall system design and build and the component testing findings.

Lithium Circuit Test Section Design and Fabrication

NASA Astrophysics Data System (ADS)

Godfroy, Thomas; Garber, Anne; Martin, James

2006-01-01

The Early Flight Fission - Test Facilities (EFF-TF) team has designed and built an actively pumped lithium flow circuit. Modifications were made to a circuit originally designed for NaK to enable the use of lithium that included application specific instrumentation and hardware. Component scale freeze/thaw tests were conducted to both gain experience with handling and behavior of lithium in solid and liquid form and to supply anchor data for a Generalized Fluid System Simulation Program (GFSSP) model that was modified to include the physics for freeze/thaw transitions. Void formation was investigated. The basic circuit components include: reactor segment, lithium to gas heat exchanger, electromagnetic (EM) liquid metal pump, load/drain reservoir, expansion reservoir, instrumentation, and trace heaters. This paper discusses the overall system design and build and the component testing findings.

New insights in permafrost modelling

NASA Astrophysics Data System (ADS)

Tubini, Niccolò; Serafin, Francesco; Gruber, Stephan; Casulli, Vincenzo; Rigon, Riccardo

2017-04-01

Simulating freezing soil has ignored for long time in mainstream surface hydrology. However, it has indubitably a large influence on soil infiltrability and an even larger influence on the soil energy budget, and, over large spatial scales, a considerable feedback on climate. The topic is difficult because it involves concepts of disequilibrium Thermodynamics and also because, once solved the theoretical problem, integration of the resulting partial differential equations in a robust manner, is not trivial at all. In this abstract, we are presenting a new algorithm to estimate the water and energy budget in freezing soils. The first step is a derivation of a new equation for freezing soil mass budget (called generalized Richards equation) based on the freezing equals drying hypothesis (Miller 1965). The second step is the re-derivation of the energy budget. Finally there is the application of new techniques based on the double nested Newton algorithm (Casulli and Zanolli, 2010) to integrate the coupled equations. Some examples of the freezing dynamics and comparison with the Dall'Amico et al. (2011) algorithm are also shown. References Casulli, V., & Zanolli,P. (2010). A nested newton-type algorithm for finite colume methods solving Richards' equation in mixed form. SIAM J. SCI. Comput., 32(4), 2225-2273. Dall'Amico, M., Endrizzi, S., Gruber, S., & Rigon, R. (2011). A robust and energy-conserving model of freezing variably-saturated soil. The Cryosphere, 5(2), 469-484. http://doi.org/10.5194/tc-5-469-2011 Miller, R.: Phase equilibria and soil freezing, in: Permafrost: Proceedings of the Second International Conference. Washington DC: National Academy of Science-National Research Council, 287, 193-197, 1965.

Sample handling for mass spectrometric proteomic investigations of human urine.

PubMed

Petri, Anette Lykke; Høgdall, Claus; Christensen, Ib Jarle; Simonsen, Anja Hviid; T'jampens, Davy; Hellmann, Marja-Leena; Kjaer, Susanne Krüger; Fung, Eric T; Høgdall, Estrid

2008-09-01

Because of its non-invasive sample collection method, human urine is an attractive biological material both for discovering biomarkers and for use in future screening trials for different diseases. Before urine can be used for these applications, standardized protocols for sample handling that optimize protein stability are required. In this explorative study, we examine the influence of different urine collection methods, storage temperatures, storage times, and repetitive freeze-thaw procedures on the protein profiles obtained by surface-enhanced laser desorption/ionization time-of-flight mass spectrometry (SELDI-TOF-MS). Prospectively collected urine samples from 11 women were collected as either morning or midday specimens. The effects of storage temperature, time to freezing, and freeze-thaw cycles were assessed by calculating the number, intensity, and reproducibility of peaks visualized by SELDI-TOF-MS. On the CM10 array, 122 peaks were detected and 28 peaks were found to be significantly different between urine types, storage temperature and time to freezing. On the IMAC-Cu array, 65 peaks were detected and 1 peak was found to be significantly different according to time to freezing. No significant differences were demonstrated for freeze-thaw cycles. Optimal handling and storage conditions are necessary in clinical urine proteomic investigations. Collection of urine with a single and consistently performed protocol is needed to reduce analytical bias. Collecting only one urine type, which is stored for a limited period at 4°C until freezing at -80°C prior to analysis will provide the most stable profiles. Copyright © 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dark Matter Decay between Phase Transitions at the Weak Scale.

PubMed

Baker, Michael J; Kopp, Joachim

2017-08-11

We propose a new alternative to the weakly interacting massive particle paradigm for dark matter. Rather than being determined by thermal freeze-out, the dark matter abundance in this scenario is set by dark matter decay, which is allowed for a limited amount of time just before the electroweak phase transition. More specifically, we consider fermionic singlet dark matter particles coupled weakly to a scalar mediator S_{3} and to auxiliary dark sector fields, charged under the standard model gauge groups. Dark matter freezes out while still relativistic, so its abundance is initially very large. As the Universe cools down, the scalar mediator develops a vacuum expectation value (VEV), which breaks the symmetry that stabilizes dark matter. This allows dark matter to mix with charged fermions and decay. During this epoch, the dark matter abundance is reduced to give the value observed today. Later, the SM Higgs field also develops a VEV, which feeds back into the S_{3} potential and restores the dark sector symmetry. In a concrete model we show that this "VEV flip-flop" scenario is phenomenologically successful in the most interesting regions of its parameter space. We also comment on detection prospects at the LHC and elsewhere.

Dark Matter Decay between Phase Transitions at the Weak Scale

NASA Astrophysics Data System (ADS)

Baker, Michael J.; Kopp, Joachim

2017-08-01

We propose a new alternative to the weakly interacting massive particle paradigm for dark matter. Rather than being determined by thermal freeze-out, the dark matter abundance in this scenario is set by dark matter decay, which is allowed for a limited amount of time just before the electroweak phase transition. More specifically, we consider fermionic singlet dark matter particles coupled weakly to a scalar mediator S3 and to auxiliary dark sector fields, charged under the standard model gauge groups. Dark matter freezes out while still relativistic, so its abundance is initially very large. As the Universe cools down, the scalar mediator develops a vacuum expectation value (VEV), which breaks the symmetry that stabilizes dark matter. This allows dark matter to mix with charged fermions and decay. During this epoch, the dark matter abundance is reduced to give the value observed today. Later, the SM Higgs field also develops a VEV, which feeds back into the S3 potential and restores the dark sector symmetry. In a concrete model we show that this "VEV flip-flop" scenario is phenomenologically successful in the most interesting regions of its parameter space. We also comment on detection prospects at the LHC and elsewhere.

Oxidative stability of soybean oil in oleosomes as affected by pH and iron.

PubMed

Kapchie, Virginie N; Yao, Linxing; Hauck, Catherine C; Wang, Tong; Murphy, Patricia A

2013-12-01

The oxidative stability of oil in soybean oleosomes, isolated using the Enzyme-Assisted Aqueous Extraction Process (EAEP), was evaluated. The effects of ferric chloride, at two concentration levels (100 and 500 μM), on lipid oxidation, was examined under pH 2 and 7. The peroxide value (PV) and thiobarbituric acid-reactive substance (TBARS) value of oil, in oleosome suspensions stored at 60 °C, were measured over a 12 day period. The presence of ferric chloride significantly (P<0.05) affected the oxidative stability of oil in the isolated oleosome, as measured by the PV and TBARS. Greater lipid oxidation occurred under an acidic pH. In the pH 7 samples, the positively charged transition metals were strongly attracted to the negatively charged droplets. However, the low ζ-potential and the high creaming rate at this pH, may have limited the oxidation. Freezing, freeze-drying or heating of oleosomes have an insignificant impact on the oxidative stability of oil in isolated soybean oleosomes. Manufacturers should be cautious when adding oleosomes as ingredients in food systems containing transition metal ions. Published by Elsevier Ltd.

An ultrastructural analysis of the epithelial-fiber interface (EFI) in primate lenses.

PubMed

Kuszak, J R; Novak, L A; Brown, H G

1995-11-01

The purpose of this study was to conduct a comprehensive ultrastructural analysis of the epithelial-fiber interface (EFI) in normal adult primate (Macaque nemestrina and fascicularis; 6-9 years old, n = 10) lenses. Scanning electron microscopy (SEM) was used to initially characterize the gross size, shape and three-dimensional organization of central zone (cz) epithelial cells and the anterior ends of elongating fibers beneath these cells. This fiducial information was essential to properly orient lens pieces in freeze fracture specimen carriers for the production of replicas with unambiguously identifiable EFI. Transmission electron microscopy (TEM) of replicas and thin-sectioned material were used to ultrastructurally analyse the cz EFI. TEM thin-sectioned material was also used to ultrastructurally analyse the pregerminative (pgz), germinative (gz) and transitional zone (tz) EFI. Correlative SEM and TEM of cz EFI components revealed that the apical membrane of both epithelial and elongating fiber cells were irregularly polygonal in shape, and aligned in parallel as smooth, concave-convex surfaces. However, whereas epithelial cell apical surfaces had minimal size variation, elongating fibers were larger and considerably variable in size. Quantitative analysis of > 10000 micron2 cz elongating fiber apical surfaces failed to detect any gap junctions defined in freeze fracture replicas as complementary aggregates of transmembrane proteins (connexons) conjoined across a narrowed extracellular space. However, a comparable frequency of vesicular events was noted in this region as quantified previously in adult and embryonic chick lens. Correlative TEM analysis > 1500 linear micrometers of thin-sectioned EFI from this region confirmed the presence of epithelial-epithelial gap junctions, elongating fiber-elongating fiber gap junctions, and an extreme paucity of epithelial-elongating fiber gap junctions. In contrast, TEM analysis of > 1000 linear micrometers of thin-sectioned pgz, gz and tz EFI, confirmed the presence of epithelial-epithelial gap junctions, elongating fiber-elongating fiber gap junctions, numerous epithelial-elongating fiber adherens junctions and a few epithelial-elongating fiber gap junctions. Thus, the results of this and previous quantitative morphological and physiological studies (electronic and dye coupling) demonstrate that there is limited coupling between cz epithelial cells and underlying elongating fibers. Furthermore, the absence of gap junctional plaques in cz EFI freeze-fracture replicas and either pentalaminar or septalaminar profiles in correlative thin-sections, suggests that this limited coupling could be mediated via isolated gap junction channels. However, the results of this and previous quantitative studies further show that a greater degree of coupling exists across the pgz, gz and tz regions of the EFI and that this coupling is likely to be mediated by gap junction plaques. Finally, this and other studies continue to demonstrate that transcytotic processes play a role in lens physiology at the EFI.

Suspension freezing of bottom sediment and biota in the Northwest Passage and implications for Arctic Ocean sedimentation

USGS Publications Warehouse

Reimnitz, E.; Marincovich, L.; McCormick, M.; Briggs, W.M.

