Borgå, Katrine; Fjeld, Eirik; Kierkegaard, Amelie; McLachlan, Michael S
2013-12-17
Cyclic volatile methyl siloxanes (cVMS) concentrations were analyzed in the pelagic food web of two Norwegian lakes (Mjøsa, Randsfjorden), and in brown trout (Salmo trutta) and Arctic char (Salvelinus alpinus) collected in a reference lake (Femunden), in 2012. Lakes receiving discharge from wastewater treatment plants (Mjøsa and Randsfjorden) had cVMS concentrations in trout that were up to 2 orders of magnitude higher than those in Femunden, where most samples were close to the limit of quantification (LOQ). Food web biomagnification of cVMS in Mjøsa and Randsfjorden was quantified by estimation of trophic magnification factors (TMFs). TMF for legacy persistent organic pollutants (POPs) were analyzed for comparison. Both decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) biomagnified with TMFs of 2.9 (2.1-4.0) and 2.3 (1.8-3.0), respectively. Octamethylcyclotetrasiloxane (D4) was below the LOQ in the majority of samples and had substantially lower biomagnification than for D5 and D6. The cVMS TMFs did not differ between the lakes, whereas the legacy POP TMFs were higher in Mjøsa than inRandsfjorden. Whitefish had lower cVMS bioaccumulation compared to legacy POPs, and affected the TMF significance for cVMS, but not for POPs. TMFs of D5 and legacy contaminants in Lake Mjøsa were consistent with those previously measured in Mjøsa.
Krogseth, Ingjerd Sunde; Whelan, Michael John; Christensen, Guttorm Normann; Breivik, Knut; Evenset, Anita; Warner, Nicholas Alexander
2017-01-03
Cyclic volatile methyl siloxanes (cVMS) are emitted to aquatic environments with wastewater effluents. Here, we evaluate the environmental behavior of three cVMS compounds (octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6)) in a high latitude lake (Storvannet, 70°N 23°E), experiencing intermittent wastewater emissions and high latitude environmental conditions (low temperatures and seasonal ice cover). Measured cVMS concentrations in lake water were below detection limits in both March and June 2014. However, mean concentrations in sediments were 207 ± 30, 3775 ± 973 and 848 ± 211 ng g -1 organic carbon for D4, D5 and D6, respectively. To rationalize measurements, a fugacity-based model for lakes (QWASI) was parametrized for Storvannet. The key removal process for cVMS from the lake was predicted to be advection due to the low hydraulic retention time of the lake, followed by volatilization. Predicted cVMS behavior was highly sensitive to the partition coefficient between organic carbon and water (K OC ) and its temperature dependence. Predictions indicated lower overall persistence with decreasing temperature due to enhanced partitioning from sediments to water. Inverse modeling to predict steady-state emissions from cVMS concentrations in sediment provided unrealistically high emissions, when evaluated against measured concentrations in sewage. However, high concentrations of cVMS in sediment and low concentrations in water could be explained via a hypothetical dynamic emission scenario consistent with combined sewer overflows. The study illustrates the importance of considering compound-specific behavior of emerging contaminants that may differ from legacy organic contaminants.
Panagopoulos, Dimitri; Jahnke, Annika; Kierkegaard, Amelie; MacLeod, Matthew
2015-10-20
The sorption of cyclic volatile methyl siloxanes (cVMS) to organic matter has a strong influence on their fate in the aquatic environment. We report new measurements of the partition ratios between freshwater sediment organic carbon and water (KOC) and between Aldrich humic acid dissolved organic carbon and water (KDOC) for three cVMS, and for three polychlorinated biphenyls (PCBs) that were used as reference chemicals. Our measurements were made using a purge-and-trap method that employs benchmark chemicals to calibrate mass transfer at the air/water interface in a fugacity-based multimedia model. The measured log KOC of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) were 5.06, 6.12, and 7.07, and log KDOC were 5.05, 6.13, and 6.79. To our knowledge, our measurements for KOC of D6 and KDOC of D4 and D6 are the first reported. Polyparameter linear free energy relationships (PP-LFERs) derived from training sets of empirical data that did not include cVMS generally did not predict our measured partition ratios of cVMS accurately (root-mean-squared-error (RMSE) for logKOC 0.76 and for logKDOC 0.73). We constructed new PP-LFERs that accurately describe partition ratios for the cVMS as well as for other chemicals by including our new measurements in the existing training sets (logKOC RMSEcVMS: 0.09, logKDOC RMSEcVMS: 0.12). The PP-LFERs we have developed here should be further evaluated and perhaps recalibrated when experimental data for other siloxanes become available.
McGoldrick, Daryl J; Durham, Jeremy; Leknes, Henriette; Kierkegaard, Amelie; Gerhards, Reinhard; Powell, David E; McLachlan, Michael S
2011-11-01
Cyclic volatile methyl siloxanes (cVMS) are high volume production chemicals used in a wide range of industrial and consumer products. Three cVMS compounds (D4, D5, and D6) have and are undergoing environmental risk evaluations in several countries and have been proposed for legal regulation in Canada. As interest in monitoring concentrations of these chemicals in the environment increase, there is a need to evaluate the analytical procedures for cVMS in biological matrices in order to assess the quality of data produced. The purpose of this study was to determine laboratory testing performance for measuring residues of D4, D5, and D6 in a standard set of fish homogenate samples and to estimate limits of determination for each substance. The samples sent to each laboratory consisted of homogenized whole body tissues of hatchery raised rainbow trout which were fed food fortified with D4, D5, and D6 (dosed) and trout that were fed standard food rations (control). The participants analyzed each sample using their analytical method of choice using their own standards and procedures for quantification and quality control. With a few exceptions, participating laboratories generated comparable results for D4, D5, and D6 in both the dosed and control samples having z-scores between 2 and -2. Method detection limits for the whole fish matrix were on average 2.4 ng g(-1) ww for D4, 2.3 ng g(-1) ww for D5, and 1.8 ng g(-1) ww for D6. Crown Copyright © 2011. Published by Elsevier Ltd. All rights reserved.
Occurrence and seasonality of cyclic volatile methyl siloxanes in Arctic air.
Krogseth, Ingjerd S; Kierkegaard, Amelie; McLachlan, Michael S; Breivik, Knut; Hansen, Kaj M; Schlabach, Martin
2013-01-02
Cyclic volatile methyl siloxanes (cVMS) are present in technical applications and personal care products. They are predicted to undergo long-range atmospheric transport, but measurements of cVMS in remote areas remain scarce. An active air sampling method for decamethylcyclopentasiloxane (D5) was further evaluated to include hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), and dodecamethylcyclohexasiloxane (D6). Air samples were collected at the Zeppelin observatory in the remote Arctic (79° N, 12° E) with an average sampling time of 81 ± 23 h in late summer (August-October) and 25 ± 10 h in early winter (November-December) 2011. The average concentrations of D5 and D6 in late summer were 0.73 ± 0.31 and 0.23 ± 0.17 ng/m(3), respectively, and 2.94 ± 0.46 and 0.45 ± 0.18 ng/m(3) in early winter, respectively. Detection of D5 and D6 in the Arctic atmosphere confirms their long-range atmospheric transport. The D5 measurements agreed well with predictions from a Eulerian atmospheric chemistry-transport model, and seasonal variability was explained by the seasonality in the OH radical concentrations. These results extend our understanding of the atmospheric fate of D5 to high latitudes, but question the levels of D3 and D4 that have previously been measured at Zeppelin with passive air samplers.
Junge relationships in measurement data for cyclic siloxanes in air.
MacLeod, Matthew; Kierkegaard, Amelie; Genualdi, Susie; Harner, Tom; Scheringer, Martin
2013-10-01
In 1974, Junge postulated a relationship between variability of concentrations of gases in air at remote locations and their atmospheric residence time, and this Junge relationship has subsequently been observed empirically for a range of trace gases. Here, we analyze two previously-published datasets of concentrations of cyclic volatile methyl siloxanes (cVMS) in air and find Junge relationships in both. The first dataset is a time series of concentrations of decamethylcyclopentasiloxane (D5) measured between January and June, 2009 at a rural site in southern Sweden that shows a Junge relationship in the temporal variability of the measurements. The second dataset consists of measurements of hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4) and D5 made simultaneously at 12 sites in the Global Atmospheric Passive Sampling (GAPS) network that shows a Junge relationship in the spatial variability of the three cVMS congeners. We use the Junge relationship for the GAPS dataset to estimate atmospheric lifetimes of dodecamethylcyclohexasiloxane (D6), 8:2-fluorotelomer alcohol and trichlorinated biphenyls that are within a factor of 3 of estimates based on degradation rate constants for reaction with hydroxyl radical determined in laboratory studies. Copyright © 2012 Elsevier Ltd. All rights reserved.
Safron, Andreas; Strandell, Michael; Kierkegaard, Amelie
2015-01-01
ABSTRACT Reaction with hydroxyl radicals (OH) is the major pathway for removal of cyclic volatile methyl siloxanes (cVMS) from air. We present new measurements of second‐order rate constants for reactions of the cVMS octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) with OH determined at temperatures between 313 and 353 K. Our measurements were made using the method of relative rates with cyclohexane as a reference substance and were conducted in a 140‐mL gas‐phase reaction chamber with online mass spectrometry analysis. When extrapolated to 298 K, our measured reaction rate constants of D4 and D5 with the OH radical are 1.9 × 10−12 (95% confidence interval (CI): (1.7–2.2) × 10−12) and 2.6 × 10−12 (CI: (2.3–2.9) × 10−12) cm3 molecule−1 s−1, respectively, which are 1.9× and 1.7× faster than previous measurements. Our measured rate constant for D6 is 2.8 × 10−12 (CI: (2.5–3.2) × 10−12) cm3 molecule−1 s−1 and to our knowledge there are no comparable laboratory measurements in the literature. Reaction rates for D5 were 33% higher than for D4 (CI: 30–37%), whereas the rates for D6 were only 8% higher than for D5 (CI: 5–10%). The activation energies of the reactions of D4, D5, and D6 with OH were not statistically different and had a value of 4300 ± 2800 J/mol. PMID:27708500
Safron, Andreas; Strandell, Michael; Kierkegaard, Amelie; Macleod, Matthew
2015-07-01
Reaction with hydroxyl radicals (OH) is the major pathway for removal of cyclic volatile methyl siloxanes (cVMS) from air. We present new measurements of second-order rate constants for reactions of the cVMS octamethylcyclotetrasiloxane (D 4 ), decamethylcyclopentasiloxane (D 5 ), and dodecamethylcyclohexasiloxane (D 6 ) with OH determined at temperatures between 313 and 353 K. Our measurements were made using the method of relative rates with cyclohexane as a reference substance and were conducted in a 140-mL gas-phase reaction chamber with online mass spectrometry analysis. When extrapolated to 298 K, our measured reaction rate constants of D 4 and D 5 with the OH radical are 1.9 × 10 -12 (95% confidence interval (CI): (1.7-2.2) × 10 -12 ) and 2.6 × 10 -12 (CI: (2.3-2.9) × 10 -12 ) cm 3 molecule -1 s -1 , respectively, which are 1.9× and 1.7× faster than previous measurements. Our measured rate constant for D 6 is 2.8 × 10 -12 (CI: (2.5-3.2) × 10 -12 ) cm 3 molecule -1 s -1 and to our knowledge there are no comparable laboratory measurements in the literature. Reaction rates for D 5 were 33% higher than for D 4 (CI: 30-37%), whereas the rates for D 6 were only 8% higher than for D 5 (CI: 5-10%). The activation energies of the reactions of D 4 , D 5 , and D 6 with OH were not statistically different and had a value of 4300 ± 2800 J/mol.
Xiao, Ruiyang; Zammit, Ian; Wei, Zongsu; Hu, Wei-Ping; MacLeod, Matthew; Spinney, Richard
2015-11-17
The ubiquitous presence of cyclic volatile methylsiloxanes (cVMS) in the global atmosphere has recently raised environmental concern. In order to assess the persistence and long-range transport potential of cVMS, their second-order rate constants (k) for reactions with hydroxyl radical ((•)OH) in the gas phase are needed. We experimentally and theoretically investigated the kinetics and mechanism of (•)OH oxidation of a series of cVMS, hexamethylcyclotrisiloxane (D3), octamethycyclotetrasiloxane (D4), and decamethycyclopentasiloxane (D5). Experimentally, we measured k values for D3, D4, and D5 with (•)OH in a gas-phase reaction chamber. The Arrhenius activation energies for these reactions in the temperature range from 313 to 353 K were small (-2.92 to 0.79 kcal·mol(-1)), indicating a weak temperature dependence. We also calculated the thermodynamic and kinetic behaviors for reactions at the M06-2X/6-311++G**//M06-2X/6-31+G** level of theory over a wider temperature range of 238-358 K that encompasses temperatures in the troposphere. The calculated Arrhenius activation energies range from -2.71 to -1.64 kcal·mol(-1), also exhibiting weak temperature dependence. The measured k values were approximately an order of magnitude higher than the theoretical values but have the same trend with increasing size of the siloxane ring. The calculated energy barriers for H-atom abstraction at different positions were similar, which provides theoretical support for extrapolating k for other cyclic siloxanes from the number of abstractable hydrogens.
Rauert, Cassandra; Shoieb, Mahiba; Schuster, Jasmin K; Eng, Anita; Harner, Tom
2018-07-01
Poly- and per-fluoroalkyl substances (PFAS) and volatile methyl siloxanes (VMS) were monitored at 21 sites in the Global Atmospheric Passive Sampling (GAPS) Network. Atmospheric concentrations previously reported from 2009 were compared to concentrations measured at these sites in 2013 and 2015, to assess trends over 7 years of monitoring. Concentrations of the fluorotelomer alcohols (FTOHs) and fluorinated sulfonamides and sulfonamidoethanols (FOSAs and FOSEs) were stable at these sites from 2009 to 2015 with no significant difference (p > 0.05) in concentrations. Elevated concentrations of all the neutral PFAS were detected at the urban sites as compared to the polar/background sites. The perfluorosulfonic acids (PFSAs), meanwhile, saw a significant increase (p < 0.001) in concentrations from 2009 to 2015. The perfluorocarboxylic acids (PFCAs) had elevated concentrations in 2015, however, the difference was not statistically significant (p > 0.05). Concentrations of the PFSAs and the PFCAs were similar at all location types, showing the global reach of these persistent compounds. Concentrations of the cyclic VMS (cVMS) were at least an order of magnitude higher than the linear VMS (lVMS) and the PFAS. Octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) saw a weak significant increase in concentrations from 2009 to 2013 (p < 0.05), however, hexamethylcyclotrisiloxane (D3) had a strong significant decrease in concentrations from 2009 to 2015 (p < 0.01). Copyright © 2018 The Authors. Published by Elsevier Ltd.. All rights reserved.
Determination of cyclic volatile methylsiloxanes in personal care products by gas chromatography.