1992-01-01

No evidence was seen for entrainment by bottom adfreezing, bluff slumping, river flooding, dragging ice keels, or significant eolian transport from land to sea. Muddy sediment with pebbles and cobbles, algae with holdfasts, ostracodes with appendages, and well-preserved mollusks and sea urchins were collected from two sites in a 50 km long stretch of turbid ice. These materials indicate that suspension freezing reaching to a water depth of 25-30 m during the previous fall was responsible for entrainment. This mechanism requires rapid ice formation in open, shallow water during a freezing storm, when the ocean becomes supercooled, and frazil and anchor ice attach to and ultimately lift sediment and living organisms to the sea surface. -from Authors

Experimental simulation of frost wedging-induced crack propagation in alpine rockwall

NASA Astrophysics Data System (ADS)

Jia, Hailiang; Leith, Kerry; Krautblatter, Michael

2016-04-01

Frost wedging is widely presumed to be the principal mechanism responsible for shattering jointed low-porosity rocks in high alpine rockwalls. The interaction of ice and rock physics regulates the efficacy of frost wedging. In order to better understand temporal aspects of this interaction, we present results of a series of laboratory experiments monitoring crack widening as a result of ice formation in an artificial crack (4mm wide, 80mm deep) cut 20 mm from the end of a rectangular granite block. Our results indicate that i) freezing direction plays a key role in determining the magnitude of crack widening; in short-term (1 day) experiments, maximum crack widening during top-down freezing (associated with 'autumn' conditions) was around 0.11mm, while inside-out freezing (resulting from 'spring' conditions) produced only 0.02 mm of deformation; ii) neither ice, nor water pressure (direct tension and hydraulic fracturing respectively) caused measurable irreversible crack widening during short-term tests, as the calculated maximum stress intensity at the crack tip was less than the fracture toughness of our granite sample; iii) development of ice pressure is closely related to the mechanical properties of the fracture in which it forms, and as such, the interaction of ice and rock is intrinsically dynamic; iv) irreversible crack widening (about 0.03mm) was only observed following a long-term (53 day) experiment representing a simplified transition from autumn to winter conditions. We suggest this is the result of stress corrosion aided by strong opening during freezing, and to a lesser degree by ice segregation up to one week after the initial freezing period, and downward migration of liquid water during the remainder of the test. Our results suggest the fundamental assumption of frost wedging, that rapid freezing from open ends of cracks can seal water inside the crack and thus cause damage through excessive stresses induced by volumetric expansion seems questionable.

Crystallization features of normal alkanes in confined geometry.

PubMed

Su, Yunlan; Liu, Guoming; Xie, Baoquan; Fu, Dongsheng; Wang, Dujin

2014-01-21

How polymers crystallize can greatly affect their thermal and mechanical properties, which influence the practical applications of these materials. Polymeric materials, such as block copolymers, graft polymers, and polymer blends, have complex molecular structures. Due to the multiple hierarchical structures and different size domains in polymer systems, confined hard environments for polymer crystallization exist widely in these materials. The confined geometry is closely related to both the phase metastability and lifetime of polymer. This affects the phase miscibility, microphase separation, and crystallization behaviors and determines both the performance of polymer materials and how easily these materials can be processed. Furthermore, the size effect of metastable states needs to be clarified in polymers. However, scientists find it difficult to propose a quantitative formula to describe the transition dynamics of metastable states in these complex systems. Normal alkanes [CnH2n+2, n-alkanes], especially linear saturated hydrocarbons, can provide a well-defined model system for studying the complex crystallization behaviors of polymer materials, surfactants, and lipids. Therefore, a deeper investigation of normal alkane phase behavior in confinement will help scientists to understand the crystalline phase transition and ultimate properties of many polymeric materials, especially polyolefins. In this Account, we provide an in-depth look at the research concerning the confined crystallization behavior of n-alkanes and binary mixtures in microcapsules by our laboratory and others. Since 2006, our group has developed a technique for synthesizing nearly monodispersed n-alkane containing microcapsules with controllable size and surface porous morphology. We applied an in situ polymerization method, using melamine-formaldehyde resin as shell material and nonionic surfactants as emulsifiers. The solid shell of microcapsules can provide a stable three-dimensional (3-D) confining environment. We have studied multiple parameters of these microencapsulated n-alkanes, including surface freezing, metastability of the rotator phase, and the phase separation behaviors of n-alkane mixtures using differential scanning calorimetry (DSC), temperature-dependent X-ray diffraction (XRD), and variable-temperature solid-state nuclear magnetic resonance (NMR). Our investigations revealed new direct evidence for the existence of surface freezing in microencapsulated n-alkanes. By examining the differences among chain packing and nucleation kinetics between bulk alkane solid solutions and their microencapsulated counterparts, we also discovered a mechanism responsible for the formation of a new metastable bulk phase. In addition, we found that confinement suppresses lamellar ordering and longitudinal diffusion, which play an important role in stabilizing the binary n-alkane solid solution in microcapsules. Our work also provided new insights into the phase separation of other mixed system, such as waxes, lipids, and polymer blends in confined geometry. These works provide a profound understanding of the relationship between molecular structure and material properties in the context of crystallization and therefore advance our ability to improve applications incorporating polymeric and molecular materials.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Souza, Douglas F., E-mail: souzadf@outlook.com; Nunes, Eduardo H.M., E-mail: eduardohmn@gmail.com; Pimenta, Daiana S.

In this work we fabricated alumina samples by the freeze-casting technique using tert-butanol as the solvent. The prepared materials were examined by scanning electron microscopy and X-ray microtomography. Next, they were coated with sol–gel silica films by dip-coating. Permeability tests were carried out in order to assess the permeation behavior of the materials processed in this study. We observed that the sintering time and alumina loading showed a remarkable effect on both the structural properties and flexural strength of the freeze-cast samples. Nitrogen adsorption tests revealed that the silica prepared in this study exhibited a microporous structure. It was observedmore » that the presence of silica coatings on the alumina surface decreased the CO{sub 2} permeance by about one order of magnitude. Because of the similar kinetic diameters of nitrogen and carbon dioxide, the CO{sub 2}/N{sub 2} system showed a separation efficiency that was lower than that observed for the He/CO{sub 2} and He/N{sub 2} systems. We noticed that increasing the feed pressure improved the separation capacity of the obtained materials. - Highlights: • Porous alumina samples obtained by the freeze-casting technique • Microporous silica coating prepared by a simple sol–gel dip-coating methodology • Samples examined by SEM, μ-CT, and nitrogen sorption tests • Mechanical tests were carried out in the freeze-cast samples. • The presence of silica coatings on the alumina surface decreased the CO{sub 2} permeance.« less

On the consistency of the Oppenheimer-Snyder solution for a dust star. Reply to Marshall's criticism

NASA Astrophysics Data System (ADS)

Zakir, Zahid

2018-02-01

The recent alternative to the Oppenheimer-Snyder (OS) solution for a dust star proposed by Marshall in the paper "Gravitational collapse without black holes" (Astrophys. Space Sci. 342:329, 2012) is analyzed. It is shown that this proposal leads to a non-diagonal metric, with which the Einstein equations become practically unsolvable. Any ansatz proposed as their exact solution turns out to be arbitrary and may be unlimited number of the such solutions. This is due to the fact that an auxiliary function y(R,r), introduced by OS as t=M(y), is unambiguously fixed by the diagonality condition and the matching on the surface, and thus in the non-diagonal case it remains arbitrary. It is also shown that the OS solution, as a description in terms of the Schwarzschild coordinates, leads to a frozen star (or frozar) picture not only for the surface, asymptotically freezing outside the gravitational radius, but for interior layers too which also freeze near their own asymptotes. At most of the inner region these asymptotes are located almost equidistantly and only for layers initially close to the surface they become denser. The reason for the such densifying is not "a gravitational repulsion", but their later freezing and higher spatial contractions, while they remain be uniform and free falling in the comoving frames.

Effect of whey protein isolate-pullulan edible coatings on the quality and shelf life of freshly roasted and freeze-dried Chinese chestnut.

PubMed

Gounga, M E; Xu, S-Y; Wang, Z; Yang, W G

2008-05-01

Harvested chestnut is characterized by a short shelf life, exposing many Chinese producers to a storage problem as product losses are very high. The objective of this study was to develop a suitable technology to extend the shelf life of harvested chestnut fruits for commercial use. The effect of whey protein isolate-pullulan (WPI-Pul) coating on fresh-roasted chestnuts (FRC) and roasted freeze-dried chestnut (RFDC) quality and shelf life was studied under 2 different storage temperature (4 and 20 degrees C) conditions. Coatings were formed directly onto the surface of the fruits by dipping them into a film solution. SEM micrographs showed homogeneous WPI-Pul to cover the whole surface of chestnut with good adherence and perfect integrity. Moisture loss or gain, fruit quality, and shelf life were evaluated by weight loss or gain, surface color development, and visible decay during the storage period of 15 to 120 d at 4 and 20 degrees C, respectively. WPI-Pul coating had a low, yet significant effect on reducing moisture loss and decay incidence of FRC, hence delaying changes in their external color. The results were satisfactory when the coating was done with freeze-drying at low temperature storage, thus improving the quality and increasing the shelf life. This provides an alternative strategy to minimize the significant losses in harvested chestnut.

Ice nucleation efficiency of AgI: review and new insights

NASA Astrophysics Data System (ADS)

Marcolli, Claudia; Nagare, Baban; Welti, André; Lohmann, Ulrike

2016-07-01

AgI is one of the best-investigated ice-nucleating substances. It has relevance for the atmosphere since it is used for glaciogenic cloud seeding. Theoretical and experimental studies over the last 60 years provide a complex picture of silver iodide as an ice-nucleating agent with conflicting and inconsistent results. This review compares experimental ice nucleation studies in order to analyze the factors that influence the ice nucleation ability of AgI. The following picture emerges from this analysis: the ice nucleation ability of AgI seems to be enhanced when the AgI particle is on the surface of a droplet, which is indeed the position that a particle takes when it can freely move in a droplet. The ice nucleation by particles with surfaces exposed to air depends on water adsorption. AgI surfaces seem to be most efficient at nucleating ice when they are exposed to relative humidity at or even above water saturation. For AgI particles that are completely immersed in water, the freezing temperature increases with increasing AgI surface area. Higher threshold freezing temperatures seem to correlate with improved lattice matches as can be seen for AgI-AgCl solid solutions and 3AgI·NH4I·6H2O, which have slightly better lattice matches with ice than AgI and also higher threshold freezing temperatures. However, the effect of a good lattice match is annihilated when the surfaces have charges. Also, the ice nucleation ability seems to decrease during dissolution of AgI particles. This introduces an additional history and time dependence for ice nucleation in cloud chambers with short residence times.

Phase transitions and kinetic properties of gold nanoparticles confined between two-layer graphene nanosheets

NASA Astrophysics Data System (ADS)

Wang, Gang; Wu, Nanhua; Chen, Jionghua; Wang, Jinjian; Shao, Jingling; Zhu, Xiaolei; Lu, Xiaohua; Guo, Lucun

2016-11-01

The thermodynamic and kinetic behaviors of gold nanoparticles confined between two-layer graphene nanosheets (two-layer-GNSs) are examined and investigated during heating and cooling processes via molecular dynamics (MD) simulation technique. An EAM potential is applied to represent the gold-gold interactions while a Lennard-Jones (L-J) potential is used to describe the gold-GNS interactions. The MD melting temperature of 1345 K for bulk gold is close to the experimental value (1337 K), confirming that the EAM potential used to describe gold-gold interactions is reliable. On the other hand, the melting temperatures of gold clusters supported on graphite bilayer are corrected to the corresponding experimental values by adjusting the εAu-C value. Therefore, the subsequent results from current work are reliable. The gold nanoparticles confined within two-layer GNSs exhibit face center cubic structures, which is similar to those of free gold clusters and bulk gold. The melting points, heats of fusion, and heat capacities of the confined gold nanoparticles are predicted based on the plots of total energies against temperature. The density distribution perpendicular to GNS suggests that the freezing of confined gold nanoparticles starts from outermost layers. The confined gold clusters exhibit layering phenomenon even in liquid state. The transition of order-disorder in each layer is an essential characteristic in structure for the freezing phase transition of the confined gold clusters. Additionally, some vital kinetic data are obtained in terms of classical nucleation theory.

Sleep alterations following exposure to stress predict fear-associated memory impairments in a rodent model of PTSD.

PubMed

Vanderheyden, William M; George, Sophie A; Urpa, Lea; Kehoe, Michaela; Liberzon, Israel; Poe, Gina R

2015-08-01

Sleep abnormalities, such as insomnia, nightmares, hyper-arousal, and difficulty initiating or maintaining sleep, are diagnostic criteria of posttraumatic stress disorder (PTSD). The vivid dream state, rapid eye movement (REM) sleep, has been implicated in processing emotional memories. We have hypothesized that REM sleep is maladaptive in those suffering from PTSD. However, the precise neurobiological mechanisms regulating sleep disturbances following trauma exposure are poorly understood. Using single prolonged stress (SPS), a well-validated rodent model of PTSD, we measured sleep alterations in response to stressor exposure and over a subsequent 7-day isolation period during which the PTSD-like phenotype develops. SPS resulted in acute increases in REM sleep and transition to REM sleep, and decreased waking in addition to alterations in sleep architecture. The severity of the PTSD-like phenotype was later assessed by measuring freezing levels on a fear-associated memory test. Interestingly, the change in REM sleep following SPS was significantly correlated with freezing behavior during extinction recall assessed more than a week later. Reductions in theta (4-10 Hz) and sigma (10-15 Hz) band power during transition to REM sleep also correlated with impaired fear-associated memory processing. These data reveal that changes in REM sleep, transition to REM sleep, waking, and theta and sigma power may serve as sleep biomarkers to identify individuals with increased susceptibility to PTSD following trauma exposure.

Sleep Alterations Following Exposure to Stress Predict Fear-Associated Memory Impairments in a Rodent Model of PTSD

PubMed Central

Vanderheyden, William M.; George, Sophie A.; Urpa, Lea; Kehoe, Michaela; Liberzon, Israel; Poe, Gina R.

2015-01-01

Sleep abnormalities such as insomnia, nightmares, hyper-arousal, and difficulty initiating or maintaining sleep, are diagnostic criteria of post-traumatic stress disorder (PTSD). The vivid dream state, rapid eye movement (REM) sleep, has been implicated in processing emotional memories. We have hypothesized that REM sleep is maladaptive in those suffering from PTSD. However, the precise neurobiological mechanisms regulating these sleep disturbances following trauma exposure are poorly understood. Using single prolonged stress (SPS), a well-validated rodent model of PTSD, we measured sleep alterations in response to stress exposure and over a subsequent 7-day isolation period during which the PTSD-like phenotype develops in rats. SPS resulted in acutely increased REM sleep, transition to REM sleep, and decreased waking in addition to alterations in sleep architecture. The severity of the PTSD-like phenotype was later assessed by measuring freezing levels on a fear-associated memory test. Interestingly, the change in REM sleep following SPS was significantly correlated with freezing behavior during extinction recall assessed more than a week later. We also report reductions in theta (4–10 Hz) and sigma (10–15 Hz) band power during transition to REM sleep which also correlated with impaired fear-associated memory processing. These data reveal that changes in REM sleep, transition to REM sleep, waking, and theta and sigma power may serve as sleep biomarkers to identify individuals with increased susceptibility to PTSD following trauma exposure. PMID:26019008

Nucleation via an unstable intermediate phase.

PubMed

Sear, Richard P

2009-08-21

The pathway for crystallization from dilute vapors and solutions is often observed to take a detour via a liquid or concentrated-solution phase. For example, in moist subzero air, droplets of liquid water form, which then freeze. In this example and in many others, an intermediate phase (here liquid water) is dramatically accelerating the kinetics of a phase transition between two other phases (water vapor and ice). Here we study this phenomenon via exact computer simulations of a simple lattice model. Surprisingly, we find that the rate of nucleation of the new equilibrium phase is actually fastest when the intermediate phase is slightly unstable in the bulk, i.e., has a slightly higher free energy than the phase we start in. Nucleation occurs at a concave part of the surface and microscopic amounts of the intermediate phase can form there even before the phase is stable in the bulk. As the nucleus of the equilibrium phase is microscopic, this allows nucleation to occur effectively in the intermediate phase before it is stable in the bulk.

Environment and initial state engineered dynamics of quantum and classical correlations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Cheng-Zhi, E-mail: czczwang@outlook.com; Li, Chun-Xian; Guo, Yu

Based on an open exactly solvable system coupled to an environment with nontrivial spectral density, we connect the features of quantum and classical correlations with some features of the environment, initial states of the system, and the presence of initial system–environment correlations. Some interesting features not revealed before are observed by changing the structure of environment, the initial states of system, and the presence of initial system–environment correlations. The main results are as follows. (1) Quantum correlations exhibit temporary freezing and permanent freezing even at high temperature of the environment, for which the necessary and sufficient conditions are given bymore » three propositions. (2) Quantum correlations display a transition from temporary freezing to permanent freezing by changing the structure of environment. (3) Quantum correlations can be enhanced all the time, for which the condition is put forward. (4) The one-to-one dependency relationship between all kinds of dynamic behaviors of quantum correlations and the initial states of the system as well as environment structure is established. (5) In the presence of initial system–environment correlations, quantum correlations under local environment exhibit temporary multi-freezing phenomenon. While under global environment they oscillate, revive, and damp, an explanation for which is given. - Highlights: • Various interesting behaviors of quantum and classical correlations are observed in an open exactly solvable model. • The important effects of the bath structure on quantum and classical correlations are revealed. • The one-to-one correspondence between the type of dynamical behavior of quantum discord and the initial state is given. • Quantum correlations are given in the presence of initial qubits–bath correlations.« less

Advancing Methods for Estimating Soil Nitrous Oxide Emissions by Incorporating Freeze-Thaw Cycles into a Tier 3 Model-Based Assessment

NASA Astrophysics Data System (ADS)

Ogle, S. M.; DelGrosso, S.; Parton, W. J.

2017-12-01

Soil nitrous oxide emissions from agricultural management are a key source of greenhouse gas emissions in many countries due to the widespread use of nitrogen fertilizers, manure amendments from livestock production, planting legumes and other practices that affect N dynamics in soils. In the United States, soil nitrous oxide emissions have ranged from 250 to 280 Tg CO2 equivalent from 1990 to 2015, with uncertainties around 20-30 percent. A Tier 3 method has been used to estimate the emissions with the DayCent ecosystem model. While the Tier 3 approach is considerably more accurate than IPCC Tier 1 methods, there is still the possibility of biases in emission estimates if there are processes and drivers that are not represented in the modeling framework. Furthermore, a key principle of IPCC guidance is that inventory compilers estimate emissions as accurately as possible. Freeze-thaw cycles and associated hot moments of nitrous oxide emissions are one of key drivers influencing emissions in colder climates, such as the cold temperate climates of the upper Midwest and New England regions of the United States. Freeze-thaw activity interacts with management practices that are increasing N availability in the plant-soil system, leading to greater nitrous oxide emissions during transition periods from winter to spring. Given the importance of this driver, the DayCent model has been revised to incorproate freeze-thaw cycles, and the results suggests that including this driver can significantly modify the emissions estimates in cold temperate climate regions. Consequently, future methodological development to improve estimation of nitrous oxide emissions from soils would benefit from incorporating freeze-thaw cycles into the modeling framework for national territories with a cold climate.

The effect of ice nuclei on a deep convective cloud in South China

NASA Astrophysics Data System (ADS)

Deng, Xin; Xue, Huiwen; Meng, Zhiyong

2018-07-01

This study uses the Weather Research and Forecasting Model to simulate a deep convective cloud under a relatively polluted condition in South China. Ice nuclei (IN) aerosols near the surface are effectively transported upwards to above the 0 °C level by the strong updrafts in the convective cloud. Four cases with initial surface IN aerosol concentrations of 1, 10, 100, and 1000 L-1 are simulated. All simulations can well reproduce the major characteristics of the deep convective cloud in terms of the evolution, spatial distribution, and its track. IN aerosols have little effect on these macrophysical characteristics but can significantly affect ice formation. When IN concentration is increased, all heterogeneous nucleation modes are significantly enhanced, whereas the homogeneous freezing of cloud droplets is unchanged or weakened depending on the IN concentration and the development stages of the deep convective cloud. The homogeneous freezing of haze particles is generally not affected by increased IN but is slightly weakened in the extremely high IN case. As IN concentration is increased by 10 and 100 times, the enhanced heterogeneous nucleation is still not strong enough to compete with homogeneous freezing. Ice formation is hence still dominated by the homogenous freezing of cloud droplets and haze particles in the layer of 9-14 km, where most of the ice crystals are produced. The microphysical properties are generally unaffected in all the stages of cloud evolution. As IN concentration is increased by 1000 times and heterogeneous nucleation is further enhanced, the homogeneous freezing of cloud droplets and haze particles dominates only in the mature and dissipating stages, leading to unaffected ice number mixing ratio in the anvil region (approximately above 9 km) for these two stages. However, in the developing stage, when the supply of cloud droplets is limited, the homogeneous freezing of cloud droplets is weakened or even suppressed due to the very strong competition for liquid water with heterogeneous nucleation, leading to significantly lower ice number mixing ratio in the anvil regions. In addition, the microphysical properties in the convective core regions below the cloud anvil (approximately below 9 km) are also affected in the case of 1000 L-1. The enhanced heterogeneous nucleation produces more ice crystals below 9 km, leading to a stronger conversion from ice crystals to snow particles, and hence higher number and mass mixing ratios of snow. The IN effect on the spatial distributions and temporal evolutions of the surface precipitation and updraft velocity is generally insignificant.