Brothers, H M; Boehmer, T; Campbell, R A; Dorn, S; Kerbleski, J J; Lewis, S; Mund, C; Pero, D; Saito, K; Wieser, M; Zoller, W
2017-12-01
Organosiloxanes are prevalent in personal care products (PCPs) due to the desired properties they impart in the usage and application of such products. However, the European Chemical Agency (ECHA) has recently published restriction proposals on the amount of two cyclic siloxanes, octamethylcyclotetrasiloxane (D4) and decamethylcyclotetrasiloxane (D5), allowed in wash off products such as shampoos and conditioners which are discharged down the drain during consumer use. This legislation will require that reliable analytical methods are available for manufacturers and government agencies to use in documenting compliance with the restrictions. This article proposes a simple analytical method to enable accurate measurement of these compounds down to the circa 0.1 weight per cent level in PCPs. Although gas chromatography methods are reported in the literature for quantitation of D4 and D5 in several matrices including PCPs, the potential for generation of false positives due to contamination, co-elution and in situ generation of cyclic volatile methylsiloxanes (cVMS) is always present and needs to be controlled. This report demonstrates the applicability of using a combination of emulsion break, liquid-liquid extraction and silylation sample preparation followed by GC-FID analysis as a suitable means of analysing PCPs for specific cVMS. The reliability and limitations of such methodology were demonstrated through several round-robin studies conducted in the laboratories of a consortium of silicone manufacturers. In addition, this report presents examples of false positives encountered during development of the method and presents a comparative analysis between this method and a published QuEChERS sample preparation procedure to illustrate the potential for generation of false positives when an inappropriate approach is applied to determination of cVMS in personal care products. This report demonstrates that an approach to determine cVMS levels in personal care products is to perform an emulsion break on the sample, isolate the non-polar phase from the emulsion break and treat with a silylation reagent to abate potential in situ formation of cyclics during the course of GC-FID analysis. Round-robin studies conducted in laboratories representing multiple siloxane manufacturers demonstrated the reliability of the GC-FID method when measuring cVMS in PCPs down to circa 0.1%. © 2017 CES - Silicones Europe. International Journal of Cosmetic Science published by John Wiley & Sons Ltd on behalf of Society of Cosmetic Scientists and the Société Française de Cosmétologie.
Xu, Lin; Shi, Yali; Liu, Nannan; Cai, Yaqi
2015-02-01
We investigated human exposure to methyl siloxanes in three general industries (building, automobile, and textile industries) and residential areas in China. Usage volumes of methyl siloxanes per capita in these industries were 2-5 orders of magnitudes higher than those in residential areas. Methyl siloxane concentrations in indoor air and dust samples from industrial facilities were 1-3 orders of magnitudes higher than those in residential houses. Both cyclic (D4-D6) and linear (L5-L16) siloxanes were detected in plasma of industrial workers (1.00-252 ng/mL, detection frequencies=3.7-71%, n=528), while only cyclic compounds (D4-D6) were detected in plasma of general population (n=519) with much lower concentrations (1.10-7.50 ng/mL) and detection frequencies (1.7-3.7%). During the occupational exposure, anti-dust mask can reduce 30% of intake of cyclic siloxanes and 74% of intake of linear siloxanes, respectively. In addition, PM-10 could elevate intake of linear siloxanes. Calculated fat-plasma partition ratios of methyl siloxanes (D4-D6, L6-L11) in the present study were 5.3-241 mL/g. Linear rather than cyclic siloxanes had an apparent accumulation in abdominal fat. Population's half-lives of L8-L10 in abdominal fat of general population were approximately 1.49-1.80 years. Copyright © 2014 Elsevier B.V. All rights reserved.
Fathead minnow (Pimephales promelas) embryo to adult exposure to decamethylcyclopentasiloxane (D5).
Parrott, J L; Alaee, M; Wang, D; Sverko, E
2013-10-01
The cyclic siloxane decamethylcyclopentasiloxane (D5) is a high production volume chemical which has recently been assessed under the Canadian Chemicals Management Plan (CMP). Cyclic volatile methyl siloxanes (cVMS) are one of the challenge substances in the CMP batches. To provide toxicity and growth information on a species of relevance to the Canadian environment, we assessed D5 in a fathead minnow (Pimephales promelas) embryo to young adult assay. The test was 65d in length, and exposed fathead minnow eggs to juveniles until near maturity (60d post-hatch). The D5 concentrations in flow-through fish exposure aquaria were about one-third of nominal D5 concentrations. Fathead minnows were exposed to 0.25, 0.82, 1.7, 3.6, and 8.7μgL(-1) D5. During the exposure of fathead minnows to D5 there were few effects seen. Egg hatching and larval fish survival and growth were normal. Juvenile fish survival and growth were good in all environmentally-relevant concentrations of D5, and were similar to control fish. The two highest D5 concentrations (8.7μgL(-1) and 3.6μgL(-1), mean measured D5) increased the condition factors of fathead minnows compared to water control and DMSO control fish. Although there were few effects of D5 in our fathead minnow study, the compound was taken up and stored in fish bodies over the 65-d exposure. The bioconcentration factor for D5 in fathead minnows was 4450, for the lowest environmentally-relevant D5 exposure water concentrations, and 4920 for all D5 exposure concentrations tested. Crown Copyright © 2012. Published by Elsevier Ltd. All rights reserved.
The Incidence and Fate of Volatile Methyl Siloxanes in a Crewed Spacecraft Cabin
NASA Technical Reports Server (NTRS)
Perry, Jay L.; Kayatin, Matthew J.
2017-01-01
Volatile methyl siloxanes (VMS) arise from diverse, pervasive sources aboard crewed spacecraft ranging from materials offgassing to volatilization from personal care products. These sources lead to a persistent VMS compound presence in the cabin environment that must be considered for robust life support system design. Volatile methyl siloxane compound stability in the cabin environment presents an additional technical issue because degradation products such as dimethylsilanediol (DMSD) are highly soluble in water leading to a unique load challenge for water purification processes. The incidence and fate of VMS compounds as observed in the terrestrial atmosphere, water, and surface (soil) environmental compartments have been evaluated as an analogy for a crewed cabin environment. Volatile methyl siloxane removal pathways aboard crewed spacecraft are discussed and a material balance accounting for a DMSD production mechanism consistent with in-flight observations is presented.
Capela, Daniela; Homem, Vera; Alves, Arminda; Santos, Lúcia
2018-03-01
Recently, Pierre Germain from CES - Silicon Europe published a comment on the paper "Volatile methylsiloxanes in personal care products - Using QuEChERS as a "green" analytical approach", raising concerns that the artefacts employed in the analysis of cyclic volatile methylsiloxanes (cVMS) were not adequately controlled, while using this example as an opportunity to emphasize the difficulties associated with siloxanes analyses in complex matrices such as personal care products (PCPs). We are now addressing these concerns and conveying some clarifications regarding the experiments performed to validate the analytical method adequately. Those details were not included in the original publication because the objective was the quantification of VMS in several PCPs. Copyright © 2017 Elsevier B.V. All rights reserved.
Coggon, Matthew M; McDonald, Brian C; Vlasenko, Alexander; Veres, Patrick R; Bernard, François; Koss, Abigail R; Yuan, Bin; Gilman, Jessica B; Peischl, Jeff; Aikin, Kenneth C; DuRant, Justin; Warneke, Carsten; Li, Shao-Meng; de Gouw, Joost A
2018-05-15
Decamethylcyclopentasiloxane (D 5 ) is a cyclic volatile methyl siloxane (cVMS) that is widely used in consumer products and commonly observed in urban air. This study quantifies the ambient mixing ratios of D 5 from ground sites in two North American cities (Boulder, CO, USA, and Toronto, ON, CA). From these data, we estimate the diurnal emission profile of D 5 in Boulder, CO. Ambient mixing ratios were consistent with those measured at other urban locations; however, the diurnal pattern exhibited similarities with those of traffic-related compounds such as benzene. Mobile measurements and vehicle experiments demonstrate that emissions of D 5 from personal care products are coincident in time and place with emissions of benzene from motor vehicles. During peak commuter times, the D 5 /benzene ratio (w/w) is in excess of 0.3, suggesting that the mass emission rate of D 5 from personal care product usage is comparable to that of benzene due to traffic. The diurnal emission pattern of D 5 is estimated using the measured D 5 /benzene ratio and inventory estimates of benzene emission rates in Boulder. The hourly D 5 emission rate is observed to peak between 6:00 and 7:00 AM and subsequently follow an exponential decay with a time constant of 9.2 h. This profile could be used by models to constrain temporal emission patterns of personal care products.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Tansel, Berrin, E-mail: tanselb@fiu.edu; Surita, Sharon C.
2014-11-15
Highlights: • In the digester gas, D4 and D5 comprised the 62% and 27% if siloxanes, respectively. • In landfill gas, the bulk of siloxanes were TMSOH (58%) followed by D4 (17%). • Methane utilization may be a possible mechanism for TMSOH formation in the landfills. • The geometric configurations of D4 and D5 molecules make them very stable. - Abstract: The objectives of this study were to compare the types and levels of volatile methyl siloxanes (VMS) present in biogas generated in the anaerobic digesters and landfills, evaluate the energetics of siloxane transformations under anaerobic conditions, compare the conditionsmore » in anaerobic digesters and municipal solid waste (MSW) landfills which result in differences in siloxane compositions. Biogas samples were collected at the South District Wastewater Treatment Plant and South Dade Landfill in Miami, Florida. In the digester gas, D4 and D5 comprised the bulk of total siloxanes (62% and 27%, respectively) whereas in the landfill gas, the bulk of siloxanes were trimethylsilanol (TMSOH) (58%) followed by D4 (17%). Presence of high levels of TMSOH in the landfill gas indicates that methane utilization may be a possible reaction mechanism for TMSOH formation. The free energy change for transformation of D5 and D4 to TMSOH either by hydrogen or methane utilization are thermodynamically favorable. Either hydrogen or methane should be present at relatively high concentrations for TMSOH formation which explains the high levels present in the landfill gas. The high bond energy and bond distance of the Si–O bond, in view of the atomic sizes of Si and O atoms, indicate that Si atoms can provide a barrier, making it difficult to break the Si–O bonds especially for molecules with specific geometric configurations such as D4 and D5 where oxygen atoms are positioned inside the frame formed by the large Si atoms which are surrounded by the methyl groups.« less
Degradation of polymer electrolyte membrane fuel cell by siloxane in biogas
NASA Astrophysics Data System (ADS)
Seo, Ji-Sung; Kim, Da-Yeong; Hwang, Sun-Mi; Seo, Min Ho; Seo, Dong-Jun; Yang, Seung Yong; Han, Chan Hui; Jung, Yong-Min; Guim, Hwanuk; Nahm, Kee Suk; Yoon, Young-Gi; Kim, Tae-Young
2016-06-01
We studied the degradation and durability of polymer electrolyte membrane fuel cell (PEMFC) at membrane-electrode-assembly (MEA) level by injection of octamethylcyclotetrasiloxane (D4) as a representative siloxane, which has been found in many industrial and personal products. Specifically, i) GC/MS analysis demonstrated that the ring-opening polymerization of D4 could result in the formation of various linear and cyclic siloxanes in both electrodes of MEA; ii) post-test analysis revealed that the transformed siloxanes were transported from the anode to the cathode via free-volumes in the polymer membrane; iii) RDE measurement and DFT calculation revealed that D4 was not directly responsible for the electrocatalytic activity of Pt; iv) electrochemical analysis demonstrated that the residual methyl groups of siloxane and various siloxanes did not hinder the proton transport in the polymer membrane; and v) siloxanes accumulated in the primary and secondary pores with the exception of an external surface of carbon, causing an increase in the oxygen reactant's resistance and resulting in a decrease of the cell performance. In addition, we confirmed that injection of D4 did not affect the carbon corrosion adversely because the siloxane had little influence on water sorption in the catalyst layer.
Lai, Eddie Hsiang-Hua; Liu, Jen-Pei; Chang, Jenny Zwei-Chieng; Tsai, Shih-Jaw; Yao, Chung-Chen Jane; Chen, Mu-Hsiung; Chen, Yi-Jane; Lin, Chun-Pin
2008-04-01
The skeletal maturation status of a growing patient can influence the selection of orthodontic treatment procedures. Either lateral cephalometric or hand-wrist radiography can be used to assess skeletal development. In this study, we examined the correlation between the maturation stages of cervical vertebrae and hand-wrist bones in Taiwanese individuals. The study group consisted of 330 male and 379 female subjects ranging in age from 8 to 18 years. A total of 709 hand-wrist and 709 lateral cephalometric radiographs were analyzed. Hand-wrist maturation stages were assessed using National Taiwan University Hospital Skeletal Maturation Index (NTUH-SMI). Cervical vertebral maturation stages were determined by the latest Cervical Vertebral Maturation Stage (CVMS) Index. Spearman's rank correlation was used to correlate the respective maturation stages assessed from the hand-wrist bones and the cervical vertebrae. The values of Spearman's rank correlation were 0.910 for males and 0.937 for females, respectively. These data confirmed a strong and significant correlation between CVMS and NTUH-SMI systems (p less than 0.001). After comparison of the mean ages of subjects in different stages of CVMS and NTU-SMI systems, we found that CVMS I corresponded to NTUH-SMI stages 1 and 2, CVMS II to NTUH-SMI stage 3, CVMS III to NTUHSMI stage 4, CVMS IV to NTUH-SMI stage 5, CVMS V to NTUH-SMI stages 6, 7 and 8, and CVMS VI to NTUH-SMI stage 9. Our results indicate that cervical vertebral maturation stages can be used to replace hand-wrist bone maturation stages for evaluation of skeletal maturity in Taiwanese individuals.
Chongcharueyskul, Pathomporn; Wangsrimonkol, Tasanee; Pisek, Poonsak; Pisek, Araya; Manosudprasit, Montian
2015-08-01
To examine correlations between cervical vertebral maturation stages (CVMs) and dental development stages, and cervical vertebral maturation (CVM) stage 6 and completion of root formation of mandibular third molar in Thai cleft patients. Lateral cephalograms of 366 cleft subjects aged 7-9 years were assessed for CVMs using Baccetti method. Calcication stages of all left mandibular teeth within each CVMs were assessed from panoramic films using Demirjian method. Spearman rank correlation coefficients comparing CVMs and teeth were 0.51-0.79 (p<0.001). Second molar had the highest and central incisor had the lowest correlations. In CVMs 6, 2.9% of third molars had completed root formation. However, only CVMs 6 could be predicted from third molar stage G that had a high likelihood ratio (30.94). Dental development was highly correlated with CVM in clefts. Third molar stage G could predict completed growth of mandible in individual patients, but it should be combined with other maturation indicators.
Riehle, Natascha; Götz, Tobias; Kandelbauer, Andreas; Tovar, Günter E M; Lorenz, Günter
2018-06-01
This article contains data on the synthesis and mechanical characterization of polysiloxane-based urea-elastomers (PSUs) and is related to the research article entitled "Influence of PDMS molecular weight on transparency and mechanical properties of soft polysiloxane-urea-elastomers for intraocular lens application" (Riehle et al., 2018) [1]. These elastomers were prepared by a two-step polyaddition using the aliphatic diisocyanate 4,4'-Methylenbis(cyclohexylisocyanate) (H 12 MDI), a siloxane-based chain extender 1,3-Bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane (APTMDS) and amino-terminated polydimethylsiloxanes (PDMS) or polydimethyl-methyl-phenyl-siloxane-copolymers (PDMS-Me,Ph), respectively. (More details about the synthesis procedure and the reaction scheme can be found in the related research article (Riehle et al., 2018) [1]). Amino-terminated polydimethylsiloxanes with varying molecular weights and PDMS-Me,Ph-copolymers were prepared prior by a base-catalyzed ring-chain equilibration of a cyclic siloxane and the endblocker APTMDS. This DiB article contains a procedure for the synthesis of the base catalyst tetramethylammonium-3-aminopropyl-dimethylsilanolate and a generic synthesis procedure for the preparation of a PDMS having a targeted number average molecular weight M ¯ n of 3000 g mol -1 . Molecular weights and the amount of methyl-phenyl-siloxane within the polysiloxane-copolymers were determined by 1 H NMR and 29 Si NMR spectroscopy. The corresponding NMR spectra and data are described in this article. Additionally, this DiB article contains processed data on in line and off line FTIR-ATR spectroscopy, which was used to follow the reaction progress of the polyaddition by showing the conversion of the diisocyanate. All relevant IR band assignments of a polydimethylsiloxane-urea spectrum are described in this article. Finally, data on the tensile properties and the mechanical hysteresis-behaviour at 100% elongation of PDMS-based polyurea-elastomers are shown in dependence to the PDMS molecular weight.