Crystal Initiation Structures in Developing Enamel: Possible Implications for Caries Dissolution of Enamel Crystals

PubMed Central

Robinson, Colin; Connell, Simon D.

2017-01-01

Investigations of developing enamel crystals using Atomic and Chemical Force Microscopy (AFM, CFM) have revealed a subunit structure. Subunits were seen in height images as collinear swellings about 30 nM in diameter on crystal surfaces. In friction mode they were visible as positive regions. These were similar in size (30–50 nM) to collinear spherical structures, presumably mineral matrix complexes, seen in developing enamel using a freeze fracturing/freeze etching procedure. More detailed AFM studies on mature enamel suggested that the 30–50 nM structures were composed of smaller units, ~10–15 nM in diameter. These were clustered in hexagonal or perhaps a spiral arrangement. It was suggested that these could be the imprints of initiation sites for mineral precipitation. The investigation aimed at examining original freeze etched images at high resolution to see if the smaller subunits observed using AFM in mature enamel were also present in developing enamel i.e., before loss of the organic matrix. The method used was freeze etching. Briefly samples of developing rat enamel were rapidly frozen, fractured under vacuum, and ice sublimed from the fractured surface. The fractured surface was shadowed with platinum or gold and the metal replica subjected to high resolution TEM. For AFM studies high-resolution tapping mode imaging of human mature enamel sections was performed in air under ambient conditions at a point midway between the cusp and the cervical margin. Both AFM and freeze etch studies showed structures 30–50 nM in diameter. AFM indicated that these may be clusters of somewhat smaller structures ~10–15 nM maybe hexagonally or spirally arranged. High resolution freeze etching images of very early enamel showed ~30–50 nM spherical structures in a disordered arrangement. No smaller units at 10–15 nM were clearly seen. However, when linear arrangements of 30–50 nM units were visible the picture was more complex but also smaller units including ~10–15 nM units could be observed. Conclusions: Structures ~10–15 nM in diameter were detected in developing enamel. While the appearance was complex, these were most evident when the 30–5 nM structures were in linear arrays. Formation of linear arrays of subunits may be associated with the development of mineral initiation sites and attendant processing of matrix proteins. PMID:28670283

Freeze-thaw stress of Alhydrogel ® alone is sufficient to reduce the immunogenicity of a recombinant hepatitis B vaccine containing native antigen.

PubMed

Clapp, Tanya; Munks, Michael W; Trivedi, Ruchit; Kompella, Uday B; Braun, LaToya Jones

2014-06-24

Preventing losses in vaccine potency due to accidental freezing has recently become a topic of interest for improving vaccines. All vaccines with aluminum-containing adjuvants are susceptible to such potency losses. Recent studies have described excipients that protect the antigen from freeze-induced inactivation, prevent adjuvant agglomeration and retain potency. Although these strategies have demonstrated success, they do not provide a mechanistic understanding of freeze-thaw (FT) induced potency losses. In the current study, we investigated how adjuvant frozen in the absence of antigen affects vaccine immunogenicity and whether preventing damage to the freeze-sensitive recombinant hepatitis B surface antigen (rHBsAg) was sufficient for maintaining vaccine potency. The final vaccine formulation or Alhydrogel(®) alone was subjected to three FT-cycles. The vaccines were characterized for antigen adsorption, rHBsAg tertiary structure, particle size and charge, adjuvant elemental content and in-vivo potency. Particle agglomeration of either vaccine particles or adjuvant was observed following FT-stress. In vivo studies demonstrated no statistical differences in IgG responses between vaccines with FT-stressed adjuvant and no adjuvant. Adsorption of rHBsAg was achieved; regardless of adjuvant treatment, suggesting that the similar responses were not due to soluble antigen in the frozen adjuvant-containing formulations. All vaccines with adjuvant, including the non-frozen controls, yielded similar, blue-shifted fluorescence emission spectra. Immune response differences could not be traced to differences in the tertiary structure of the antigen in the formulations. Zeta potential measurements and elemental content analyses suggest that FT-stress resulted in a significant chemical alteration of the adjuvant surface. This data provides evidence that protecting a freeze-labile antigen from subzero exposure is insufficient to maintain vaccine potency. Future studies should focus on adjuvant protection. To our knowledge, this is the first study to systematically investigate how FT-stress to adjuvant alone affects immunogenicity. It provides definitive evidence that this damage is sufficient to reduce vaccine potency. Copyright © 2014 Elsevier Ltd. All rights reserved.

Effects of Freezing and Thawing on Consolidation Behavior of Clayey Soils

NASA Astrophysics Data System (ADS)

Binal, Adil; Adeli, Parisa

2015-04-01

An apprehending of freezing and thawing effects on cohesive soil is considerable for many construction and environmental subjects. This paper relates the effects of freezing and thawing on consolidation behaviour of clayey soils. The Capital of Ankara settled on a sequence of lacustrine sediments. These sediments include fine grain soils, locally. Collected samples were undisturbed grey clay and clayey sand that were obtained from the bottom of a construction zone at about 1m depth below the ground surface. Total of 32 moulded samples were prepared with constant water content to reflect the moisture condition in the active surface layer. Gray clay and clayey sand were analysed in the laboratory, and found to have the plastic limits (PL) of 33.01% and 22.56%, the liquid limits (LL) of 75.05% and 36.97%, and the plasticity indexes (PI) of 42.04% and 14.41%. The soil samples were classified as "CH" and "SC" in accordance with the unified soil classification system. Soil samples for all tests were placed in a freezer that has -18°C temperature. Samples have been waited in it for twenty-four hours. Then, they have been removed from the freezer and allowed to stand for twenty-four hours at a constant room temperature (21°C) and humidity (80% RH). As a result, one freezing and thawing cycle was achieved between -18°C (24 hours) and 21°C (24 hours), and it took two days. Freezing and thawing (FT) sequences were selected as 1, 3, 7, 14 and 21. After each FT sequence, Atterberg limits and consolidation tests were carried out in accordance with ASTM standards. Liquid and plastic limits of soil samples, suddenly, were decreased after first FT cycle. That state is a sign of the clay mineral orientation due to freezing and thawing process. The soil classification of clayey sand was changed from "SC" to "SM" after first FT cycle. Furthermore, the coefficient of consolidation and permeability of grey clay had been increased by rising in FT cycles up to 7 and then continue to decline as well as these values of clayey sand start to decrease after 14 FT cycles.

Preparative free-flow electrophoresis as a method of fractionation of natural organic materials

USGS Publications Warehouse

Leenheer, J.A.; Malcolm, R.L.

1973-01-01

Preparative free-flow electrophoresis was found to be an efficient method of conducting large-scale fractionations of the natural organic polyelectrolytes occurring in many surface waters and soils. The method of free-flow electrophoresis obviates, the problem of adsorption upon a supporting medium and permits the use of high potential gradients and currents because of an efficient cooling system. Separations were monitored by determining organic carbon concentration with a dissolved carbon analyzer, and color was measured by absorbance at 400 nanometers. Organic materials from waters and soils were purified by filtration, hydrogen exchange, and dialysis and were concentrated by freeze drying or freeze concentration. In electrophoretic fractionations of natural organic materials typically found in surface waters and soils, color was found to increase with the charge of the fraction.

Freeze/thaw conditions at periglacial landforms in Kapp Linné, Svalbard, investigated using field observations, in situ, and radar satellite monitoring

NASA Astrophysics Data System (ADS)

Eckerstorfer, M.; Malnes, E.; Christiansen, H. H.

2017-09-01

In periglacial landscapes, snow dynamics and microtopography have profound implications of freeze-thaw conditions and thermal regime of the ground. We mapped periglacial landforms at Kapp Linné, central Svalbard, where we chose six widespread landforms (solifluction sheet, nivation hollow, palsa and peat in beach ridge depressions, raised marine beach ridge, and exposed bedrock ridge) as study sites. At these six landforms, we studied ground thermal conditions, freeze-thaw cycles, and snow dynamics using a combination of in situ monitoring and C-band radar satellite data in the period 2005-2012. Based on these physical parameters, the six studied landforms can be classified into raised, dry landforms with minor ground ice content and a thin, discontinuous snow cover and into wet landforms with high ice content located in the topographical depressions in-between with medium to thick snow cover. This results in a differential snow-melting period inferred from the C-band radar satellite data, causing the interseasonal and interlandform variability in the onset of ground surface thawing once the ground becomes snow free. Therefore, variability also exists in the period of thawed ground surface conditions. However, the length of the season with thawed ground surface conditions does not determine the mean annual ground surface temperature, it only correlates well with the active layer depths. From the C-band radar satellite data series, measured relative backscatter trends hint toward a decrease in snow cover through time and a more frequent presence of ice layers from mid-winter rain on snow events at Kapp Linné, Svalbard.

Fundamental differences between glassy dynamics in two and three dimensions

PubMed Central

Flenner, Elijah; Szamel, Grzegorz

2015-01-01

The two-dimensional freezing transition is very different from its three-dimensional counterpart. In contrast, the glass transition is usually assumed to have similar characteristics in two and three dimensions. Using computer simulations, here we show that glassy dynamics in supercooled two- and three-dimensional fluids are fundamentally different. Specifically, transient localization of particles on approaching the glass transition is absent in two dimensions, whereas it is very pronounced in three dimensions. Moreover, the temperature dependence of the relaxation time of orientational correlations is decoupled from that of the translational relaxation time in two dimensions but not in three dimensions. Last, the relationships between the characteristic size of dynamically heterogeneous regions and the relaxation time are very different in two and three dimensions. These results strongly suggest that the glass transition in two dimensions is different than in three dimensions. PMID:26067877

Can we define an asymptotic value for the ice active surface site density for heterogeneous ice nucleation?