Determination of soil–water sorption coefficients of volatile methylsiloxanes
Kozerski, Gary E; Xu, Shihe; Miller, Julie; Durham, Jeremy
2014-01-01
The sorption behaviors of 4 cyclic and linear volatile methyl siloxane (VMS) compounds between water and organic matter in 3 United Kingdom soils were studied by a batch equilibrium method using13C-enriched sorbates. Sorption and desorption kinetics and isotherms were determined for octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), octamethyltrisiloxane (L3), and decamethyltetrasiloxane (L4). Concentrations of [13C]-VMS in the soil and aqueous phases were measured directly by extraction and gas chromatography–mass spectrometry techniques. All VMS compounds were sorbed rapidly, reaching constant distributions in all soils by 24 h. Desorption kinetics were very rapid, with reattainment of equilibrium within 1 h. In the main, linear isotherms were observed for aqueous concentrations at or below 4% of the solubility limits. The average sorption organic carbon partition coefficient (log KOC) values across soils were 4.23 for D4, 5.17 for D5, 4.32 for L3, and 5.13 for L4, with standard deviations of 0.09 to 0.34. Desorption KOC values were systematically greater by 0.1 log units to 0.3 log units. The linear isotherms and low variation in KOC values across soils suggested partitioning-dominated sorption of the VMS. Compared with traditional hydrophobic organic compounds, KOC values for the VMS compounds were significantly lower than expected on the basis of their octanol–water partition coefficients. A linear free energy relationship analysis showed that these differences could be rationalized quantitatively in terms of the inherent characteristics of the VMS compounds, combined with the differences in solvation properties of organic matter and octanol. Environ Toxicol Chem 2014; 33:1937–1945. PMID:24862578
Rare DNA copy number variants in cardiovascular malformations with extracardiac abnormalities
USDA-ARS?s Scientific Manuscript database
Clinically significant cardiovascular malformations (CVMs) occur in 5-8 per 1000 live births. Recurrent copy number variations (CNVs) are among the known causes of syndromic CVMs, accounting for an important fraction of cases. We hypothesized that many additional rare CNVs also cause CVMs and can be...
USDA-ARS?s Scientific Manuscript database
Polyvinyl alcohols-based nanocomposite films were fabricated with four types of montmorillonite (MMT) nanoclay, including 18-amino stearic acid (I.24TL), methyl, bis hydroxyethyl, octadecyl ammonium (I.34TCN), di-methyl, di-hydrogenated tallow ammonium/siloxane (I.44PSS) organically modified MMT, an...
Ultrahigh Molecular Weight Aromatic Siloxane Polymers
NASA Technical Reports Server (NTRS)
Ludwick, L. M.
1983-01-01
Silphenylene-siloxane polymers can be prepared by a condensation reaction of a diol 1,4-bis(hydroxydimethylsilyl)benzene and a silane bis(dimethylamino)dimethylsilane. Using a stepwise condensation technique, a polymer (R=CH3) with a molecular weight in excess of 1.0 x 1 million has been produced. The polymer exhibits increased thermal stability, compared to a methyl siloxane polymer without the aromatic phenyl ring in the backbone. The use of bis(dimethylamino)methylvinylsilane should allow for ready crosslinking at the vinyl sites (R=-CH=CH2) introduced into the backbone. However, under the conditions of the reaction system a high molecular weight polymer was not obtained or the polymer underwent a crosslinking process during the synthesis.
Manoso, Amy S; Ahn, Chuljin; Soheili, Arash; Handy, Christopher J; Correia, Reuben; Seganish, W Michael; Deshong, Philip
2004-11-26
General reaction conditions for the synthesis of aryl(trialkoxy)silanes from aryl Grignard and lithium reagents and tetraalkyl orthosilicates (Si(OR)(4)) have been developed. Ortho-, meta-, and para-substituted bromoarenes underwent efficient metalation and silylation at low temperature to provide aryl siloxanes. Mixed results were obtained with heteroaromatic substrates: 3-bromothiophene, 3-bromo-4-methoxypyridine, 5-bromoindole, and N-methyl-5-bromoindole underwent silylation in good yield, whereas a low yield of siloxane was obtained from 2-bromofuran, and 2-bromopyridine failed to give silylated product. The synthesis of siloxanes via organolithium and magnesium reagents was limited by the formation of di- and triarylated silanes (Ar(2)Si(OR)(2) and Ar(3)SiOR, respectively) and dehalogenated (Ar-H) byproducts. Silylation at low temperature gave predominantly monoaryl siloxanes, without requiring a large excess of the electrophile. Optimal reaction conditions for the synthesis of siloxanes from aryl Grignard reagents entailed addition of arylmagnesium reagents to 3 equiv of tetraethyl- or tetramethyl orthosilicate at -30 degrees C in THF. Aryllithium species were silylated using 1.5 equiv of tetraethyl- or tetramethyl orthosilicate at -78 degrees C in ether.
Krogseth, Ingjerd S; Undeman, Emma; Evenset, Anita; Christensen, Guttorm N; Whelan, Mick J; Breivik, Knut; Warner, Nicholas A
2017-11-07
Cyclic volatile methylsiloxanes (cVMS) are used in personal care products and emitted to aquatic environments through wastewater effluents, and their bioaccumulation potential is debated. Here, a new bentho-pelagic version of the ACC-HUMAN model was evaluated for polychlorinated biphenyls (PCBs) and applied to cVMS in combination with measurements to explore their bioaccumulation behavior in a subarctic lake. Predictions agreed better with measured PCB concentrations in Arctic char (Salvelinus alpinus) and brown trout (Salmo trutta) when the benthic link was included than in the pelagic-only model. Measured concentrations of decamethylcyclopentasiloxane (D5) were 60 ± 1.2 (Chironomidae larvae), 107 ± 4.5 (pea clams Pisidium sp.), 131 ± 105 (three-spined sticklebacks: Gasterosteus aculeatus), 41 ± 38 (char), and 9.9 ± 5.9 (trout) ng g -1 wet weight. Concentrations were lower for octamethylcyclotetrasiloxane (D4) and dodecamethylcyclohexasiloxane (D6), and none of the cVMS displayed trophic magnification. Predicted cVMS concentrations were lower than measured in benthos, but agreed well with measurements in fish. cVMS removal through ventilation was an important predicted loss mechanism for the benthic-feeding fish. Predictions were highly sensitive to the partition coefficient between organic carbon and water (K OC ) and its temperature dependence, as this controlled bioavailability for benthos (the main source of cVMS for fish).
A comparison of hand-wrist bone and cervical vertebral analyses in measuring skeletal maturation.
Gandini, Paola; Mancini, Marta; Andreani, Federico
2006-11-01
To compare skeletal maturation as measured by hand-wrist bone analysis and by cervical vertebral analysis. A radiographic hand-wrist bone analysis and cephalometric cervical vertebral analysis of 30 patients (14 males and 16 females; 7-18 years of age) were examined. The hand-wrist bone analysis was evaluated by the Bjork index, whereas the cervical vertebral analysis was assessed by the cervical vertebral maturation stage (CVMS) method. To define vertebral stages, the analysis consisted of both cephalometric (13 points) and morphologic evaluation of three cervical vertebrae (concavity of second, third, and fourth vertebrae and shape of third and fourth vertebrae). These measurements were then compared with the hand-wrist bone analysis, and the results were statistically analyzed by the Cohen kappa concordance index. The same procedure was repeated after 6 months and showed identical results. The Cohen kappa index obtained (mean +/- SD) was 0.783 +/- 0.098, which is in the significant range. The results show a concordance of 83.3%, considering that the estimated percentage for each case is 23.3%. The results also show a correlation of CVMS I with Bjork stages 1-3 (interval A), CVMS II with Bjork stage 4 (interval B), CVMS III with Bjork stage 5 (interval C), CVMS IV with Bjork stages 6 and 7 (interval D), and CVMS V with Bjork stages 8 and 9 (interval E). Vertebral analysis on a lateral cephalogram is as valid as the hand-wrist bone analysis with the advantage of reducing the radiation exposure of growing subjects.
Development of novel cycloaliphatic siloxanes for thermal and UV-curable applications
NASA Astrophysics Data System (ADS)
Chakraborty, Ruby
Siloxanes have been extensively used as additives to modulate surface properties such as surface tension, hydrophobicity/hydrophobicity, and adhesion, etc. Although, polydimethyl -siloxane and polydiphenylsiloxane are the most commonly used siloxanes, the properties are at extremes in terms of glass transition temperature and flexibility. It is proposed that the ability to control the properties in between the these extremes can be provided by cycloaliphatic substitutions at the siloxane backbone. It is expected that this substitution might work due to the intermediate backbone rigidity. In order to achieve the above objectives, a synthetic route was developed to prepare cycloaliphatic (cyclopentane and cyclohexane) silane monomers followed by subsequent polymerization and functionalizations to obtain glycidyl epoxy, aliphatic amine and methacrylate telechelic siloxanes. The siloxanes were either thermally or UV-cured depending on end functionalizations. Chemical characterization of monomers, oligomers and polymers were performed using 1H, 13C, 29Si-NMR, FT-IR and GPC. The curing kinetics of photo-induced reactions were investigated through photo-differential scanning calorimetry (PDSC). The oxygen permeability, mechanical, coatings, and release properties of siloxanes were studied as a function of the backbone substitutions. The mechanical, coatings and released properties of cycloaliphatic siloxanes improved with respect to polydimethylsiloxanes. The thermal analysis of the cured films were carried out using differential scanning calorimetry (DSC). Viscoelastic properties of the cured siloxanes due to the variation of substitution at the siloxane backbone were measured using dynamic mechanical thermal analysis (DMTA). The cycloaliphatic substituted siloxanes showed an increased glass transition temperature and permeability but reduced crosslink density, conversion, and rate of curing with respect to polydimethylsiloxanes. Hybrids of siloxanes were prepared with linseed oil based alkyds to study the effect of variation of alkyd oil lengths and cycloaliphatic substitutions on siloxane backbone. The oil length of an alkyd resin is defined as the number of grams of oil used to produce 100 grams of resin. Three linseed oil based alkyds representing long, medium, and short oil lengths were grafted with siloxanes substituted with methyl, cyclopentyl, and cyclohexyl groups. The reaction was monitored through FTIR and 1H-NMR. The hybrids were formulated with standard drier package and thermally cured for detailed film characterization. Improvement in crosslink density, flexibility, and reverse impact resistance were found as function of oil length. However, tensile modulus, elongation, glass transition temperature, drying time and fracture toughness decreased with increase in oil length. For hybrids, the cycloaliphatic substituents at the siloxane backbone showed enhanced mechanical and coating properties as compared to hybrids with polydimethylsiloxanes. Random and block copolymer of polydimethylsiloxanes with polydicycloaliphatic-siloxanes were synthesized and compared with homopolymers of polydicycloaliphatic siloxanes. The chemical characterization of the copolymers and homopolymers were carried out through 1H, 13C, 29Si-NMR, and FT-IR. The glass transition temperatures (Tg) of the synthesized polymers were obtained through DSC and advanced rheometric expansion system (ARES). The Tg of random copolymers were found to be higher than the corresponding block copolymers. There was very small difference in T g between cycloaliphaticsiloxanes homopolymers and corresponding random copolymers. From the above results, it can be inferred that the cycloaliphatic substitutions at the siloxane backbone can be used as a means to obtain properties intermediate to polydimethyl- and polydiphenyl siloxanes.
Farkas, József; Kovács, László Á; Gáspár, László; Nafz, Anna; Gaszner, Tamás; Ujvári, Balázs; Kormos, Viktória; Csernus, Valér; Hashimoto, Hitoshi; Reglődi, Dóra; Gaszner, Balázs
2017-06-23
Major depression is a common cause of chronic disability. Despite decades of efforts, no equivocally accepted animal model is available for studying depression. We tested the validity of a new model based on the three-hit concept of vulnerability and resilience. Genetic predisposition (hit 1, mutation of pituitary adenylate cyclase-activating polypeptide, PACAP gene), early-life adversity (hit 2, 180-min maternal deprivation, MD180) and chronic variable mild stress (hit 3, CVMS) were combined. Physical, endocrinological, behavioral and functional morphological tools were used to validate the model. Body- and adrenal weight changes as well as corticosterone titers proved that CVMS was effective. Forced swim test indicated increased depression in CVMS PACAP heterozygous (Hz) mice with MD180 history, accompanied by elevated anxiety level in marble burying test. Corticotropin-releasing factor neurons in the oval division of the bed nucleus of the stria terminalis showed increased FosB expression, which was refractive to CVMS exposure in wild-type and Hz mice. Urocortin1 neurons became over-active in CMVS-exposed PACAP knock out (KO) mice with MD180 history, suggesting the contribution of centrally projecting Edinger-Westphal nucleus to the reduced depression and anxiety level of stressed KO mice. Serotoninergic neurons of the dorsal raphe nucleus lost their adaptation ability to CVMS in MD180 mice. In conclusion, the construct and face validity criteria suggest that MD180 PACAP HZ mice on CD1 background upon CVMS may be used as a reliable model for the three-hit theory. Copyright © 2017 IBRO. Published by Elsevier Ltd. All rights reserved.
Multilayer screen gives cathode ray tube high contrast
NASA Technical Reports Server (NTRS)
Bullinger, H.; Hilborn, E. H.
1970-01-01
Fabrication method for cathode ray tubes uses low-cost siloxane resin formulations. The resins contain sufficient methyl or phenyl groups for solubility in organic solvents. After vaporization and baking, the polymerized material is stable under vacuum and under temperatures required for tube fabrication.
Volatile methyl siloxanes (VMS) concentrations in outdoor air of several Catalan urban areas
NASA Astrophysics Data System (ADS)
Gallego, E.; Perales, J. F.; Roca, F. J.; Guardino, X.; Gadea, E.
2017-04-01
Volatile methyl siloxanes (VMS) were evaluated in ten Catalan urban areas with different industrial impacts, such as petrochemical industry, electrical and mechanical equipment, metallurgical and chemical industries, municipal solid waste treatment plant and cement and food industries, during 2013-2015. 24 h samples were taken with LCMA-UPC pump samplers specially designed in our laboratory, with a flow range of 70 ml min-1. A sorbent-based sampling method, successfully developed to collect a wide-range of VOC, was used. The analysis was performed by automatic thermal desorption coupled with capillary gas chromatography/mass spectrometry detector. The presented methodology allows the evaluation of VMS together with a wide range of other VOC, increasing the number of compounds that can be determined in outdoor air quality assessment of urban areas. This aspect is especially relevant as a restriction of several VMS (D4 and D5) in consumer products has been made by the European Chemicals Agency and US EPA is evaluating to include D4 in the Toxic Substances Control Act, regarding the concern of the possible effects of these compounds in human health and the environment. ΣVMS concentrations (L2-L5, D3-D6 and trimethylsilanol) varied between 0.3 ± 0.2 μg m-3 and 18 ± 12 μg m-3, determined in a hotspot area. Observed VMS concentrations were generally of the same order of magnitude than the previously determined in Barcelona, Chicago and Zurich urban areas, but higher than the published from suburban sites and Arctic locations. Cyclic siloxanes concentrations were up to two-three orders of magnitude higher than those of linear siloxanes, accounting for average contributions to the total concentrations of 97 ± 6% for all samples except for the hotspot area, where cyclic VMS accounted for 99.9 ± 0.1%. D5 was the most abundant siloxane in 5 sampling points; however, differing from the generally observed in previous studies, D3 was the most abundant compound in the other 5 sampling points.