NASA Astrophysics Data System (ADS)

Niedermeier, Dennis; Augustin-Bauditz, Stefanie; Hartmann, Susan; Wex, Heike; Ignatius, Karoliina; Stratmann, Frank

2015-04-01

The formation of ice in atmospheric clouds has a substantial influence on the radiative properties of clouds as well as on the formation of precipitation. Therefore much effort has been made to understand and quantify the major ice formation processes in clouds. Immersion freezing has been suggested to be a dominant primary ice formation process in low and mid-level clouds (mixed-phase cloud conditions). It also has been shown that mineral dust particles are the most abundant ice nucleating particles in the atmosphere and thus may play an important role for atmospheric ice nucleation (Murray et al., 2012). Additionally, biological particles like bacteria and pollen are suggested to be potentially involved in atmospheric ice formation, at least on a regional scale (Murray et al., 2012). In recent studies for biological particles (SNOMAX and birch pollen), it has been demonstrated that freezing is induced by ice nucleating macromolecules and that an asymptotic value for the mass density of these ice nucleating macromolecules can be determined (Hartmann et al., 2013; Augustin et al., 2013, Wex et al., 2014). The question arises whether such an asymptotic value can also be determined for the ice active surface site density ns, a parameter which is commonly used to describe the ice nucleation activity of e.g., mineral dust. Such an asymptotic value for ns could be an important input parameter for atmospheric modeling applications. In the presented study, we therefore investigated the immersion freezing behavior of droplets containing size-segregated, monodisperse feldspar particles utilizing the Leipzig Aerosol Cloud Interaction Simulator (LACIS). For all particle sizes considered in the experiments, we observed a leveling off of the frozen droplet fraction reaching a plateau within the heterogeneous freezing temperature regime (T > -38°C) which was proportional to the particle surface area. Based on these findings, we could determine an asymptotic value for the ice active surface site density, which we named ns*, for the investigated feldspar sample. The comparison of these results with those of other studies elucidates the general feasibility of determining such an asymptotic value and also show that the value of ns* strongly depends on the method of the particle surface area determination. Acknowledgement This work is partly funded by the Federal Ministry of Education and Research (BMBF - project CLOUD 12) and by the German Research Foundation (DFG project WE 4722/1-1, part of the research unit INUIT, FOR 1525). D. Niedermeier acknowledges financial support from the Alexander von Humboldt-foundation. References Augustin et al.: Immersion freezing of birch pollen washing water, Atmos. Chem. Phys., 13, 10989-11003, doi:10.5194/acp-13-10989-2013, 2013. Hartmann et al.: Immersion freezing of ice nucleation active protein complexes, Atmos. Chem. Phys., 13, 5751-5766, doi:10.5194/acp-13-5751-2013, 2013. Murray et al.: Ice nucleation by particles immersed in supercooled cloud droplets, Chem. Soc. Rev., 41, 6519-6554, 2012. Wex et al.: Intercomparing different devices for the investigation of ice nucleating particles using Snomax® as test substance, Atmos. Chem. Phys. Discuss., 14, 22321-22384, doi:10.5194/acpd-14-22321-2014, 2014.

Results of chemical and isotopic analyses of sediment and water from alluvium of the Canadian River near a closed municipal landfill, Norman, Oklahoma

USGS Publications Warehouse

Breit, George N.; Tuttle, Michele L.W.; Cozzarelli, Isabelle M.; Christenson, Scott C.; Jaeschke, Jeanne B.; Fey, David L.; Berry, Cyrus J.

2005-01-01

Results of physical and chemical analyses of sediment and water collected near a closed municipal landfill at Norman, Oklahoma are presented in this report. Sediment analyses are from 40 samples obtained by freeze-shoe coring at 5 sites, and 14 shallow (depth <1.3 m) sediment samples. The sediment was analyzed to determine grain size, the abundance of extractable iron species and the abundances and isotopic compositions of forms of sulfur. Water samples included pore water from the freeze-shoe core, ground water, and surface water. Pore water from 23 intervals of the core was collected and analyzed for major and trace dissolved species. Thirteen ground-water samples obtained from wells within a few meters of the freeze-shoe core sites and one from the landfill were analyzed for major and trace elements as well as the sulfur and oxygen isotope composition of dissolved sulfate. Samples of surface water were collected at 10 sites along the Canadian River from New Mexico to central Oklahoma. These river-water samples were analyzed for major elements, trace elements, and the isotopic composition of dissolved sulfate.

Seasonally frozen layer in natural and drained peatlands at the South of West Siberia, Russia

NASA Astrophysics Data System (ADS)

Dyukarev, Egor; Kiselev, Maxim; Voropay, Nadezhda; Preis, Yulia

2017-04-01

The temperature regime of soils in natural and drained peatlands at Bakchar bog located in the South Taiga zone of West Siberia is studied. Soil temperature for depths up to 320 cm was registered using autonomous temperature profile recorder during the period from August 2010 to September 2016. Maximal and minimal temperatures were registered at surface in July and February, consequently. Extreme soil temperatures at 320 cm depth shifts to December (maximum) and July (minimum) reducing absolute values. Annual peat soil temperature amplitude decrease with depth from 21,8 °C on surface to 1,1 °C at 320 cm. The analysis of daily, month and annual mean data of temperature in peat soil has shown that seasonally frozen layer was registered up to 20-60 cm depth. The duration of seasonally freeze layer existence varies from 130 to 180 days. Drained peatlands with the lowest water table have highest freeze depth. Soil at water-logged sedge-sphagnum fen in winter is warmer than soil in ryam ecosystem and mineral soil at upland. Maximal freezing depth in peatlands is up to 3 times lower than at drain areas.

Mixed ice accretion on aircraft wings

NASA Astrophysics Data System (ADS)

Janjua, Zaid A.; Turnbull, Barbara; Hibberd, Stephen; Choi, Kwing-So

2018-02-01

Ice accretion is a problematic natural phenomenon that affects a wide range of engineering applications including power cables, radio masts, and wind turbines. Accretion on aircraft wings occurs when supercooled water droplets freeze instantaneously on impact to form rime ice or runback as water along the wing to form glaze ice. Most models to date have ignored the accretion of mixed ice, which is a combination of rime and glaze. A parameter we term the "freezing fraction" is defined as the fraction of a supercooled droplet that freezes on impact with the top surface of the accretion ice to explore the concept of mixed ice accretion. Additionally we consider different "packing densities" of rime ice, mimicking the different bulk rime densities observed in nature. Ice accretion is considered in four stages: rime, primary mixed, secondary mixed, and glaze ice. Predictions match with existing models and experimental data in the limiting rime and glaze cases. The mixed ice formulation however provides additional insight into the composition of the overall ice structure, which ultimately influences adhesion and ice thickness, and shows that for similar atmospheric parameter ranges, this simple mixed ice description leads to very different accretion rates. A simple one-dimensional energy balance was solved to show how this freezing fraction parameter increases with decrease in atmospheric temperature, with lower freezing fraction promoting glaze ice accretion.

Role of freeze-thaw cycles and chlorpyrifos insecticide use on diffuse Cd loss and sediment accumulation

NASA Astrophysics Data System (ADS)

Wang, Fangli; Ouyang, Wei; Hao, Fanghua; Jiao, Wei; Shan, Yushu; Lin, Chunye

2016-06-01

Freeze-thaw cycles are predicted to increase in cold temperate regions. The potential influence of the interactions of freeze-thaw cycles and agrochemicals on the release of Cd into river water is unknown. In this study, the interactions of freeze-thaw cycles and chlorpyrifos (FC) on Cd mobility in soils were analysed. The spatial variability of soil Cd under long-term intensive tillage in a freeze-thaw agro-system was also identified. The temporal variation of sediment Cd was detected based on analysis of the sediment geochemistry. The results showed that FC increased soil Cd mobility, with an increase of approximately 10% in CaCl2-extractable Cd. The increased mobile fractions of water-soluble and exchangeable Cd originated from the decreased fraction of Fe-Mn-oxide-associated Cd and organic matter-bound Cd. The total Cd content in the surface soil followed the zonally decreasing trend of dry land > paddy land > natural land. The Cd concentrations and sedimentation rates of the sediment core generally increased from 1943 to 2013 due to agricultural exploration and farmland irrigation system construction, indicating an increase of the Cd input flux into water. The results provide valuable information about the soil Cd transport response to the influence of climatic and anthropogenic factors in cold intensive agro-systems.

Design of experiments reveals critical parameters for pilot-scale freeze-and-thaw processing of L-lactic dehydrogenase.

PubMed

Roessl, Ulrich; Humi, Sebastian; Leitgeb, Stefan; Nidetzky, Bernd

2015-09-01

Freezing constitutes an important unit operation of biotechnological protein production. Effects of freeze-and-thaw (F/T) process parameters on stability and other quality attributes of the protein product are usually not well understood. Here a design of experiments (DoE) approach was used to characterize the F/T behavior of L-lactic dehydrogenase (LDH) in a 700-mL pilot-scale freeze container equipped with internal temperature and pH probes. In 24-hour experiments, target temperature between -10 and -38°C most strongly affected LDH stability whereby enzyme activity was retained best at the highest temperature of -10°C. Cooling profile and liquid fill volume also had significant effects on LDH stability and affected the protein aggregation significantly. Parameters of the thawing phase had a comparably small effect on LDH stability. Experiments in which the standard sodium phosphate buffer was exchanged by Tris-HCl and the non-ionic surfactant Tween 80 was added to the protein solution showed that pH shift during freezing and protein surface exposure were the main factors responsible for LDH instability at the lower freeze temperatures. Collectively, evidence is presented that supports the use of DoE-based systematic analysis at pilot scale in the identification of F/T process parameters critical for protein stability and in the development of suitable process control strategies. Copyright © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cryopreservation of boar semen in mini- and maxi-straws.

PubMed

Bwanga, C O; de Braganca, M M; Einarsson, S; Rodriguez-Martinez, H

1990-10-01

Split ejaculates from four boars were frozen with a programmable freezing machine, in mini- (0.25 ml) and maxi- (5 ml) plastic straws with an extender at either acidic (6.3) or alkaline (7.4) pH. Glycerol (3%) was used as cryoprotectant. The freezing of the semen was monitored by way of thermocouples placed in the straws. Post-thaw motility and acrosome integrity were evaluated; the latter using phase contrast microscopy, eosin-nigrosin stain and electron microscopy. Post-thaw sperm motility was significantly higher when semen was frozen in mini-straws than in maxi-straws. For the mini-straws, the motility was better when semen was exposed to an acidic environment during freezing, but this beneficial effect of the low extracellular pH was not evident when maxi-straws were thawed. The motility of the spermatozoa diminished significantly during the thermoresistance test (0 h and 2 h time) at 37 degrees C in a similar way for both straws and extracellular pH's. The freezing procedure, no matter the extracellular pH, did not cause major acrosomal damages, but significantly more normal apical ridges were present in the mini-straws than in the maxi-straws. This in vitro evaluation indicated that the freezing method employed was better for mini- than for maxi-straws since the freezing of the 5 ml volumes was not homogeneous, due to the large section area between the surface and the core of the straw.

United States Coast Guard Fiscal Year 2009 Performance Report

DTIC Science & Technology

2010-02-01

flooding. The International Ice Patrol facilitates interna- tional commerce by broadcasting information on iceberg locations to vessels transiting...SEA also provided back-up capability for the U.S. Antarctic Deep Freeze resupply mission. • The United States Coast Guard International Ice Patrol...tracked over 1,200 icebergs which drifted into the transatlantic shipping lanes continuing its perfect record, 96 years, of preventing ship collisions

Elastic and anelastic relaxation behaviour of perovskite multiferroics II: PbZr0.53Ti0.47O3 (PZT)-PbFe0.5Ta0.5O3 (PFT).