50 CFR 300.117 - Prohibitions.
Code of Federal Regulations, 2013 CFR
2013-10-01
.... (9) Fail to use real-time C-VMS port-to-port on board U.S. vessels harvesting AMLR in the Convention... documentation of the use of real-time C-VMS port-to-port by the vessel that harvested such Dissostichus species... fish, from sorting the catch to the storage of the finished product. (bb) Vessel monitoring systems. (1...
Federal Register 2010, 2011, 2012, 2013, 2014
2010-04-09
.... 0907141130-0112-02] RIN 0648-AX80 Antarctic Marine Living Resources; Use of Centralized-Vessel Monitoring... documentation that the harvesting vessel participated in the Centralized-Vessel Monitoring System (C-VMS... Centralized-Vessel Monitoring System (C-VMS) regardless of where the fish was harvested. This final rule also...
50 CFR 300.117 - Prohibitions.
Code of Federal Regulations, 2014 CFR
2014-10-01
.... (9) Fail to use real-time C-VMS port-to-port on board U.S. vessels harvesting AMLR in the Convention... documentation of the use of real-time C-VMS port-to-port by the vessel that harvested such Dissostichus species... board the vessel at all times as specified in this subpart. (4) Tamper with, damage, destroy, alter, or...
50 CFR 300.117 - Prohibitions.
Code of Federal Regulations, 2012 CFR
2012-10-01
.... (9) Fail to use real-time C-VMS port-to-port on board U.S. vessels harvesting AMLR in the Convention... documentation of the use of real-time C-VMS port-to-port by the vessel that harvested such Dissostichus species... board the vessel at all times as specified in this subpart. (4) Tamper with, damage, destroy, alter, or...
Powell, David E; Suganuma, Noriyuki; Kobayashi, Keiji; Nakamura, Tsutomu; Ninomiya, Kouzo; Matsumura, Kozaburo; Omura, Naoki; Ushioka, Satoshi
2017-02-01
Bioaccumulation and trophic transfer of cyclic volatile methylsiloxanes (cVMS), specifically octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6), were evaluated in the pelagic marine food web of Tokyo Bay, Japan. Polychlorinated biphenyl (PCB) congeners that are "legacy" chemicals known to bioaccumulate in aquatic organisms and biomagnify across aquatic food webs were used as a benchmark chemical (CB-180) to calibrate the sampled food web and as a reference chemical (CB-153) to validate the results. Trophic magnification factors (TMFs) were calculated from slopes of ordinary least-squares (OLS) regression models and slopes of bootstrap regression models, which were used as robust alternatives to the OLS models. Various regression models were developed that incorporated benchmarking to control bias associated with experimental design, food web dynamics, and trophic level structure. There was no evidence from any of the regression models to suggest biomagnification of cVMS in Tokyo Bay. Rather, the regression models indicated that trophic dilution of cVMS, not trophic magnification, occurred across the sampled food web. Comparison of results for Tokyo Bay to results from other studies indicated that bioaccumulation of cVMS was not related to type of food web (pelagic vs demersal), environment (marine vs freshwater), species composition, or location. Rather, results suggested that differences between study areas was likely related to food web dynamics and variable conditions of exposure resulting from non-uniform patterns of organism movement across spatial concentration gradients. Copyright © 2016 The Authors. Published by Elsevier B.V. All rights reserved.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Miller, David C.; Kempe, Michael D.; Muller, Matthew T.
We examined the durability of polymeric encapsulation materials using outdoor exposure at the nominal geometric concentration of 500 suns. The results for 36-month cumulative field deployment are presented for materials including: poly(ethylene-co-vinyl acetate), (EVA); polyvinyl butyral (PVB); ionomer; polyethylene/polyoctene copolymer (PO); thermoplastic polyurethane (TPU); poly(dimethylsiloxane) (PDMS); poly(diphenyl dimethyl siloxane) (PDPDMS); and poly(phenyl-methyl siloxane) (PPMS). Measurements of the field conditions including ambient temperature and ultraviolet (UV) dose were recorded at the test site during the experiment. Our measurements for the experiment included optical transmittance (with subsequent analysis of solar-weighted transmittance, UV cut-off wavelength, and yellowness index), mass, visual photography, photoelastic imaging,more » and fluorescence spectroscopy. While the results to date for EVA are presented and discussed, examination here focuses more on the siloxane materials. A specimen recently observed to fail by thermal decomposition is discussed in terms of the implementation of the experiment as well as its fluorescence signature, which was observed to become more pronounced with age. Modulated thermogravimetry (allowing determination of the activation energy of thermal decomposition) was performed on a subset of the siloxanes to quantify the propensity for decomposition at elevated temperatures. Supplemental, Pt-catalyst- and primer-solutions as well as peroxide-cured PDMS specimens were examined to assess the source of the luminescence. Furthermore, our results, including the change in optical transmittance, observed failure modes, and subsequent analyses of the failure modes are described in the conclusions.« less
Powell, David E; Schøyen, Merete; Øxnevad, Sigurd; Gerhards, Reinhard; Böhmer, Thomas; Koerner, Martin; Durham, Jeremy; Huff, Darren W
2018-05-01
The trophic transfer of cyclic methylsiloxanes (cVMS) in aquatic ecosystems is an important criterion for assessing bioaccumulation and ecological risk. Bioaccumulation and trophic transfer of cVMS, specifically octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6), were evaluated for the marine food webs of the Inner and Outer Oslofjord, Norway. The sampled food webs included zooplankton, benthic macroinvertebrates, shellfish, and finfish species. Zooplankton, benthic macroinvertebrates, and shellfish occupied the lowest trophic levels (TL ≈2 to 3); northern shrimp (Pandalus borealis) and Atlantic herring (Clupea harengus) occupied the middle trophic levels (TL ≈3 to 4), and Atlantic cod (Gadus morhua) occupied the highest tropic level (TL>4.0). Trophic dynamics in the Oslofjord were best described as a compressed food web defined by demersal and pelagic components that were confounded by a diversity in prey organisms and feeding relationships. Lipid-normalized concentrations of D4, D5, and D6 were greatest in the lowest trophic levels and significantly decreased up the food web, with the lowest concentrations being observed in the highest trophic level species. Trophic magnification factors (TMF) for D4, D5, and D6 were <1.0 (range 0.3 to 0.9) and were consistent between the Inner and Outer Oslofjord, indicating that exposure did not impact TMF across the marine food web. There was no evidence to suggest biomagnification of cVMS in the Oslofjord. Rather, results indicated that trophic dilution of cVMS, not trophic magnification, occurred across the sampled food webs. Copyright © 2017 The Authors. Published by Elsevier B.V. All rights reserved.
Brocal, Josep; De Decker, Steven; José-López, Roberto; Guevar, Julien; Ortega, Maria; Parkin, Tim; Ter Haar, Gert; Gutierrez-Quintana, Rodrigo
2018-05-19
Congenital vertebral malformations (CVM) are common in brachycephalic 'screw-tailed' dogs; they can be associated with neurological deficits and a genetic predisposition has been suggested. The purpose of this study was to evaluate radiography as a screening method for congenital thoracic vertebral malformations in brachycephalic 'screw-tailed' dogs by comparing it with CT. Forty-nine dogs that had both radiographic and CT evaluations of the thoracic vertebral column were included. Three observers retrospectively reviewed the images independently to detect CVMs. When identified, they were classified according to a previously published radiographic classification scheme. A CT consensus was then reached. All observers identified significantly more affected vertebrae when evaluating orthogonal radiographic views compared with lateral views alone; and more affected vertebrae with the CT consensus compared with orthogonal radiographic views. Given the high number of CVMs per dog, the number of dogs classified as being CVM free was not significantly different between CT and radiography. Significantly more midline closure defects were also identified with CT compared with radiography. Malformations classified as symmetrical or ventral hypoplasias on radiography were frequently classified as ventral and medial aplasias on CT images. Our results support that CT is better than radiography for the classification of CVMs and this will be important when further evidence of which are the most clinically relevant CVMs is identified. These findings are of particular importance for designing screening schemes of CVMs that could help selective breeding programmes based on phenotype and future studies. © British Veterinary Association (unless otherwise stated in the text of the article) 2018. All rights reserved. No commercial use is permitted unless otherwise expressly granted.
The reliability of clinical decisions based on the cervical vertebrae maturation staging method.
Sohrabi, Aydin; Babay Ahari, Sahar; Moslemzadeh, Hossein; Rafighi, Ali; Aghazadeh, Zahra
2016-02-01
Of the various techniques used to determine the optimum timing for growth modification treatments, the cervical vertebrae maturation method has great advantages, including validity and no need for extra X-ray exposure. Recently, the reproducibility of this method has been questioned. The aim of this study was to investigate the cause of poor reproducibility of this method and to assess the reproducibility of the clinical decisions made based on it. Seventy lateral cephalograms of Iranian patients aged 9‒15 years were observed twice by five experienced orthodontists. In addition to determining the developmental stage, each single parameter involved in this method was assessed in terms of inter- and intra-observer reproducibility. In order to evaluate the reproducibility of clinical decisions based on this method, cervical vertebrae maturation staging (CVMS) I and II were considered as phase 1 and CVMS IV and V were considered as phase 3. By considering the clinical approach of the CVMS method, inter-observer reproducibility of this method increased from 0.48 to 0.61 (moderate to substantial) and intra-observer reproducibility enhanced from 0.72 to 0.74. 1. Complete visualization of the first four cervical vertebrae was an inclusion criterion, which also limits the clinical application of CVMS method. 2. These results can be generalized when determining growth modification treatments solely for Class II patients. Difficulty in determining the morphology of C3 and C4 leads to poor reproducibility of the CVMS method. Despite this, it has acceptable reproducibility in determining the timing of functional treatment for Class II patients. © The Author 2015. Published by Oxford University Press on behalf of the European Orthodontic Society. All rights reserved. For permissions, please email: journals.permissions@oup.com.
Accessibility of condoms to young people in Manchester, UK.
Sixsmith, Judith; Griffiths, John; Hughes, John; Wren, Joanne; Penfold, Steve; Natusch, Hilary
2006-10-01
Issues relevant to the accessibility of male condoms for young people in the Greater Manchester area (UK) were investigated, using semi-structured, in-depth interviews and a questionnaire survey. Family planning clinics and condom vending machines (CVMs) were the most cited sources for condom acquisition. Young people's knowledge of where and when they could access condoms varied by age and gender. Suitable positioning of CVMs would need to take such variations into account when targeting potential customers. Levels of embarrassment about acquiring condoms also varied according to gender. The lifestyles of young people indicated the sorts of places in which CVMs might offer increased accessibility. For younger men and women this tended to involve low-cost, semi-private places such as local parks, school toilets and shopping malls/streets. Older men with higher spending power and increased confidence could access condoms through pub and club toilets and chemist shops. Accessible positioning of CVMs was related to the age, gender and lifestyle of the participants, and programmes to enhance accessibility should reflect this. Increased accessibility for younger groups, and especially women, needs to take into account issues of cost, confidence and embarrassment. For older groups, lifestyle choices indicated pubs and clubs as key locations for both men and women.
Litsas, G; Ari-Demirkaya, A
2010-12-01
The purpose of this study was to predict the skeletal maturation status based on the assessment of cervical vertebrae from lateral cephalometric radiographs and to compare these findings with the skeletal maturity of the same individuals judged from the hand-wrist radiographs. Lateral cephalometric and left hand-wrist radiographs of 393 Caucasian children from 8 to 18 years old were evaluated. On the hand-wrist radiographs the classification of Bjork [1972] and Grave and Brown [1976] was used to assess skeletal maturity (HWSS). Cervical vertebral maturation was also evaluated on lateral cephalometric radiographs using the improved CVMS method described by Baccetti, Franchi, and McNamara [2002]. These methods were correlated using the chi-square test. The chi-square test showed that skeletal maturational values obtained by the CVMS method were significantly correlated with the skeletal values obtained from the hand-wrist analysis for both genders (p<0.05). However, gender differentiation exists in CVMS method regarding the peak of growth spurt. The results of this study show that the CVMS method was compatible with a commonly used hand-wrist analysis method. The lateral cephalometric radiograph belonging to the standard set of records would be sufficient to evaluate skeletal maturity.
Elwell, Anthony C; Elsayed, Nada H; Kuhn, John N; Joseph, Babu
2018-03-01
Separation of volatile methyl siloxanes from landfill gas using fixed adsorption beds was modeled with the objective of identifying appropriate technology and the economics associated with this purification step. A general adsorption model assuming plug flow and radial symmetry was developed and used to conduct a parametric sweep of 162 unique cases. The varied parameters were adsorbent type (activated carbon and silica gel), bed height (3.05-9.15 m/10-30 ft), inlet siloxane concentration (5-15 mg/m 3 ), moisture content (0-100% relative humidity at STP or RH), and siloxane tolerance limit (0.094-9.4 mg/m 3 ) that correlated to three distinct energy conversion technologies (electricity production using engines or fuels cells or catalytic conversion to liquid hydrocarbon fuels). Due to the detrimental effect of RH on siloxane absorption, the maximum allowable moisture content of LFG before purification is 50% RH and moisture removal processes are also required. The design calculations using a selected case study show that the adsorption bed height required needed for 6 months minimum breakthrough time for catalytic fuel production is twice that for engine applications. Fuel cell applications require 3 times the bed height compared to engine applications. However, the purification costs amounted to 94%, 16% and 52% of recovered product value for engine, liquefaction, and fuel cell applications, respectively indicating the need for a high value product to justify purification costs. The approaches and conclusions can be extended to specific process conditions for landfill gas purification and to other processes that use biogas produced from waste as a feedstock. Copyright © 2017 Elsevier Ltd. All rights reserved.
ERIC Educational Resources Information Center
Dlutowski, Jay; Cardenas-Valencia, Andres M.; Fries, David; Langebrake, Larry
2006-01-01
An experiment which enables students to determine the index of refraction at various wavelengths is demonstrated by using two polymers examples, poly(dimethyl siloxane) (PDMS) and poly(methyl methacrylate) (PMMA). This experiment would be suitable for a course in organic chemistry or any course discussing the optical properties of polymeric…
Diffuse polymer interfaces in lobed nanoemulsions preserved in aqueous media.
Kim, Ginam; Sousa, Alioscka; Meyers, Deborah; Shope, Marilyn; Libera, Matthew
2006-05-24
Using valence electron energy loss spectroscopy (EELS) in the cryo-scanning transmission electron microscopy (STEM), we found that the polymer-polymer interface in two-phase nanocolloids of polydimethyl siloxane (PDMS) and copolymer (methyl acrylate (MA)-methyl methacrylate (MMA)-vinyl acetate (VA)) preserved in water was diffuse despite the fact that equilibrium thermodynamics indicates it should only be on the order of a few nanometers. The diffuse interface is a result of the kinetic trapping of the copolymer within the PDMS phase, and this finding suggests new nonequilibrium pathways to control interfaces during the synthesis of multicomponent polymeric nanostructures.