PubMed

Schiemer, J A; Lascu, I; Harrison, R J; Kumar, A; Katiyar, R S; Sanchez, D A; Ortega, N; Mejia, C Salazar; Schnelle, W; Shinohara, H; Heap, A J F; Nagaratnam, R; Dutton, S E; Scott, J F; Nair, B; Mathur, N D; Carpenter, M A

2017-01-01

Elastic and anelastic properties of ceramic samples of multiferroic perovskites with nominal compositions across the binary join PbZr 0.53 Ti 0.47 O 3 -PbFe 0.5 Ta 0.5 O 3 (PZT-PFT) have been assembled to create a binary phase diagram and to address the role of strain relaxation associated with their phase transitions. Structural relationships are similar to those observed previously for PbZr 0.53 Ti 0.47 O 3 -PbFe 0.5 Nb 0.5 O 3 (PZT-PFN), but the magnitude of the tetragonal shear strain associated with the ferroelectric order parameter appears to be much smaller. This leads to relaxor character for the development of ferroelectric properties in the end member PbFe 0.5 Ta 0.5 O 3 . As for PZT-PFN, there appear to be two discrete instabilities rather than simply a reorientation of the electric dipole in the transition sequence cubic-tetragonal-monoclinic, and the second transition has characteristics typical of an improper ferroelastic. At intermediate compositions, the ferroelastic microstructure has strain heterogeneities on a mesoscopic length scale and, probably, also on a microscopic scale. This results in a wide anelastic freezing interval for strain-related defects rather than the freezing of discrete twin walls that would occur in a conventional ferroelastic material. In PFT, however, the acoustic loss behaviour more nearly resembles that due to freezing of conventional ferroelastic twin walls. Precursor softening of the shear modulus in both PFT and PFN does not fit with a Vogel-Fulcher description, but in PFT there is a temperature interval where the softening conforms to a power law suggestive of the role of fluctuations of the order parameter with dispersion along one branch of the Brillouin zone. Magnetic ordering appears to be coupled only weakly with a volume strain and not with shear strain but, as with multiferroic PZT-PFN perovskites, takes place within crystals which have significant strain heterogeneities on different length scales.

7 CFR 51.2763 - Damage.

Code of Federal Regulations, 2010 CFR

2010-01-01

... cuts, web or frass; (d) Freezing injury causing hard, translucent or discolored flesh; and, (e) Dirt when the surface of the kernel is heavily smeared, thickly flecked or coated with dirt, seriously...

Cooler?

ERIC Educational Resources Information Center

Firth, Ian

1971-01-01

Presents experiments, models, and interpretations of reports that hot water begins to freeze faster than cooler water. Preliminary conclusions show that the surface area, side wall cooling, evaporation, and environment are the most important parameters. (DS)

Experimental Study of Supercooled Large Droplet Impingement Effects

NASA Technical Reports Server (NTRS)

Papadakis, M.; Rachman, A.; Wong, S. C.; Hung, K. E.; Vu, G. T.

2003-01-01

Typically, ice accretion results from small supercooled droplets (droplets cooled below freezing), usually 5 to 50 microns in diameter, which can freeze upon impact with an aircraft surface. Recently, ice accretions resulting from supercooled large droplet (SLD) conditions have become a safety concern. Current ice accretion codes have been extensively tested for Title 14 Code of Federal Regulations Part 25, Appendix C icing conditions but have not been validated for SLD icing conditions. This report presents experimental methods for investigating large droplet impingement dynamics and for obtaining small and large water droplet impingement data.

Inhibition of ice nucleation by slippery liquid-infused porous surfaces (SLIPS).

PubMed

Wilson, Peter W; Lu, Weizhe; Xu, Haojun; Kim, Philseok; Kreder, Michael J; Alvarenga, Jack; Aizenberg, Joanna

2013-01-14

Ice repellent coatings have been studied and keenly sought after for many years, where any advances in the durability of such coatings will result in huge energy savings across many fields. Progress in creating anti-ice and anti-frost surfaces has been particularly rapid since the discovery and development of slippery, liquid infused porous surfaces (SLIPS). Here we use SLIPS-coated differential scanning calorimeter (DSC) pans to investigate the effects of the surface modification on the nucleation of supercooled water. This investigation is inherently different from previous studies which looked at the adhesion of ice to SLIPS surfaces, or the formation of ice under high humidity conditions. Given the stochastic nature of nucleation of ice from supercooled water, multiple runs on the same sample are needed to determine if a given surface coating has a real and statistically significant effect on the nucleation temperature. We have cycled supercooling to freezing and then thawing of deionized water in hydrophilic (untreated aluminum), hydrophobic, superhydrophobic, and SLIPS-treated DSC pans multiple times to determine the effects of surface treatment on the nucleation and subsequent growth of ice. We find that SLIPS coatings lower the nucleation temperature of supercooled water in contact with statistical significance and show no deterioration or change in the coating performance even after 150 freeze-thaw cycles.

High ice nucleation activity located in blueberry stem bark is linked to primary freeze initiation and adaptive freezing behaviour of the bark

PubMed Central

Kishimoto, Tadashi; Yamazaki, Hideyuki; Saruwatari, Atsushi; Murakawa, Hiroki; Sekozawa, Yoshihiko; Kuchitsu, Kazuyuki; Price, William S.; Ishikawa, Masaya

2014-01-01

Controlled ice nucleation is an important mechanism in cold-hardy plant tissues for avoiding excessive supercooling of the protoplasm, for inducing extracellular freezing and/or for accommodating ice crystals in specific tissues. To understand its nature, it is necessary to characterize the ice nucleation activity (INA), defined as the ability of a tissue to induce heterogeneous ice nucleation. Few studies have addressed the precise localization of INA in wintering plant tissues in respect of its function. For this purpose, we recently revised a test tube INA assay and examined INA in various tissues of over 600 species. Extremely high levels of INA (−1 to −4 °C) in two wintering blueberry cultivars of contrasting freezing tolerance were found. Their INA was much greater than in other cold-hardy species and was found to be evenly distributed along the stems of the current year's growth. Concentrations of active ice nuclei in the stem were estimated from quantitative analyses. Stem INA was localized mainly in the bark while the xylem and pith had much lower INA. Bark INA was located mostly in the cell wall fraction (cell walls and intercellular structural components). Intracellular fractions had much less INA. Some cultivar differences were identified. The results corresponded closely with the intrinsic freezing behaviour (extracellular freezing) of the bark, icicle accumulation in the bark and initial ice nucleation in the stem under dry surface conditions. Stem INA was resistant to various antimicrobial treatments. These properties and specific localization imply that high INA in blueberry stems is of intrinsic origin and contributes to the spontaneous initiation of freezing in extracellular spaces of the bark by acting as a subfreezing temperature sensor. PMID:25082142

Investigation of Freeze and Thaw Cycles of a Gas-Charged Heat Pipe

NASA Technical Reports Server (NTRS)

Ku, Jentung; Ottenstein, Laura; Krimchansky, Alexander

2012-01-01

The traditional constant conductance heat pipes (CCHPs) currently used on most spacecraft run the risk of bursting the pipe when the working fluid is frozen and later thawed. One method to avoid pipe bursting is to use a gas-charged heat pipe (GCHP) that can sustain repeated freeze/thaw cycles. The construction of the GCHP is similar to that of the traditional CCHP except that a small amount of non-condensable gas (NCG) is introduced and a small length is added to the CCHP condenser to serve as the NCG reservoir. During the normal operation, the NCG is mostly confined to the reservoir, and the GCHP functions as a passive variable conductance heat pipe (VCHP). When the liquid begins to freeze in the condenser section, the NCG will expand to fill the central core of the heat pipe, and ice will be formed only in the grooves located on the inner surface of the heat pipe in a controlled fashion. The ice will not bridge the diameter of the heat pipe, thus avoiding the risk of pipe bursting during freeze/thaw cycles. A GCHP using ammonia as the working fluid was fabricated and then tested inside a thermal vacuum chamber. The GCHP demonstrated a heat transport capability of more than 200W at 298K as designed. Twenty-seven freeze/thaw cycles were conducted under various conditions where the evaporator temperature ranged from 163K to 253K and the condenser/reservoir temperatures ranged from 123K to 173K. In all tests, the GCHP restarted without any problem with heat loads between 10W and 100W. No performance degradation was noticed after 27 freeze/thaw cycles. The ability of the GCHP to sustain repeated freeze/thaw cycles was thus successfully demonstrated.

Kinetic arrest of field-temperature induced first order phase transition in quasi-one dimensional spin system Ca{sub 3}Co{sub 2}O{sub 6}

DOE Office of Scientific and Technical Information (OSTI.GOV)

De, Santanu, E-mail: santanujuphys91@gmail.com; Kumar, Kranti; Banerjee, A.

We have found that the geometrically frustrated spin chain compound Ca{sub 3}Co{sub 2}O{sub 6} belonging to Ising like universality class with uniaxial anisotropy shows kinetic arrest of first order intermediate phase (IP) to ferrimagnetic (FIM) transition. In this system, dc magnetization measurements followed by different protocols suggest the coexistence of high temperature IP with equilibrium FIM phase in low temperature. Formation of metastable state due to hindered first order transition has also been probed through cooling and heating in unequal field (CHUF) protocol. Kinetically arrested high temperature IP appears to persist down to almost the spin freezing temperature in thismore » system.« less

Liquid–solid phase transition of hydrogen and deuterium in silica aerogel

DOE PAGES

Van Cleve, E.; Worsley, M. A.; Kucheyev, S. O.

2014-10-30

Behavior of hydrogen isotopes confined in disordered low-density nanoporous solids remains essentially unknown. Here, we use relaxation calorimetry to study freezing and melting of H 2 and D 2 in an ~85%-porous base-catalyzed silica aerogel. In this work, we find that liquid–solid transition temperatures of both isotopes inside the aerogel are depressed. The phase transition takes place over a wide temperature range of ~4 K and non-trivially depends on the liquid filling fraction, reflecting the broad pore size distribution in the aerogel. Undercooling is observed for both H 2 and D 2 confined inside the aerogel monolith. Lastly, results formore » H 2 and D 2 are extrapolated to tritium-containing hydrogens with the quantum law of corresponding states.« less

Using the Space-Borne NASA Scatterometer (NSCAT) to Determine The Frozen and Thawed Seasons of a Boreal Landscape

NASA Technical Reports Server (NTRS)

Frolking, S.; McDonald, K. C.; Kimball, J. S.; Way, J. B.; Zimmermann, R.; Running, S. W.

1998-01-01

We hypothesize that the strong sensitivity of radar backscatter to surface dielectric properties, and hence to the phase (solid or liquid) of any water near the surface, should make space-borne radar observations a powerful tool for large-scale spatial monitoring of the freeze/thaw state of the land surface, and thus ecosystem growing season length.

A comprehensive laboratory study on the immersion freezing behavior of illite NX particles: a comparison of seventeen ice nucleation measurement techniques

NASA Astrophysics Data System (ADS)

Hiranuma, N.; Augustin-Bauditz, S.; Bingemer, H.; Budke, C.; Curtius, J.; Danielczok, A.; Diehl, K.; Dreischmeier, K.; Ebert, M.; Frank, F.; Hoffmann, N.; Kandler, K.; Kiselev, A.; Koop, T.; Leisner, T.; Möhler, O.; Nillius, B.; Peckhaus, A.; Rose, D.; Weinbruch, S.; Wex, H.; Boose, Y.; DeMott, P. J.; Hader, J. D.; Hill, T. C. J.; Kanji, Z. A.; Kulkarni, G.; Levin, E. J. T.; McCluskey, C. S.; Murakami, M.; Murray, B. J.; Niedermeier, D.; Petters, M. D.; O'Sullivan, D.; Saito, A.; Schill, G. P.; Tajiri, T.; Tolbert, M. A.; Welti, A.; Whale, T. F.; Wright, T. P.; Yamashita, K.