Durability of Polymeric Encapsulation Materials for a PMMA/glass Concentrator Photovoltaic System
DOE Office of Scientific and Technical Information (OSTI.GOV)
Miller, David C.; Kempe, Michael D.; Muller, Matthew T
2014-04-08
The durability of polymeric encapsulation materials was examined using outdoor exposure at the nominal geometric concentration of 500 suns. The results for 36 months cumulative field deployment are presented for materials including: poly(ethylene-co-vinyl acetate), (EVA); polyvinyl butyral (PVB); ionomer; polyethylene/ polyoctene copolymer (PO); thermoplastic polyurethane (TPU); poly(dimethylsiloxane) (PDMS); poly(diphenyl dimethyl siloxane) (PDPDMS); and poly(phenyl-methyl siloxane) (PPMS). Measurements of the field conditions including ambient temperature and ultraviolet (UV) dose were recorded at the test site during the experiment. Measurements for the experiment included optical transmittance (with subsequent analysis of solar-weighted transmittance, UV cut-off wavelength, and yellowness index), mass, visual photography, photoelasticmore » imaging, and fluorescence spectroscopy. While the results to date for EVA are presented and discussed, examination here focuses more on the siloxane materials. A specimen recently observed to fail by thermal decomposition is discussed in terms of the implementation of the experiment as well as its fluorescence signature, which was observed to become more pronounced with age. Modulated thermogravimetry (allowing determination of the activation energy of thermal decomposition) was performed on a subset of the siloxanes to quantify the propensity for decomposition at elevated temperatures. Supplemental, Pt-catalyst- and primer-solutions as well as peroxide-cured PDMS specimens were examined to assess the source of the luminescence. The results of the study including the change in optical transmittance, observed failure modes, and subsequent analyses of the failure modes are described in the conclusions.« less
Durability of polymeric encapsulation materials in a PMMA/glass concentrator photovoltaic system
Miller, David C.; Kempe, Michael D.; Muller, Matthew T.; ...
2016-07-13
We examined the durability of polymeric encapsulation materials using outdoor exposure at the nominal geometric concentration of 500 suns. The results for 36-month cumulative field deployment are presented for materials including: poly(ethylene-co-vinyl acetate), (EVA); polyvinyl butyral (PVB); ionomer; polyethylene/polyoctene copolymer (PO); thermoplastic polyurethane (TPU); poly(dimethylsiloxane) (PDMS); poly(diphenyl dimethyl siloxane) (PDPDMS); and poly(phenyl-methyl siloxane) (PPMS). Measurements of the field conditions including ambient temperature and ultraviolet (UV) dose were recorded at the test site during the experiment. Our measurements for the experiment included optical transmittance (with subsequent analysis of solar-weighted transmittance, UV cut-off wavelength, and yellowness index), mass, visual photography, photoelastic imaging,more » and fluorescence spectroscopy. While the results to date for EVA are presented and discussed, examination here focuses more on the siloxane materials. A specimen recently observed to fail by thermal decomposition is discussed in terms of the implementation of the experiment as well as its fluorescence signature, which was observed to become more pronounced with age. Modulated thermogravimetry (allowing determination of the activation energy of thermal decomposition) was performed on a subset of the siloxanes to quantify the propensity for decomposition at elevated temperatures. Supplemental, Pt-catalyst- and primer-solutions as well as peroxide-cured PDMS specimens were examined to assess the source of the luminescence. Furthermore, our results, including the change in optical transmittance, observed failure modes, and subsequent analyses of the failure modes are described in the conclusions.« less
Bruemmer, Janine; Falcon, Raquel; Greenwood, Richard; Mills, Graham A; Hastie, Colin; Sparham, Chris; van Egmond, Roger
2015-03-01
Cyclic volatile methylsiloxanes (cVMS) are used in personal care products and are hydrophobic, volatile and persistent. Their environmental water concentrations are low and are difficult to detect using conventional sampling methods. This study shows the potential of passive sampling for cVMS. We used low-density polyethylene (LDPE) samplers and in-field calibration methods for octamethylcyclotetrasiloxane (D4) and decamethylcyclopentasiloxane (D5). (13)C-D4 and (13)C-D5, methyltris(trimethylsiloxy)silane (MT), tetrakis(trimethylsiloxy)silane (TK), and five deuterated polycyclic aromatic hydrocarbons (PAHs) were used as performance reference compounds (PRCs). Samplers were calibrated (7-d) using effluent at a treatment plant, with uptake of cVMS and losses of the PRCs measured at 12 time-points. Concentrations of D4 (53ngL(-1)) and D5 (1838ngL(-1)) were stable in the effluent. Uptake of D4 and loss of (13)C-D4 were isotropic and equilibrium was approached by 7-d. Two estimates of sampler uptake rate (Rs) were 2.1Ld(-1) and 2.5Ld(-1). The estimated log LDPE/water partition coefficient was 4.4. The uptake of D5 was slower (Rs=0.32Ld(-1)) and equilibrium was not reached. Offloading of (13)C-D5, MT and TK were slow, and isotropic behaviour was not demonstrated for D5. Offloading of PAHs followed the predicted pattern for LDPE. Uptake of cVMS appeared to be under membrane control, due to low diffusion coefficients in LDPE. Samplers can monitor time-weighted average concentrations of D4 for less than a week, and D5 for longer periods. LDPE samplers allow cVMS to be determined at lower concentrations than by spot sampling methods. Copyright © 2014 Elsevier Ltd. All rights reserved.
Lai, Eddie Hsiang-Hua; Chang, Jenny Zwei-Chieng; Jane Yao, Chung-Chen; Tsai, Shih-Jaw; Liu, Jen-Pei; Chen, Yi-Jane; Lin, Chun-Pin
2008-07-01
The age at menarche reflects a pubertal girl's physiologic maturity. The aims of this study were to evaluate the relationship between the age at menarche and skeletal maturation in female orthodontic patients. Hand-wrist radiographs and lateral cephalometric radiographs from 304 adolescent female subjects (age, 8-18.9 years) were selected from the files of the Department of Orthodontics, National Taiwan University Hospital (NTUH). Hand-wrist bone maturation stages were assessed using the NTUH Skeletal Maturation Index (NTUH-SMI). Cervical vertebral maturation stages (CVMS) were determined using the latest CVMS Index. Menarcheal ages were self-reported by the patients and verified by the patients' mothers. The relationships between the NTUH-SMI or CVM stages and menarcheal status were investigated. More than 90% of the 148 subjects who had already attained menstruation had skeletal maturation beyond the NTUH-SMI stage four or CVMS III. However, the subjects who had never experienced menarche mostly had skeletal maturation before NTUH-SMI stage five or CVMS IV. During the period of orthodontic treatment, 19 females experienced their menarche. The mean age at menarche for the 167 female patients in total was 11.97 years. In average, menarche occurred between NTUH-SMI stages four and five or between CVM stages III and IV. The percentage of girls with menses increased from 1.2% at age 9 to 6.6% at age 10, 39.5% at age 11, 81.4% at age 12, 97% at age 13, and 100% at age 14. Compared with the results obtained 20 years previously, we found a downward shift of 0.47 years per decade for the mean age at menarche in female orthodontic patients. The majority of female orthodontic patients have passed the pubertal growth spurt when they experience their menarche. Menarche usually follows the pubertal growth spurt by about 1 year and occurs after NTUH-SMI stage four or CVMS III.
The Sol-Gel-Xerogel Transition
1993-11-01
basic pH. Bioactive sol-gel glasses obtained by a surface adsorption of trypsin to a readymade xerogel were also completley * L...presence of siloxane chains and hydrophobic methyl groups an easy film deposition on glass sheets can be obtained. Rhodamine 6G and Coumarin 4 were...Research Proposal was prepared (early 1989) have witnessed a tremendous, almost explosive, progress in the field of organically doped sol-gel glasses
Buser, Andreas M; Kierkegaard, Amelie; Bogdal, Christian; MacLeod, Matthew; Scheringer, Martin; Hungerbühler, Konrad
2013-07-02
Tens of thousands of tonnes of cyclic volatile methylsiloxanes (cVMS) are used each year globally, which leads to high and continuous cVMS emissions to air. However, field measurements of cVMS in air and empirical information about emission rates to air are still limited. Here we present measurements of decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) in air for Zurich, Switzerland. The measurements were performed in January and February 2011 over a period of eight days and at two sites (city center and background) with a temporal resolution of 6-12 h. Concentrations of D5 and D6 are higher in the center of Zurich and range from 100 to 650 ng m(-3) and from 10 to 79 ng m(-3), respectively. These values are among the highest levels of D5 and D6 reported in the literature. In a second step, we used a multimedia environmental fate model parametrized for the region of Zurich to interpret the levels and time trends in the cVMS concentrations and to back-calculate the emission rates of D5 and D6 from the city of Zurich. The average emission rates obtained for D5 and D6 are 120 kg d(-1) and 14 kg d(-1), respectively, which corresponds to per-capita emissions of 310 mg capita(-1) d(-1) for D5 and 36 mg capita(-1) d(-1) for D6.
Posey, R Daniel; Hoffsis, Glen F; Cullor, James S; Naylor, Jonathan M; Chaddock, Michael; Ames, Trevor R
2012-01-01
The real and/or perceived shortage of veterinarians serving food-supply veterinary medicine has been a topic of considerable discussion for decades. Regardless of this debate, there are issues still facing colleges of veterinary medicine (CVMs) about the best process of educating future food-supply veterinarians. Over the past several years, there have been increasing concerns by some that the needs of food-supply veterinary medicine have not adequately been met through veterinary educational institutions. The food-supply veterinary medical curriculum offered by individual CVMs varies depending on individual curricular design, available resident animal population, available food-animal caseload, faculty, and individual teaching efforts of faculty. All of the institutional members of the Association of American Veterinary Medical Colleges (AAVMC) were requested to share their Food Animal Veterinary Career Incentives Programs. The AAVMC asked all member institutions what incentives they used to attract and educate students interested in, or possibly considering, a career in food-supply veterinary medicine (FSVM). The problem arises as to how we continue to educate veterinary students with ever shrinking budgets and how to recruit and retain faculty with expertise to address the needs of society. Several CVMs use innovative training initiatives to help build successful FSVM programs. This article focuses on dairy, beef, and swine food-animal education and does not characterize colleges' educational efforts in poultry and aquaculture. This review highlights the individual strategies used by the CVMs in the United States.
NASA Astrophysics Data System (ADS)
Stanier, C. O.; Janechek, N. J.; Bryngelson, N.; Marek, R. F.; Lersch, T.; Bunker, K.; Casuccio, G.; Brune, W. H.; Hornbuckle, K. C.
2017-12-01
Cyclic volatile methyl siloxanes are anthropogenic chemicals present in personal care products such as antiperspirants and lotions. These are volatile chemicals that are readily released into the atmosphere by product use. Due to their emission and relatively slow kinetics of their major transformation pathway, reaction with hydroxyl radicals (OH), these compounds are present in high concentrations in indoor environments and widespread in outdoor environments. Cyclic siloxane reaction with OH can lead to secondary organic aerosols, and due to the widespread prevalence of the parent compounds, may be an important source of ambient aerosols. Atmospheric aerosols have important influences to the climate by affecting the radiative balance and by serving as cloud condensation nuclei (CCN) which influence clouds. While the parent compounds have been well-studied, the oxidation products have received much less attention, with almost no ambient measurements or experimental physical property data. We report physical properties of aerosols generated by reacting the cyclic siloxane D5 with OH using a Potential Aerosol Mass (PAM) photochemical chamber. The particles were characterized by SMPS, imaging and elemental analysis using both Transmission Electron Microscopy and Scanning Transmission Electron Microscopy equipped with Energy Dispersive X-ray Spectroscopy systems (TEM-EDS and STEM-EDS), volatility measurements using Volatility Tandem Differential Mobility Analyzer (V-TDMA), and hygroscopicity measurements to determine CCN potential using a Droplet Measurement Technologies Cloud Condensation Nuclei Counter (DMT-CCN). Aerosol yield sensitivity to D5 and OH concentrations, residence time, and seed aerosols were analyzed. TEM-EDS and STEM-EDS analysis show spherical particle morphology with elemental composition consistent with aerosols derived from cyclic siloxane sources. Measured aerosol yields were 20-50% with typical aerosol concentrations 300,000 particles cm-3, up to 200 μg m-3, and diameters of 30-90 nm. Particles experienced little diameter change after heating up to 200°C suggesting low volatility, while particle activation was shifted to higher supersaturations compared to ammonium sulfate suggesting moderate hygroscopicity in line with other secondary organics.
Rojas Devia, Carolina; Subrenat, Albert
2013-01-01
Hydrophobic volatile methyl siloxanes (VMS), such as hexamethyldisiloxane (L2) and octamethylcyclotetrasiloxane (D4), present a low solubility in water. An alternative treatment by absorption into hydrophobic absorbents was therefore studied. For this purpose, three different absorbents, motor oil, cutting oil and a water-cutting oil mixture, were selected with the aim of re-using a waste product. The set of experiments was carried out in a bubble column, where parameters such as inlet concentration, residence time and temperature were studied. The best performance for the removal of both siloxanes, in terms of absorption capacity, was observed for motor oil, particularly for D4. In fact, motor oil removal efficiency for D 4 was 80%, whereas for L2 it was 60%, indicating that D 4 is more easily absorbed than L2. In the case of water-cutting oil, this showed a mass transfer enhancement from the gas phase to the liquid phase compared with water alone. Furthermore, a removal efficiency of 70% was observed for D 4, showing that the addition of an oil fraction to a water system improves the absorption of VMS. These results show that VMS absorption into oils could be a promising way to achieve their abatement.
NASA Astrophysics Data System (ADS)
Lee, En-Jui; Chen, Po
2017-04-01
More precise spatial descriptions of fault systems play an essential role in tectonic interpretations, deformation modeling, and seismic hazard assessments. The recent developed full-3D waveform tomography techniques provide high-resolution images and are able to image the material property differences across faults to assist the understanding of fault systems. In the updated seismic velocity model for Southern California, CVM-S4.26, many velocity gradients show consistency with surface geology and major faults defined in the Community Fault Model (CFM) (Plesch et al. 2007), which was constructed by using various geological and geophysical observations. In addition to faults in CFM, CVM-S4.26 reveals a velocity reversal mainly beneath the San Gabriel Mountain and Western Mojave Desert regions, which is correlated with the detachment structure that has also been found in other independent studies. The high-resolution tomographic images of CVM-S4.26 could assist the understanding of fault systems in Southern California and therefore benefit the development of fault models as well as other applications, such as seismic hazard analysis, tectonic reconstructions, and crustal deformation modeling.
Assessment of skeletal maturation based on cervical vertebrae in CBCT.
Shim, Jocelyne J; Heo, Giseon; Lagravère, Manuel O
2012-12-01
Diagnosis of skeletal age in adolescents helps orthodontists select and time treatments. Currently this is done using lateral cephalometric radiographs. This study evaluates the application of the conventional method in cone-beam computer tomographic (CBCT) images to bring forth assessment of skeletal maturation in three-dimensions. Ninety-eight lateral cephalometric radiographs and CBCT scans were collected from orthodontic patients between 11 to 17 years of age over an 18-month period. CBCT scans were examined in seven sagittal slices based on cervical vertebral maturation staging (CVMS). Collected CVMS values were compared with those from corresponding lateral cephalometric radiograph. CVMS measured from CBCT and lateral cephalometric radiographs were the same on average. However, they were not consistent with each other and scored interclass correlation coefficient of 0.155 in validity test. Interoperator reliability was weak (0.581). Adaptation of cervical vertebrae maturation staging in CBCT requires further clarifications or modifications to become consistent with lateral cephalometric examinations and to become a reliable method. Alternatively, a completely new method may be developed consisting of maturational indicators or landmarks unique to CBCT imaging. Copyright © 2012. Published by Elsevier Masson SAS.