2014-08-01

Immersion freezing is the most relevant heterogeneous ice nucleation mechanism through which ice crystals are formed in mixed-phase clouds. In recent years, an increasing number of laboratory experiments utilizing a variety of instruments have examined immersion freezing activity of atmospherically relevant ice nucleating particles (INPs). However, an inter-comparison of these laboratory results is a difficult task because investigators have used different ice nucleation (IN) measurement methods to produce these results. A remaining challenge is to explore the sensitivity and accuracy of these techniques and to understand how the IN results are potentially influenced or biased by experimental parameters associated with these techniques. Within the framework of INUIT (Ice Nucleation research UnIT), we distributed an illite rich sample (illite NX) as a representative surrogate for atmospheric mineral dust particles to investigators to perform immersion freezing experiments using different IN measurement methods and to obtain IN data as a function of particle concentration, temperature (T), cooling rate and nucleation time. Seventeen measurement methods were involved in the data inter-comparison. Experiments with seven instruments started with the test sample pre-suspended in water before cooling, while ten other instruments employed water vapor condensation onto dry-dispersed particles followed by immersion freezing. The resulting comprehensive immersion freezing dataset was evaluated using the ice nucleation active surface-site density (ns) to develop a representative ns(T) spectrum that spans a wide temperature range (-37 °C < T < -11 °C) and covers nine orders of magnitude in ns. Our inter-comparison results revealed a discrepancy between suspension and dry-dispersed particle measurements for this mineral dust. While the agreement was good below ~ -26 °C, the ice nucleation activity, expressed in ns, was smaller for the wet suspended samples and higher for the dry-dispersed aerosol samples between about -26 and -18 °C. Only instruments making measurement techniques with wet suspended samples were able to measure ice nucleation above -18 °C. A possible explanation for the deviation between -26 and -18 °C is discussed. In general, the seventeen immersion freezing measurement techniques deviate, within the range of about 7 °C in terms of temperature, by three orders of magnitude with respect to ns. In addition, we show evidence that the immersion freezing efficiency (i.e., ns) of illite NX particles is relatively independent on droplet size, particle mass in suspension, particle size and cooling rate during freezing. A strong temperature-dependence and weak time- and size-dependence of immersion freezing efficiency of illite-rich clay mineral particles enabled the ns parameterization solely as a function of temperature. We also characterized the ns (T) spectra, and identified a section with a steep slope between -20 and -27 °C, where a large fraction of active sites of our test dust may trigger immersion freezing. This slope was followed by a region with a gentler slope at temperatures below -27 °C. A multiple exponential distribution fit is expressed as ns(T) = exp(23.82 × exp(-exp(0.16 × (T + 17.49))) + 1.39) based on the specific surface area and ns(T) = exp(25.75 × exp(-exp(0.13 × (T + 17.17))) + 3.34) based on the geometric area (ns and T in m-2 and °C, respectively). These new fits, constrained by using an identical reference samples, will help to compare IN measurement methods that are not included in the present study and, thereby, IN data from future IN instruments.

Experimental Study of Fuel Heating at Low Temperatures in a Wing Tank Model, Volume 1

NASA Technical Reports Server (NTRS)

Stockemer, F. J.

1981-01-01

Scale model fuel heating systems for use with aviation hydrocarbon fuel at low temperatures were investigated. The effectiveness of the heating systems in providing flowability and pumpability at extreme low temperature when some freezing of the fuel would otherwise occur is evaluated. The test tank simulated a section of an outer wing tank, and was chilled on the upper and lower surfaces. Turbine engine lubricating oil was heated, and recirculating fuel transferred the heat. Fuels included: a commercial Jet A; an intermediate freeze point distillate; a higher freeze point distillate blended according to Experimental Referee Broadened Specification guidelines; and a higher freeze point paraffinic distillate used in a preceding investigation. Each fuel was chilled to selected temperature to evaluate unpumpable solid formation (holdup). Tests simulating extreme cold weather flight, without heating, provided baseline fuel holdup data. Heating and recirculating fuel increased bulk temperature significantly; it had a relatively small effect on temperature near the bottom of the tank. Methods which increased penetration of heated fuel into the lower boundary layer improved the capability for reducing holdup.

Phase transition in conjugated oligomers suspended in chloroform

NASA Astrophysics Data System (ADS)

Dwivedi, Shikha; Kumar, Anupam; Yadav, S. N. S.; Mishra, Pankaj

2015-08-01

Density functional theory (DFT) has been used to investigate the isotropic-nematic (I-N) phase transition in a system of high aspect ratio conjugated oligomers suspended in chloroform. The interaction between the oligomers is modeled using Gay-Berne potential in which effect of solvent is implicit. Percus-Yevick integral equation theory has been used to evaluate the pair correlation functions of the fluid phase at several temperatures and densities. These pair correlation function has been used in the DFT to evaluate the I-N freezing parameters. Highly oriented nematic is found to stabilize at low density. The results obtained are in qualitative agreement with the simulation and are verifiable.

The democracy ochlocracy dictatorship transition in the Sznajd model and in the Ising model

NASA Astrophysics Data System (ADS)

Schneider, Johannes J.; Hirtreiter, Christian

2005-08-01

Since its introduction in 2000, the Sznajd model has been assumed to simulate a democratic community with two parties. The main flaw in this model is that a Sznajd system freezes in the long term in a non-democratic state, which can be either a dictatorship or a stalemate configuration. Here we show that the Sznajd model has better to be considered as a transition model, transferring a democratic system already at the beginning of a simulation via an ochlocratic scenario, i.e., a regime in which several mobs rule, to a dictatorship, thus reproducing the corresponding Aristotelian theory.

Effects of the interaction range on structural phases of flexible polymers.

PubMed

Gross, J; Neuhaus, T; Vogel, T; Bachmann, M

2013-02-21

We systematically investigate how the range of interaction between non-bonded monomers influences the formation of structural phases of elastic, flexible polymers. Massively parallel replica-exchange simulations of a generic, coarse-grained model, performed partly on graphics processing units and in multiple-gaussian modified ensembles, pave the way for the construction of the structural phase diagram, parametrized by interaction range and temperature. Conformational transitions between gas-like, liquid, and diverse solid (pseudo) phases are identified by microcanonical statistical inflection-point analysis. We find evidence for finite-size effects that cause the crossover of "collapse" and "freezing" transitions for very short interaction ranges.

Depositing nanoparticles on a silicon substrate using a freeze drying technique.

PubMed

Sigehuzi, Tomoo

2017-08-28

For the microscopic observation of nanoparticles, an adequate sample preparation is an essential part of this task. Much research has been performed for usable preparation methods that will yield aggregate-free samples. A freeze drying technique, which only requires a -80  ° C freezer and a freeze dryer, is shown to provide an on-substrate dispersion of mostly isolated nanoparticles. The particle density could be made sufficiently high for efficient observations using atomic force microscopy. Since this sandwich method is purely physical, it could be applied to deposit various nanoparticles independent of their surface chemical properties. Suspension film thickness, or the dimensionality of the suspension film, was shown to be crucial for the isolation of the particles. Silica nanoparticles were dispersed on a silicon substrate using this method and the sample properties were examined using atomic force microscopy.

Distribution of coniferin in freeze-fixed stem of Ginkgo biloba L. by cryo-TOF-SIMS/SEM

NASA Astrophysics Data System (ADS)

Aoki, Dan; Hanaya, Yuto; Akita, Takuya; Matsushita, Yasuyuki; Yoshida, Masato; Kuroda, Katsushi; Yagami, Sachie; Takama, Ruka; Fukushima, Kazuhiko

2016-08-01

To clarify the role of coniferin in planta, semi-quantitative cellular distribution of coniferin in quick-frozen Ginkgo biloba L. (ginkgo) was visualized by cryo time-of-flight secondary ion mass spectrometry and scanning electron microscopy (cryo-TOF-SIMS/SEM) analysis. The amount and rough distribution of coniferin were confirmed through quantitative chromatography measurement using serial tangential sections of the freeze-fixed ginkgo stem. The lignification stage of the sample was estimated using microscopic observations. Coniferin distribution visualized at the transverse and radial surfaces of freeze-fixed ginkgo stem suggested that coniferin is stored in the vacuoles, and showed good agreement with the assimilation timing of coniferin to lignin in differentiating xylem. Consequently, it is suggested that coniferin is stored in the tracheid cells of differentiating xylem and is a lignin precursor.

What Controls the Limit of Supercooling and Superheating of Pinned Ice Surfaces?

PubMed

Naullage, Pavithra M; Qiu, Yuqing; Molinero, Valeria

2018-04-05

Cold-adapted organisms produce antifreeze proteins and glycoproteins to control the growth, melting and recrystallization of ice. It has been proposed that these molecules pin the crystal surface, creating a curvature that arrests the growth and melting of the crystal. Here we use thermodynamic modeling and molecular simulations to demonstrate that the curvature of the superheated or supercooled surface depends on the temperature and distances between ice-binding molecules, but not the details of their interactions with ice. We perform simulations of ice pinned with the antifreeze protein TmAFP, polyvinyl alcohol with different degrees of polymerization, and model ice-binding molecules to determine the thermal hystereses on melting and freezing, i.e. the maximum curvature that can be attained before, respectively, ice melts or grows irreversibly over the ice-binding molecules. We find that the thermal hysteresis is controlled by the bulkiness of the ice-binding molecules and their footprint at the ice surface. We elucidate the origin of the asymmetry between freezing and melting hysteresis found in experiments and propose guidelines to design synthetic antifreeze molecules with potent thermal hysteresis activity.

Groundwater-surface water interactions across scales in a boreal landscape investigated using a numerical modelling approach

NASA Astrophysics Data System (ADS)

Jutebring Sterte, Elin; Johansson, Emma; Sjöberg, Ylva; Huseby Karlsen, Reinert; Laudon, Hjalmar

2018-05-01

Groundwater and surface-water interactions are regulated by catchment characteristics and complex inter- and intra-annual variations in climatic conditions that are not yet fully understood. Our objective was to investigate the influence of catchment characteristics and freeze-thaw processes on surface and groundwater interactions in a boreal landscape, the Krycklan catchment in Sweden. We used a numerical modelling approach and sub-catchment evaluation method to identify and evaluate fundamental catchment characteristics and processes. The model reproduced observed stream discharge patterns of the 14 sub-catchments and the dynamics of the 15 groundwater wells with an average accumulated discharge error of 1% (15% standard deviation) and an average groundwater-level mean error of 0.1 m (0.23 m standard deviation). We show how peatland characteristics dampen the effect of intense rain, and how soil freeze-thaw processes regulate surface and groundwater partitioning during snowmelt. With these results, we demonstrate the importance of defining, understanding and quantifying the role of landscape heterogeneity and sub-catchment characteristics for accurately representing catchment hydrological functioning.