NASA Astrophysics Data System (ADS)
Iwan, Agnieszka; Schab-Balcerzak, Ewa; Pociecha, Damian; Krompiec, Michal; Grucela, Marzena; Bilski, Pawel; Kłosowski, Mariusz; Janeczek, Henryk
2011-11-01
New siloxane-containing poly(azomethine)s and a six-membered poly(imide) have been developed from siloxane-containing diamine with four different dialdehydes and 3,4,9,10-perylenetetracarboxylic dianhydride, and their thermotropic behavior, optoelectrical and electrochemical properties were examined. Mesomorphic behavior of the polymers was investigated via differential scanning calorimetry (DSC), polarizing optical microscopy (POM) and X-ray diffraction (WAXRD, SAXRD) studies. The electrochemical behavior of poly(azomethine)s and poly(imide) was studied by differential pulse voltammetry (DPV). The HOMO levels of these polymers were in the range of -5.13 to -5.90 eV. UV-vis properties of the polymers were investigated in solid state as thin films and in chloroform solution. Optical energy band gap ( Egopt.) was calculated from absorption spectra and absorption coefficients α. The photoluminescence properties (PL) of obtained polymers were studied in chloroform solution. The investigated poly(azomethine)s emitted blue light, while the poly(imide) emitted green light. The polymers were irradiated with a test dose of 1 Gy Co-60 gamma-rays to detect their thermoluminescence properties in the temperature range of 50-200 °C. Polymer monolayer (ITO/polymer/Al) and bulk heterojunction (BHJ) (ITO/polymer:PCBM/Al and ITO/PEDOT:PSS/polymer:PCBM/Al) devices were prepared with PAZ and PI used as active layers and I- U curves were measured in the dark and during irradiation with light (under illumination of 1000 W/m 2). Poly(azomethine)s were blended with [6,6]-phenyl C 61 butyric acid methyl ester (PCBM). Selected properties of the investigated polymers with siloxane linkages were compared with the polymers ( PAZ1a- PAZ3a, PIa) prepared from the same dialdehydes or dianhydride and poly(1,4-butanediol)bis(4-aminobenzoate).
Novaes, Fábio Junior Moreira; Kulsing, Chadin; Bizzo, Humberto Ribeiro; de Aquino Neto, Francisco Radler; Rezende, Claudia Moraes; Marriott, Philip John
2018-02-09
Comprehensive two-dimensional gas chromatography (GC×GC) approaches with cryogenic modulation were developed for the qualitative analysis of selected low volatility compounds in raw coffee bean extracts, without derivatisation. The approaches employed short first ( 1 D) and second ( 2 D) dimension columns, specifically a 1 D 65% phenyl methyl siloxane column (11m) and a 2 D 5% phenyl methyl siloxane column (1m), which allowed elution of high molar mass compounds (e.g.>600Da). Solutes included hydrocarbons, fatty acids, diterpenes, tocopherols, sterols, diterpene esters, and di- and triacylglycerides. An oven temperature program up to 370°C was employed. The effects of experimental conditions were investigated, revealing that the GC×GC results strongly depended on the cryogenic trap T, and oven T program. An appropriate condition was selected and further applied for group type analysis of low volatility compounds in green Arabica coffee beans. Retention indices were compiled for 1D GC analysis and were similar for the composite column data in GC×GC. The elution of some compounds was confirmed by use of authentic standards. The approach allowed direct analysis of coffee extract in ethyl acetate solution, with improved analyte peak capacity (approximately 200 compounds were detected) without prior fractionation or pre-treatment of the sample. This avoided potential hydrolysis of high molar mass conjugate esters as well as degradation of thermally labile compounds such as the derivatives of the diterpenes cafestol and kahweol. Copyright © 2017 Elsevier B.V. All rights reserved.
Determination of cyclic volatile methylsiloxanes in biota with a purge and trap method.
Kierkegaard, Amelie; Adolfsson-Erici, Margaretha; McLachlan, Michael S
2010-11-15
The three cyclic volatile methylsiloxanes (cVMS), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6), are recently identified environmental contaminants. Methods for the trace analysis of these chemicals in environmental matrices are required. A purge and trap method to prepare highly purified sample extracts with a low risk of sample contamination is presented. Without prior homogenization, the sample is heated in water, and the cVMS are purged from the slurry and trapped on an Isolute ENV+ cartridge. They are subsequently eluted with n-hexane and analyzed with GC/MS. The method was tested for eight different matrices including ragworms, muscle tissue from lean and lipid-rich fish, cod liver, and seal blubber. Analyte recoveries were consistent within and between matrices, averaging 79%, 68%, and 56% for D4, D5, and D6, respectively. Good control of blank levels resulted in limits of quantification of 1.5, 0.6, and 0.6 ng/g wet weight. The repeatability was 12% (D5) and 15% (D6) at concentrations 9 and 2 times above the LOQ. The method was applied to analyze cVMS in fish from Swedish lakes, demonstrating that contamination in fish as a result of long-range atmospheric transport is low as compared to contamination from local sources.
Femtosecond laser microfabrication in polymers towards memory devices and microfluidic applications
NASA Astrophysics Data System (ADS)
Deepak, K. L. N.; Venugopal Rao, S.; Narayana Rao, D.
2011-12-01
We have investigated femtosecond laser induced microstructures, gratings, and craters in four different polymers: poly methyl methacrylate (PMMA), poly dimethyl siloxane (PDMS), polystyrene (PS) and poly vinyl alcohol (PVA) using Ti:sapphire laser delivering 800 nm, 100 femtosecond (fs) pulses at 1 kHz repetition rate with a maximum pulse energy of 1 mJ. Local chemical modifications leading to the formation of optical centers and peroxide radicals which were studied using UV-Visible absorption and emission, confocal micro-Raman and Electron Spin Resonance (ESR) spectroscopic techniques.
2016-08-01
5 Extraction Apparatus. A.5.1 Accelerated Solvent Extractor (ASE) Dionex Corporation or equal A.5.1.1 Liquid Nitrogen Cylinder to Deliver High...Chromatograph equipped with ChemStation software, or equal A.6.1 Carrier Gas Cylinder , Appropriate Regulator Set at 80psi A.6.2 Hewlett-Packard...Capillary Column, 5% Phenyl Methyl Siloxane/30.0m x 250μm 0.25μm nominal, 325oC Max, or equal. A.6.3 Split Inlet Liner , Packed with Silanized Glass
Charles, Paul T; Adams, Andre A; Howell, Peter B; Trammell, Scott A; Deschamps, Jeffrey R; Kusterbeck, Anne W
2010-01-01
Fluorescence immunoassays employing monoclonal antibodies directed against the explosive 2,4,6-trinitrotoluene (TNT) were conducted in a multi-channel microimmunosensor. The multi-channel microimmunosensor was prepared in poly (methyl methacrylate) (PMMA) via hot embossing from a brass molding tool. The multi-channeled microfluidic device was sol-gel coated to generate a siloxane surface that provided a scaffold for antibody immobilization. AlexaFluor-cadaverine-trinitrobenzene (AlexaFluor-Cad-TNB) was used as the reporter molecule in a displacement immunoassay. The limit of detection was 1-10 ng/mL (ppb) with a linear dynamic range that covered three orders of magnitude. In addition, antibody crossreactivity was investigated using hexahydro-1,3,5-triazine (RDX), HMX, 2,4-dinitrotoluene (DNT), 4-nitrotoluene (4-NT) and 2-amino-4,6-DNT.
Charles, Paul T.; Adams, Andre A.; Howell, Peter B.; Trammell, Scott A.; Deschamps, Jeffrey R.; Kusterbeck, Anne W.
2010-01-01
Fluorescence immunoassays employing monoclonal antibodies directed against the explosive 2,4,6-trinitrotoluene (TNT) were conducted in a multi-channel microimmunosensor. The multi-channel microimmunosensor was prepared in poly (methyl methacrylate) (PMMA) via hot embossing from a brass molding tool. The multi-channeled microfluidic device was sol-gel coated to generate a siloxane surface that provided a scaffold for antibody immobilization. AlexaFluor-cadaverine-trinitrobenzene (AlexaFluor-Cad-TNB) was used as the reporter molecule in a displacement immunoassay. The limit of detection was 1–10 ng/mL (ppb) with a linear dynamic range that covered three orders of magnitude. In addition, antibody crossreactivity was investigated using hexahydro-1,3,5-triazine (RDX), HMX, 2,4-dinitrotoluene (DNT), 4-nitrotoluene (4-NT) and 2-amino-4,6-DNT. PMID:22315573
Polyimides containing pendent siloxane groups
NASA Technical Reports Server (NTRS)
Connell, John W. (Inventor); St.clair, Terry L. (Inventor); Hergenrother, Paul M. (Inventor)
1994-01-01
Novel polyimides containing pendent siloxane groups (PISOX) were prepared by the reaction of functionalized siloxane compounds with hydroxy containing polyimides (PIOH). The pendent siloxane groups on the polyimide backbone offer distinct advantages such as lowering the dielectric constant and moisture resistance and enhanced atomic oxygen resistance. The siloxane containing polyimides are potentially useful as protective silicon oxide coatings and are useful for a variety of applications where atomic oxygen resistance is needed.
Tran, Tri Manh; Le, Hanh Thi; Vu, Nam Duc; Minh Dang, Giang Huong; Minh, Tu Binh; Kannan, Kurunthachalam
2017-10-01
Earlier studies have reported the occurrence of cyclic and linear siloxanes in personal care and household products. Nevertheless, there is a lack of information on the occurrence of siloxanes in indoor air. In this study, four cyclic and six linear siloxanes were measured in 97 indoor air samples collected from various micro-environments in four cities in northern, Vietnam, during September 2016 to January 2017. The total concentrations of siloxanes (TSi) in particulate and gas phases ranged from 141 to 7220 μg g -1 (mean: 1880) and 23.8-1580 ng m -3 (mean: 321), respectively. The total concentrations of cyclic siloxanes (TCSi), linear siloxanes (TLSi), and TSi in indoor air were 1.91-1500 ng m -3 , 21.8-817 ng m -3 , and 41.8-1950 ng m -3 , respectively. The highest mean concentration of siloxanes was found in indoor air from hair salons in Hanoi. The concentrations of siloxanes in air collected from homes in Hanoi were higher than those from other smaller cities such as Bacninh, Thaibinh, and Tuyenquang. The human exposures to siloxanes through inhalation were estimated for various age groups based on the measured concentrations. The mean inhalation exposure doses to total siloxanes for infants, toddlers, children, teenagers, and adults were 352, 219, 188, 132, and 95.9 ng kg-bw -1 d -1 , respectively. Copyright © 2017 Elsevier Ltd. All rights reserved.
Solid Silicone Elastomer Material(DC745U)-Historical Overview and New Experimental Results
DOE Office of Scientific and Technical Information (OSTI.GOV)
Ortiz-Acosta, Denisse
2012-08-08
DC745U is a silicone elastomer used in several weapon systems. DC745U is manufactured by Dow Corning and its formulation is proprietary. Risk changes without notification to the customer. {sup 1}H and {sup 29}Si{l_brace}{sup 1}H{r_brace} NMR have previously determined that DC745U contains {approx} 98.5% dimethyl siloxane, {approx}1.5% methyl-phenyl siloxane, and a small amount (<1%) of vinyl siloxane repeat units that are converted to crosslinking sites. The polymer is filled with {approx} 38 wt.% of a mixture of fumed silica and quartz. Some conclusions are: (1) DMA shows that crystallization does have an effect on the mechanical properties of DC745U; (2) DMAmore » shows that the crystallization is time and temperature dependent; (3) Mechanical tests show that DC745U undergo a crystalline transition at temperatures below -50 C; (4) Rate and temperature does not have an effect above crystalline transition; (5) Crystalline transition occurs faster at colder temperatures; (6) The material remains responsive and recovers after warming it to temperature above -40 C; (7) We were able to review all previous historical data on DC745U; (8) Identified specific gaps in materials understanding; (9) Developed design of experiments and testing methods to address gaps associated with post-curing and low temperature mechanical behavior; (10) Resolved questions of post-cure and alleviated concerns associated with low temperature mechanical behavior with soak time and temperature; and (11) This work is relevant to mission-critical programs and for supporting programmatic work for weapon research.« less
40 CFR 721.10119 - Siloxane modified silica nanoparticles (generic).
Code of Federal Regulations, 2010 CFR
2010-07-01
... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Siloxane modified silica nanoparticles... Specific Chemical Substances § 721.10119 Siloxane modified silica nanoparticles (generic). (a) Chemical... as siloxane modified silica nanoparticles (PMN P-05-673) is subject to reporting under this section...
40 CFR 721.10119 - Siloxane modified silica nanoparticles (generic).
Code of Federal Regulations, 2014 CFR
2014-07-01
... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Siloxane modified silica nanoparticles... Specific Chemical Substances § 721.10119 Siloxane modified silica nanoparticles (generic). (a) Chemical... as siloxane modified silica nanoparticles (PMN P-05-673) is subject to reporting under this section...
40 CFR 721.10119 - Siloxane modified silica nanoparticles (generic).
Code of Federal Regulations, 2011 CFR
2011-07-01
... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Siloxane modified silica nanoparticles... Specific Chemical Substances § 721.10119 Siloxane modified silica nanoparticles (generic). (a) Chemical... as siloxane modified silica nanoparticles (PMN P-05-673) is subject to reporting under this section...
40 CFR 721.10119 - Siloxane modified silica nanoparticles (generic).
Code of Federal Regulations, 2012 CFR
2012-07-01
... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Siloxane modified silica nanoparticles... Specific Chemical Substances § 721.10119 Siloxane modified silica nanoparticles (generic). (a) Chemical... as siloxane modified silica nanoparticles (PMN P-05-673) is subject to reporting under this section...
40 CFR 721.10119 - Siloxane modified silica nanoparticles (generic).
Code of Federal Regulations, 2013 CFR
2013-07-01
... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Siloxane modified silica nanoparticles... Specific Chemical Substances § 721.10119 Siloxane modified silica nanoparticles (generic). (a) Chemical... as siloxane modified silica nanoparticles (PMN P-05-673) is subject to reporting under this section...
Code of Federal Regulations, 2012 CFR
2012-07-01
... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Siloxanes and silicones, aminoalkyl... SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.9502 Siloxanes and silicones... subject to reporting. (1) The chemical substance identified generically as siloxanes and silicones...
Code of Federal Regulations, 2010 CFR
2010-07-01
... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Siloxanes and silicones, aminoalkyl... SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.9502 Siloxanes and silicones... subject to reporting. (1) The chemical substance identified generically as siloxanes and silicones...
Code of Federal Regulations, 2013 CFR
2013-07-01
... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Siloxanes and silicones, aminoalkyl... SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.9502 Siloxanes and silicones... subject to reporting. (1) The chemical substance identified generically as siloxanes and silicones...
Code of Federal Regulations, 2014 CFR
2014-07-01
... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Siloxanes and silicones, aminoalkyl... SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.9502 Siloxanes and silicones... subject to reporting. (1) The chemical substance identified generically as siloxanes and silicones...