The role of side chain conformational flexibility in surface recognition by Tenebrio molitor antifreeze protein

PubMed Central

Daley, Margaret E.; Sykes, Brian D.

2003-01-01

Two-dimensional nuclear magnetic resonance spectroscopy was used to investigate the flexibility of the threonine side chains in the β-helical Tenebrio molitor antifreeze protein (TmAFP) at low temperatures. From measurement of the 3Jαβ 1H-1H scalar coupling constants, the χ1 angles and preferred rotamer populations can be calculated. It was determined that the threonines on the ice-binding face of the protein adopt a preferred rotameric conformation at near freezing temperatures, whereas the threonines not on the ice-binding face sample many rotameric states. This suggests that TmAFP maintains a preformed ice-binding conformation in solution, wherein the rigid array of threonines that form the AFP-ice interface matches the ice crystal lattice. A key factor in binding to the ice surface and inhibition of ice crystal growth appears to be the close surface-to-surface complementarity between the AFP and crystalline ice, and the lack of an entropic penalty associated with freezing out motions in a flexible ligand. PMID:12824479

Superheating of ice crystals in antifreeze protein solutions

PubMed Central

Celik, Yeliz; Graham, Laurie A.; Mok, Yee-Foong; Bar, Maya; Davies, Peter L.; Braslavsky, Ido

2010-01-01

It has been argued that for antifreeze proteins (AFPs) to stop ice crystal growth, they must irreversibly bind to the ice surface. Surface-adsorbed AFPs should also prevent ice from melting, but to date this has been demonstrated only in a qualitative manner. Here we present the first quantitative measurements of superheating of ice in AFP solutions. Superheated ice crystals were stable for hours above their equilibrium melting point, and the maximum superheating obtained was 0.44 °C. When melting commenced in this superheated regime, rapid melting of the crystals from a point on the surface was observed. This increase in melting temperature was more appreciable for hyperactive AFPs compared to the AFPs with moderate antifreeze activity. For each of the AFP solutions that exhibited superheating, the enhancement of the melting temperature was far smaller than the depression of the freezing temperature. The present findings clearly show that AFPs adsorb to ice surfaces as part of their mechanism of action, and this absorption leads to protection of ice against melting as well as freezing. PMID:20215465

Behaviour of polycyclic aromatic hydrocarbons (PAH) in soils under freeze-thaw cycles

NASA Astrophysics Data System (ADS)

Zschocke, Anne; Schönborn, Maike; Eschenbach, Annette

2010-05-01

The arctic region will be one of the most affected regions by climate change due to the predicted temperature rise. As a result of anthropogenic actions as mining, exploration and refining as well as atmospheric transport pollutions can be found in arctic soils. Therefore questions on the behaviour of organic contaminants in permafrost influenced soils are of high relevance. First investigations showed that permafrost can act as a semi-permeable layer for PAH (Curtosi et al., 2007). Therefore it can be assumed that global warming could result in a mobilization of PAH in these permafrost influenced soils. On the other hand a low but detectable mineralization of organic hydrocarbons by microorganisms under repeated freeze-thaw cycles was analysed (Börresen et al. 2007, Eschenbach et al. 2000). In this study the behaviour and distribution of PAH under freezing and periodically freezing and thawing were investigated in laboratory column experiments with spiked soil materials. Two soil materials which are typical for artic regions, a organic matter containing melt water sand and a well decomposed peat, were homogeneously spiked with a composite of a crude oil and the PAH anthracene and benzo(a)pyrene. After 14days preincubation time the soil material was filled in the laboratory columns (40cm high and 10 cm in diameter). Based on studies by Chuvilin et al. (2001) the impact of freezing of the upper third of the column from the surface downwards was examined. The impact of freezing was tested in two different approaches the first one with a single freezing step and the second one with a fourfold repeated cycle of freezing and thawing which takes about 6 or 7 days each. The experimental design and very first results will be shown and discussed. In some experiments with the peat a higher concentration of anthracene and benzo(a)pyrene could be detected below the freezing front in the unfrozen part of the column. Whereas the concentration of PAH had slightly decreased in the frozen part of the column. However these results were not statistically significant they could proof results from Chuvilin et al. (2001). Who found similar results in sandy and clayey material and presumed the expulsion of petroleum hydrocarbons. Barnes et al. (2004) specified that the exclusion of petroleum hydrocarbons due to freezing is caused by displacement from the pore spaces due to expansion of the ice and the forming of crystalline ice structure. Further experimental approaches to investigate the effect of freezing and thawing of permafrost influenced soils on PAH migration will be discussed. References: Barnes, D. L.; Wolfe, S. M. & Filler, D. M. (2004): Equilibrium distribution of petroleum hydrocarbons in freezing ground, Polar Record, 40, 245-251. Börresen M.H., Barnes D.L., Rike A.G. (2007): Repeated freeze-thaw cycles and their effects on mineralization of hexadecane and phenanthrene in cold climate soils. Cold Regions Science and Technology 49, 215-225. Chuvilin, E.; Naletova, N.; Miklyaeva, E.; Kozlova, E. & Instanes, A. (2001): Factors affecting spreadability and transportation of oil in regions of frozen ground. Polar Record 37, 229-238. Curtosi, A.; Pelletier, E.; Vodopivez, C.L.; Mac Cormack, W.P. (2007): Polycyclic aromatic hydrocarbons in soil and surface marine sediment near Jubany Station (Antarctica). Role of permafrost as a low-permeability barrier. Science of The Total Environment 383, 1-3, 193-204. Eschenbach, A.; Wienberg, R.; Mahro, B. (2000): Formation, long-term stability and fate of non-extractable 14C-PAH-residues in contaminated soils. In: Wise, D.L.; Trantolo, D.J.; Cichon, E.J.; Inyang, H.J.; Stottmeister, U. (eds): Remediation Engineering of Contaminated Soils, 2nd Edition; Marcel-Dekker, New York, p. 427-446.

7 CFR 51.2721 - Damage.

Code of Federal Regulations, 2010 CFR

2010-01-01

..., web or frass; (d) Freezing injury causing hard, translucent or discolored flesh; and (e) Dirt when the surface of the kernel is heavily smeared, thickly flecked or coated with dirt, seriously affecting its...

Response of Soil Biogeochemistry to Freeze-thaw Cycles: Impacts on Greenhouse Gas Emission and Nutrient Fluxes

NASA Astrophysics Data System (ADS)

Rezanezhad, F.; Parsons, C. T.; Smeaton, C. M.; Van Cappellen, P.

2014-12-01

Freeze-thaw is an abiotic stress applied to soils and is a natural process at medium to high latitudes. Freezing and thawing processes influence not only the physical properties of soil, but also the metabolic activity of soil microorganisms. Fungi and bacteria play a crucial role in soil organic matter degradation and the production of greenhouse gases (GHG) such as CO2, CH4 and N2O. Production and consumption of these atmospheric trace gases are the result of biological processes such as photosynthesis, aerobic respiration (CO2), methanogenesis, methanotrophy (CH4), nitrification and denitrification (N2O). To enhance our understanding of the effects of freeze-thaw cycles on soil biogeochemical transformations and fluxes, a highly instrumented soil column experiment was designed to realistically simulate freeze-thaw dynamics under controlled conditions. Pore waters collected periodically from different depths of the column and solid-phase analyses on core material obtained at the initial and end of the experiment highlighted striking geochemical cycling. CO2, CH4 and N2O production at different depths within the column were quantified from dissolved gas concentrations in pore water. Subsequent emissions from the soil surface were determined by direct measurement in the head space. Pulsed CO2 emission to the headspace was observed at the onset of thawing, however, the magnitude of the pulse decreased with each subsequent freeze-thaw cycle indicating depletion of a "freeze-thaw accessible" carbon pool. Pulsed CO2 emission was due to a combination of physical release of gases dissolved in porewater and entrapped below the frozen zone and changing microbial respiration in response to electron acceptor variability (O2, NO3-, SO42-). In this presentation, we focus on soil-specific physical, chemical, microbial factors (e.g. redox conditions, respiration, fermentation) and the mechanisms that drive GHG emission and nutrient cycling in soils under freeze-thaw cycles.

Spin glass freezing and superconductivity in YBa2(Cu(1-x)Fe(x))3O7 alloys

NASA Technical Reports Server (NTRS)

Mirebeau, I.; Hennion, M.; Dianoux, J.; Caignaert, V.; Phillips, T. E.; Moorjani, K.

1991-01-01

The dynamics were studied of the iron spins in superconducting YBa2(Cu(0.94)Fe(0.06))3O7 by neutron time of flight measurements. Two samples were studied with slightly different characteristics, as shown by resistivity and neutron diffraction measurements. The same dynamical anomalies are observed by neutrons in both samples. Differences appear qualitative but not quantitative. In the whole temperature range, the q-dependence of the magnetic intensity mainly reflects the magnetic form factor of iron which shows that the iron spins are almost uncorrelated. The elastic and quasielastic intensities strongly vary with temperature. A spin glass like freezing is revealed at low temperature by a sharp decrease of the quasielastic intensity, an increase of the 'elastic' or resolution limited intensity and a minimum in the quasielastic width. The freezing temperature (T sub f - 18 K) corresponds to that already determined by a magnetic splitting in Mossbauer experiments. Above T sub f, the relaxation of the iron spins in the paramagnetic state is modified by the occurrence of superconductivity. An increase was observed of the quasielastic intensity and of the quasielastic width at the superconducting transition.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sundaramurthi, Prakash; Patapoff, Thomas W.; Suryanarayanan, Raj

To study the crystallization of trehalose in frozen solutions and to understand the phase transitions during the entire freeze-drying cycle. Aqueous trehalose solution was cooled to -40 C in a custom-designed sample holder. The frozen solution was warmed to -18 C and annealed, and then dried in the sample chamber of the diffractometer. XRD patterns were continuously collected during cooling, annealing and drying. After cooling, hexagonal ice was the only crystalline phase observed. However, upon annealing, crystallization of trehalose dihydrate was evident. Seeding the frozen solution accelerated the solute crystallization. Thus, phase separation of the lyoprotectant was observed in frozenmore » solutions. During drying, dehydration of trehalose dihydrate yielded a substantially amorphous anhydrous trehalose. Crystallization of trehalose, as trehalose dihydrate, was observed in frozen solutions. The dehydration of the crystalline trehalose dihydrate to substantially amorphous anhydrate occurred during drying. Therefore, analyzing the final lyophile will not reveal crystallization of the lyoprotectant during freeze-drying. The lyoprotectant crystallization can only become evident by continuous monitoring of the system during the entire freeze-drying cycle. In light of the phase separation of trehalose in frozen solutions, its ability to serve as a lyoprotectant warrants further investigation.« less