40 CFR 721.10484 - Siloxanes and Silicones, Me vinyl, hydroxy-terminated, reaction products with...
Code of Federal Regulations, 2013 CFR
2013-07-01
... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Siloxanes and Silicones, Me vinyl... Substances § 721.10484 Siloxanes and Silicones, Me vinyl, hydroxy-terminated, reaction products with...) The chemical substance identified as Siloxanes and Silicones, Me vinyl, hydroxy-terminated, reaction...
Code of Federal Regulations, 2011 CFR
2011-07-01
... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Siloxanes and silicones, aminoalkyl... SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.9502 Siloxanes and silicones... subject to reporting. (1) The chemical substance identified generically as siloxanes and silicones...
40 CFR 721.10484 - Siloxanes and Silicones, Me vinyl, hydroxy-terminated, reaction products with...
Code of Federal Regulations, 2014 CFR
2014-07-01
... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Siloxanes and Silicones, Me vinyl... Substances § 721.10484 Siloxanes and Silicones, Me vinyl, hydroxy-terminated, reaction products with...) The chemical substance identified as Siloxanes and Silicones, Me vinyl, hydroxy-terminated, reaction...
Control Activity in Support of NASA Turbine Based Combined Cycle (TBCC) Research
NASA Technical Reports Server (NTRS)
Stueber, Thomas J.; Vrnak, Daniel R.; Le, Dzu K.; Ouzts, Peter J.
2010-01-01
Control research for a Turbine Based Combined Cycle (TBCC) propulsion system is the current focus of the Hypersonic Guidance, Navigation, and Control (GN&C) discipline team. The ongoing work at the NASA Glenn Research Center (GRC) supports the Hypersonic GN&C effort in developing tools to aid the design of control algorithms to manage a TBCC airbreathing propulsion system during a critical operating period. The critical operating period being addressed in this paper is the span when the propulsion system transitions from one cycle to another, referred to as mode transition. One such tool, that is a basic need for control system design activities, is computational models (hereto forth referred to as models) of the propulsion system. The models of interest for designing and testing controllers are Control Development Models (CDMs) and Control Validation Models (CVMs). CDMs and CVMs are needed for each of the following propulsion system elements: inlet, turbine engine, ram/scram dual-mode combustor, and nozzle. This paper presents an overall architecture for a TBCC propulsion system model that includes all of the propulsion system elements. Efforts are under way, focusing on one of the propulsion system elements, to develop CDMs and CVMs for a TBCC propulsion system inlet. The TBCC inlet aerodynamic design being modeled is that of the Combined-Cycle Engine (CCE) Testbed. The CCE Testbed is a large-scale model of an aerodynamic design that was verified in a small-scale screening experiment. The modeling approach includes employing existing state-of-the-art simulation codes, developing new dynamic simulations, and performing system identification experiments on the hardware in the NASA GRC 10 by10-Foot Supersonic Wind Tunnel. The developed CDMs and CVMs will be available for control studies prior to hardware buildup. The system identification experiments on the CCE Testbed will characterize the necessary dynamics to be represented in CDMs for control design. These system identification models will also be the reference models to validate the CDM and CVM models. Validated models will give value to the tools used to develop the models.
NASA Technical Reports Server (NTRS)
Wohl, Christopher J.; Atkins, Brad M.; Belcher, Marcus A.; Connell, John W.
2012-01-01
Novel copoly(imide siloxane)s were synthesized from commercially available aminopropyl terminated siloxane oligomers, aromatic dianhydrides, and diamines. This synthetic approach produced copolymers with well-defined siloxane blocks linked with imide units in a random fashion. The copoly(amide acid)s were characterized by solution viscosity and subsequently used to cast thin films followed by thermal imidization in an inert atmosphere. Thin films were characterized using contact angle goniometry, attenuated total reflection Fourier transform infrared spectroscopy, confocal and optical microscopy, and tensile testing. Adhesion of micronsized particles was determined quantitatively using a sonication device. The polydimethylsiloxane (PDMS) moieties lowered the copolymer surface energy due to migration of siloxane moieties to the film s surface, resulting in a notable reduction in particle adhesion. A further reduction in particle adhesion was achieved by introducing topographical features on a scale of several to tens of microns by a laser ablation technique.
Code of Federal Regulations, 2014 CFR
2014-07-01
... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Siloxanes and Silicones, Me vinyl... SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10481 Siloxanes and Silicones, Me... uses subject to reporting. (1) The chemical substance identified as Siloxanes and Silicones, Me vinyl...
Code of Federal Regulations, 2013 CFR
2013-07-01
... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Siloxanes and Silicones, Me vinyl... SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10481 Siloxanes and Silicones, Me... uses subject to reporting. (1) The chemical substance identified as Siloxanes and Silicones, Me vinyl...
Chollet, D F; Castella, E; Goumaz, L; Anderegg, G
1999-11-01
A gas chromatography-mass spectrometry assay method suitable for the therapeutic drug monitoring of the antiepileptic drug tiagabine is described. Tiagabine and its desmethylated analogue used as internal standard were first extracted from serum by liquid-liquid extraction using an ethyl ether-isobutanol 98:2 mixture. Tiagabine and the internal standard were then methylated in the organic phase in presence of methanol by means of a safe and stable diazomethane derivative. After evaporation, the reconstituted extracts were chromatographed on a crosslinked phenyl methyl siloxane capillary column and detected by mass fragmentometry at m/z = 156. No other antiepileptic drug possibly administrated in polytherapy and no metabolite were found to interfere in the assay. The limit of quantification was 5 ng/ml. The precision and the accuracy were found to be suitable for the therapeutic drug monitoring of tiagabine.
Code of Federal Regulations, 2013 CFR
2013-07-01
... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Siloxanes and Silicones, di-Me, Me... Substances § 721.10483 Siloxanes and Silicones, di-Me, Me vinyl, hydroxy-terminated, reaction products with...) The chemical substance identified as Siloxanes and Silicones, di-Me, Me vinyl, hydroxy-terminated...
Code of Federal Regulations, 2014 CFR
2014-07-01
... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Siloxanes and Silicones, di-Me, Me... Substances § 721.10483 Siloxanes and Silicones, di-Me, Me vinyl, hydroxy-terminated, reaction products with...) The chemical substance identified as Siloxanes and Silicones, di-Me, Me vinyl, hydroxy-terminated...
Comprehensive atmospheric modeling of reactive cyclic siloxanes and their oxidation products
NASA Astrophysics Data System (ADS)
Janechek, Nathan J.; Hansen, Kaj M.; Stanier, Charles O.
2017-07-01
Cyclic volatile methyl siloxanes (cVMSs) are important components in personal care products that transport and react in the atmosphere. Octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), and their gas-phase oxidation products have been incorporated into the Community Multiscale Air Quality (CMAQ) model. Gas-phase oxidation products, as the precursor to secondary organic aerosol from this compound class, were included to quantify the maximum potential for aerosol formation from gas-phase reactions with OH. Four 1-month periods were modeled to quantify typical concentrations, seasonal variability, spatial patterns, and vertical profiles. Typical model concentrations showed parent compounds were highly dependent on population density as cities had monthly averaged peak D5 concentrations up to 432 ng m-3. Peak oxidized D5 concentrations were significantly less, up to 9 ng m-3, and were located downwind of major urban areas. Model results were compared to available measurements and previous simulation results. Seasonal variation was analyzed and differences in seasonal influences were observed between urban and rural locations. Parent compound concentrations in urban and peri-urban locations were sensitive to transport factors, while parent compounds in rural areas and oxidized product concentrations were influenced by large-scale seasonal variability in OH.
Code of Federal Regulations, 2012 CFR
2012-07-01
... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Siloxanes and silicones, Me hydrogen... Siloxanes and silicones, Me hydrogen, reaction products with 2,2,6,6-tetramethyl-4-(2-propenyloxy)piperdine... identified as siloxanes and silicones, Me hydrogen, reaction products with 2,2,6,6-tetramethyl-4-(2...
Code of Federal Regulations, 2014 CFR
2014-07-01
... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Siloxanes and silicones, Me hydrogen... Siloxanes and silicones, Me hydrogen, reaction products with 2,2,6,6-tetramethyl-4-(2-propenyloxy)piperdine... identified as siloxanes and silicones, Me hydrogen, reaction products with 2,2,6,6-tetramethyl-4-(2...
Code of Federal Regulations, 2013 CFR
2013-07-01
... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Siloxanes and silicones, Me hydrogen... Siloxanes and silicones, Me hydrogen, reaction products with 2,2,6,6-tetramethyl-4-(2-propenyloxy)piperdine... identified as siloxanes and silicones, Me hydrogen, reaction products with 2,2,6,6-tetramethyl-4-(2...
Characterisation and cleaning of biogas from sewage sludge for biomethane production.
Paolini, Valerio; Petracchini, Francesco; Carnevale, Monica; Gallucci, Francesco; Perilli, Mattia; Esposito, Giulio; Segreto, Marco; Occulti, Leandro Galanti; Scaglione, Davide; Ianniello, Antonietta; Frattoni, Massimiliano
2018-07-01
This study investigates the conversion of sewage sludge from wastewater treatment plants (WWTP) into biomethane for automotive fuel or grid injection. A prototype plant was monitored in Northern Italy, based on vacuum swing adsorption (VSA) on synthetic zeolite 13×: this biogas upgrading method is similar to pressure swing adsorption (PSA) and commonly used for other kinds of biomass. Measurements of biogas inlet, biomethane outlet and off-gas were performed including CH 4 , CO 2 , CO, H 2 , O 2 , N 2 , HCl, HF, NH 3 , H 2 S and volatile organic compounds (VOCs). Critical levels were observed in the biogas for of H 2 S and HCl, whose concentrations were 1570 and 26.8 mg m -3 , respectively. On the other hand, the concentration of halogenated VOCs (including tetrachloroethylene and traces of perfluoroalkilated substances, PFAS) and mercaptans were relatively low. A simultaneous and reversible adsorption on 13× zeolite was achieved for H 2 S and CO 2 , and carbon filters played a minor role in desulfurisation. The presence of HCl is due to clarifying agents, and its removal is necessary in order to meet the required biomethane characteristics: an additional carbon-supported basic adsorbent was successfully used to remove this contaminant. This study also highlights the interference of CO 2 towards HCl if sampling is performed in compliance with the new EU standard for biomethane. High total volatile silicon (TVS) was confirmed in sewage sludge biogas, with a major contribution of siloxane D5: the suitability of this compound as an indicator of total siloxanes is discussed. Results demonstrate that volatile methyl siloxanes (VMS) do not represent a critical issue for the VSA upgrading methodology. Copyright © 2018 Elsevier Ltd. All rights reserved.
Zhang, Kai; Wong, Jon W; Begley, Timothy H; Hayward, Douglas G; Limm, William
2012-08-01
A pressurised solvent extraction procedure coupled with a gas chromatography-mass spectrometry-selective ion monitoring (GC-MS-SIM) method was developed to determine three cyclic siloxanes, octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6) and three linear siloxanes, octamethyltrisiloxane (L3), decamethyltetrasiloxane (L4), dodecamethylpentasiloxane (L5), in silicone products. Additionally, two different extraction methods were developed to measure these siloxanes migrating into milk, infant formula and liquid simulants (50 and 95% ethanol in water). The limits of quantification (LOQs) of the six siloxanes ranged from 6 ng/g (L3) to 15 ng/g (D6). Silicone nipples and silicone bakewares were extracted using pressurised solvent extraction (PSE) and analysed using the GC-MS-SIM method. No linear siloxanes were detected in the silicone nipple samples analysed. The three cyclic siloxanes (D4, D5 and D6) were detected in all silicone nipple samples with concentrations ranging from 0.5 to 269 µg/g. In the bakeware samples, except for L3, the other five siloxanes were detected with concentrations ranging from 0.2 µg/g (L4) to 7030 µg/g (D6). To investigate the potential migration of the six siloxanes from silicone nipples to milk and infant formula, a liquid extraction and dispersive clean-up procedure was developed for the two matrices. The procedure used a mix of hexane and ethyl acetate (1 : 1, v/v) as extraction solvent and C₁₈ powder as the dispersive clean-up sorbent. For the liquid simulants, extraction of the siloxanes was achieved using hexane without any salting out or clean-up procedures. The recoveries of the six siloxanes from the milk, infant formula and simulants fortified at 50, 100, 200, 500 and 1000 µg/l ranged from 70 to 120% with a relative standard derivation (RSD) of less than 15% (n = 4). Migration tests were performed by exposing milk, infant formula and the liquid simulants to silicone baking sheets with known concentrations of the six siloxanes at 40°C. No siloxanes were detected in milk or infant formula after 6 h of direct contact with the silicone baking sheet plaques, indicating insignificant migration of the siloxanes to milk or infant formula. Migration tests in the two simulants lasted up to 72 h and the three cyclic siloxanes were detected in 50% ethanol after an 8-h exposure and after 2 h in 95% ethanol. The highest detected concentrations of D4, D5 and D6 were 42, 36 and 155 ng/ml, respectively, indicating very limited migration of D4, D5 or D6 into the two simulants.
Code of Federal Regulations, 2010 CFR
2010-07-01
... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Siloxanes and silicones, de-Me, 3-[4... Siloxanes and silicones, de-Me, 3-[4-[[[3-(dimethyl amino) propyl] amino]carbonyl]-2-oxo-1-pyrrolidinyl... substance identified as siloxanes and silicones, de-Me, 3-[4-[[[3-(dimethylamino) propyl]amino] carbonyl]-2...
Code of Federal Regulations, 2014 CFR
2014-07-01
... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Siloxanes and silicones, de-Me, 3-[4... Siloxanes and silicones, de-Me, 3-[4-[[[3-(dimethyl amino) propyl] amino]carbonyl]-2-oxo-1-pyrrolidinyl... substance identified as siloxanes and silicones, de-Me, 3-[4-[[[3-(dimethylamino) propyl]amino] carbonyl]-2...
Code of Federal Regulations, 2012 CFR
2012-07-01
... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Siloxanes and silicones, de-Me, 3-[4... Siloxanes and silicones, de-Me, 3-[4-[[[3-(dimethyl amino) propyl] amino]carbonyl]-2-oxo-1-pyrrolidinyl... substance identified as siloxanes and silicones, de-Me, 3-[4-[[[3-(dimethylamino) propyl]amino] carbonyl]-2...
Code of Federal Regulations, 2011 CFR
2011-07-01
... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Siloxanes and silicones, de-Me, 3-[4... Siloxanes and silicones, de-Me, 3-[4-[[[3-(dimethyl amino) propyl] amino]carbonyl]-2-oxo-1-pyrrolidinyl... substance identified as siloxanes and silicones, de-Me, 3-[4-[[[3-(dimethylamino) propyl]amino] carbonyl]-2...
Code of Federal Regulations, 2013 CFR
2013-07-01
... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Siloxanes and silicones, de-Me, 3-[4... Siloxanes and silicones, de-Me, 3-[4-[[[3-(dimethyl amino) propyl] amino]carbonyl]-2-oxo-1-pyrrolidinyl... substance identified as siloxanes and silicones, de-Me, 3-[4-[[[3-(dimethylamino) propyl]amino] carbonyl]-2...
Copoly(Imide Siloxane) Abhesive Materials with Varied Siloxane Oligomer Length
NASA Technical Reports Server (NTRS)
Wohl, Christopher J.; Atkins, Brad M.; Belcher, Marcus A.; Connell, John W.
2010-01-01
Incorporation of PDMS moieties into a polyimide matrix lowered the surface energy resulting in enhanced adhesive interactions. Polyimide siloxane materials were generated using amine-terminated PDMS oligomers of different lengths to study changes in surface migration behavior, phase segregation, mechanical, thermal, and optical properties. These materials were characterized using contact angle goniometry, tensile testing, and differential scanning calorimetry. The surface migration behavior of the PDMS component depended upon the siloxane molecular weight as indicated by distinct relationships between PDMS chain length and advancing water contact angles. Similar correlations were observed for percent elongation values obtained from tensile testing, while the addition of PDMS reduced the modulus. High fidelity topographical modification via laser ablation patterning further reduced the polyimide siloxane surface energy. Initial particulate adhesion testing experiments demonstrated that polyimide siloxane materials exhibited greater abhesive interactions relative to their respective homopolyimides.
Fardin-Kia, Ali Reza; Delmonte, Pierluigi; Kramer, John K G; Jahreis, Gerhard; Kuhnt, Katrin; Santercole, Viviana; Rader, Jeanne I
2013-12-01
The fatty acids contained in marine oils or products are traditionally analyzed by gas chromatography using capillary columns coated with polyethylene glycol phases. Recent reports indicate that 100 % cyanopropyl siloxane phases should also be used when the analyzed samples contain trans fatty acids. We investigated the separation of the fatty acid methyl esters prepared from menhaden oil using the more polar SLB-IL111 (200 m × 0.25 mm) ionic liquid capillary column and the chromatographic conditions previously optimized for the separation of the complex mixture of fatty acid methyl esters prepared from milk fat. Identifications of fatty acids were achieved by applying Ag(+)-HPLC fractionation and GC-TOF/MS analysis in CI(+) mode with isobutane as the ionization reagent. Calculation of equivalent chain lengths confirmed the assignment of double bond positions. This methodology allowed the identification of 125 fatty acids in menhaden oil, including isoprenoid and furanoid fatty acids, and the novel 7-methyl-6-hexadecenoic and 7-methyl-6-octadecenoic fatty acids. The chromatographic conditions applied in this study showed the potential of separating in a single 90-min analysis, among others, the short chain and trans fatty acids contained in dairy products, and the polyunsaturated fatty acids contained in marine products.
Mojsiewicz-Pieńkowska, Krystyna; Jamrógiewicz, Marzena; Szymkowska, Katarzyna; Krenczkowska, Dominika
2016-01-01
Siloxanes are commonly known as silicones. They belong to the organosilicon compounds and are exclusively obtained by synthesis. Their chemical structure determines a range of physicochemical properties which were recognized as unique. Due to the susceptibility to chemical modifications, ability to create short, long or complex polymer particles, siloxanes found an application in many areas of human life. Siloxanes differ in particle size, molecular weight, shape and chemical groups. As a result, this determines the different physico-chemical properties, that directly affect the safety or the risk of their use. The areas that can be a source of danger to human health will be commented in this paper. PMID:27303296
Tansel, Berrin; Surita, Sharon C
2016-06-01
Siloxane levels in biogas can jeopardize the warranties of the engines used at the biogas to energy facilities. The chemical structure of siloxanes consists of silicon and oxygen atoms, alternating in position, with hydrocarbon groups attached to the silicon side chain. Siloxanes can be either in cyclic (D) or linear (L) configuration and referred with a letter corresponding to their structure followed by a number corresponding to the number of silicon atoms present. When siloxanes are burned, the hydrocarbon fraction is lost and silicon is converted to silicates. The purpose of this study was to evaluate the adequacy of activated carbon gas samplers for quantitative analysis of siloxanes in biogas samples. Biogas samples were collected from a landfill and an anaerobic digester using multiple carbon sorbent tubes assembled in series. One set of samples was collected for 30min (sampling 6-L gas), and the second set was collected for 60min (sampling 12-L gas). Carbon particles were thermally desorbed and analyzed by Gas Chromatography Mass Spectrometry (GC/MS). The results showed that biogas sampling using a single tube would not adequately capture octamethyltrisiloxane (L3), hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6). Even with 4 tubes were used in series, D5 was not captured effectively. The single sorbent tube sampling method was adequate only for capturing trimethylsilanol (TMS) and hexamethyldisiloxane (L2). Affinity of siloxanes for activated carbon decreased with increasing molecular weight. Using multiple carbon sorbent tubes in series can be an appropriate method for developing a standard procedure for determining siloxane levels for low molecular weight siloxanes (up to D3). Appropriate quality assurance and quality control procedures should be developed for adequately quantifying the levels of the higher molecular weight siloxanes in biogas with sorbent tubes. Copyright © 2016 Elsevier Ltd. All rights reserved.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Mariano, García; Daniel, Prats; Arturo, Trapote, E-mail: atj@ua.es
2015-12-21
The siloxanes present in the biogas produced during anaerobic digestion damage the mechanism of cogeneration equipment and, consequently, negatively affect the energy valorization process. For this reason, the detection and elimination of these silicon-derived chemical compounds are a priority in the management of cogeneration facilities. In this regard, the objectives of this paper are, firstly, to characterize the siloxanes in the biogas and, secondly, to qualitatively evaluate the influence of the dose of iron chloride on its elimination. The research was performed at the Rincón de León Wastewater Treatment Plant (Alicante, Spain). The outflow biogas of the digesters and ofmore » the pressurized gasometers was sampled and analyzed. The results obtained made it possible to demonstrate, firstly, the absence of linear siloxanes and that, of the cyclic siloxanes, the predominant type was decamethylcyclopentasiloxane, and, secondly, that the addition of iron chloride in the digesters significantly reduces the siloxane content in the biogas. Additionally, it was demonstrated that the process of compression of the biogas, with the elimination of condensates, also produces significant reductions in the concentration of siloxanes in the biogas.« less
40 CFR 721.10120 - Siloxane modified alumina nanoparticles (generic).
Code of Federal Regulations, 2010 CFR
2010-07-01
... nanoparticles (generic). 721.10120 Section 721.10120 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.10120 Siloxane modified alumina nanoparticles (generic). (a) Chemical... as siloxane modified alumina nanoparticles (PMN P-05-687) is subject to reporting under this section...
40 CFR 721.10120 - Siloxane modified alumina nanoparticles (generic).
Code of Federal Regulations, 2014 CFR
2014-07-01
... nanoparticles (generic). 721.10120 Section 721.10120 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.10120 Siloxane modified alumina nanoparticles (generic). (a) Chemical... as siloxane modified alumina nanoparticles (PMN P-05-687) is subject to reporting under this section...
40 CFR 721.10120 - Siloxane modified alumina nanoparticles (generic).
Code of Federal Regulations, 2012 CFR
2012-07-01
... nanoparticles (generic). 721.10120 Section 721.10120 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.10120 Siloxane modified alumina nanoparticles (generic). (a) Chemical... as siloxane modified alumina nanoparticles (PMN P-05-687) is subject to reporting under this section...
40 CFR 721.10120 - Siloxane modified alumina nanoparticles (generic).
Code of Federal Regulations, 2011 CFR
2011-07-01
... nanoparticles (generic). 721.10120 Section 721.10120 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.10120 Siloxane modified alumina nanoparticles (generic). (a) Chemical... as siloxane modified alumina nanoparticles (PMN P-05-687) is subject to reporting under this section...
40 CFR 721.10120 - Siloxane modified alumina nanoparticles (generic).
Code of Federal Regulations, 2013 CFR
2013-07-01
... nanoparticles (generic). 721.10120 Section 721.10120 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.10120 Siloxane modified alumina nanoparticles (generic). (a) Chemical... as siloxane modified alumina nanoparticles (PMN P-05-687) is subject to reporting under this section...
Chemically Amplified Bilevel Resist Based on Condensation of Siloxanes
NASA Astrophysics Data System (ADS)
Sakata, Miwa; Ito, Toshio; Yamashita, Yoshio
1991-11-01
This paper deals with a negative bilevel resist which is based on the acid-catalyzed condensation reaction of poly(siloxane)s. The resist systems consist of photoacid generators and poly(siloxane). Ph3S+OTf- reveals an efficient activity for silanol condensation and the system has a high sensitivity of 0.31 mJ/cm2. Tetrafunctional silane plays the role of crosslinker in this system. Sensitivity improvement of low-sensitivity systems such as benzoin p-toluenesulfonate/poly(siloxane) can be achieved by this method.
Copoly(imide siloxane) Abhesive Materials with Varied Siloxane Oligomer Length
NASA Technical Reports Server (NTRS)
Wohl, Christoper J.; Atkins, Brad M.; Lin, Yi; Belcher, Marcus A.; Connell, John W.
2010-01-01
In this work, low surface energy copoly(imide siloxane)s were synthesized with various siloxane segment lengths. Characterization of these materials revealed that domain formation of the low surface energy component within the matrix was more prevalent for longer siloxane segments as indicated by increased opacity, decreased mechanical properties, and variation of the Tg. Incorporation of siloxanes lowered the polymer s surface energy as indicated by water contact angle values. Topographical modification of these materials by laser ablation patterning further reduced the surface energy, even generating superhydrophobic surfaces. Combined, the contact angle data and particle adhesion testing indicated that copoly(imide siloxane) materials may provide greater mitigation to particulate adhesion than polyimide materials alone. These enhanced surface properties for abhesive applications did result in a reduction of the tensile moduli of the copolymers. It is possible that lower siloxane loading levels would result in retention of the mechanical properties of the polyimide while still affording abhesive surface properties. This hypothesis is currently being investigated. Laser ablation patterning offers further reduction in particle retention as the available surface area for particle adhesion is reduced. Pattern variation and size dependencies are currently being evaluated. For the purposes of lunar dust adhesion mitigation, it is likely that this approach, termed passive due to the lack of input from an external energy source, would not be sufficient to mitigate surface contamination or clean contaminated surfaces for some lunar applications. It is feasible to combine these materials with active mitigation strategies - methods that utilize input from external energy sources - would broaden the applicability of such materials for abhesive purposes. Collaborative efforts along these lines have been initiated with researchers at NASA Kennedy Space Center where experiments are being conducted involving a series of embedded electrodes within polymeric matrices.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Nam, Sangchul; Namkoong, Wan; Kang, Jeong-Hee
Highlights: • Equilibrium test was attempted to evaluate adsorption characteristics of siloxane. • L2 had higher removal efficiency in carbon compared to noncarbon adsorbents. • Total adsorption capacity of siloxane was 300 mg/g by coal activated carbon. • Adsorption characteristics rely on size of siloxane molecule and adsorbent pore. • Conversion of siloxane was caused by adsorption of noncarbon adsorbents. - Abstract: Due to the increase in energy cost by constantly high oil prices and the obligation to reduce greenhouse effect gases, landfill gas is frequently used as an alternative energy source for producing heat and electricity. Most of landfillmore » gas utility facilities, however, are experiencing problems controlling siloxanes from landfill gas as their catalytic oxidizers are becoming fouled by silicon dioxide dust. To evaluate adsorption characteristics of siloxanes, an adsorption equilibrium test was conducted and parameters in the Freundlich and Langmuir isotherms were analyzed. Coconut activated carbon (CA1), coal activated carbon (CA2), impregnated activated carbon (CA3), silicagel (NCA1), and activated alumina (NCA2) were used for the adsorption of the mixed siloxane which contained hexamethyldisiloxane (L2), octamethylcyclotetrasiloxane (D4), and decamethylcyclopentasiloxane (D5). L2 had higher removal efficiency in noncarbon adsorbents compared to carbon adsorbents. The application of Langmuir and Freundlich adsorption isotherm demonstrated that coconut based CA1 and CA3 provided higher adsorption capacity on L2. And CA2 and NCA1 provided higher adsorption capacity on D4 and D5. Based on the experimental results, L2, D4, and D5 were converted by adsorption and desorption in noncarbon adsorbents. Adsorption affinity of siloxane is considered to be affect by the pore size distribution of the adsorbents and by the molecular size of each siloxane.« less
Amino-siloxane composition and methods of using the same
DOE Office of Scientific and Technical Information (OSTI.GOV)
O'Brien, Michael Joseph; Farnum, Rachel Lizabeth; Perry, Robert James
An amino-siloxane composition is presented. The amino-siloxane composition includes structure (I): ##STR00001## wherein R 1 is independently at each occurrence a C 1-C 5 aliphatic radical; R 2 is a C 3-C. 4 aliphatic radical; R 3 is a C 1-C 5 aliphatic radical or R 4, wherein R 4 comprises structure (II): ##STR00002## and X is an electron donating group. Methods of reducing an amount of carbon dioxide in a process stream using the amino-siloxane composition are also presented.
Structure and properties of epoxy-siloxane-silica nanocomposite coatings for corrosion protection.
Torrico, Ruben F A O; Harb, Samarah V; Trentin, Andressa; Uvida, Mayara C; Pulcinelli, Sandra H; Santilli, Celso V; Hammer, Peter
2018-03-01
The fraction of the silica/siloxane phase is a crucial parameter, which determines the structure and thus the properties of epoxy-siloxane-silica hybrid coatings. A careful adjustment of the colloidal precursor formulation allows tuning the nanostructure towards a highly condensed and cross-linked hybrid nanocomposite, suitable as an efficient anticorrosive coating. Novel epoxy-siloxane-silica hybrids have been prepared through the curing reaction of poly(bisphenol A-co-epichlorohydrin) (DGEBA) with diethyltriamine (DETA) and (3-glycidoxypropyl)methyltriethoxysilane (GPTMS), followed by hydrolytic condensation of tetraethoxysilane (TEOS) and GPTMS. At a constant proportion of the organic phase, the effects of the varying molar proportions of siloxane (GPTMS) and silica (TEOS) on the film properties have been investigated. A detailed structural analysis suggests for intermediate TEOS to GPTMS ratios a structure of highly condensed silica-siloxane domains covalently bonded to the embedding epoxy phase. The homogeneous distribution of the quasi-spherical sub-nonmetric silica-siloxane nodes is in agreement with low surface roughness (<5 nm), observed by atomic force microscopy. This dense nanostructure results in high thermal stability (>300 °C), strong adhesion to steel substrate and excellent barrier property in saline solution, with corrosion resistance in the GΩ cm 2 range. Copyright © 2017 Elsevier Inc. All rights reserved.
UV absorption and photoisomerization of p-methoxycinnamate grafted silicone.
Pattanaargson, Supason; Hongchinnagorn, Nantawan; Hirunsupachot, Piyawan; Sritana-anant, Yongsak
2004-01-01
p-Methoxycinnamate moieties, UV-B-absorptive chromophores of the widely used UV-B filter, 2-ethylhexyl p-methoxycinnamate (OMC), were grafted onto the 7 mol% amino functionalized silicone polymer through amide linkages. Comparing with OMC, the resulting poly [3-(p-methoxycinnamido)(propyl)(methyl)-dimethyl] siloxane copolymer (CAS) showed less E to Z isomerization when exposed to UV-B light. The absorption profiles of the product showed the maximum absorption wavelength to be similar to that of OMC but with less sensitivity to the type of solvent. Poly (methylhydrosiloxane) grafted with 10 mol% p-methoxycinnamoyl moieties was prepared through hydrosilylations of 2-propenyl-p-methoxycinnamate, in which the resulting copolymer showed similar results to those of CAS.
Synthesis and evaluation of novel siloxane-methacrylate monomers used as dentin adhesives
Ge, Xueping; Ye, Qiang; Song, Linyong; Misra, Anil; Spencer, Paulette
2014-01-01
Objectives The objectives of this study were to synthesize two new siloxane-methacrylate (SM) monomers for application in dentin adhesives and to investigate the influence of different functionality of the siloxane-containing monomers on the adhesive photopolymerization, water sorption, and mechanical properties. Materials and method Two siloxane-methacrylate monomers (SM1 and SM2) with four and eight methacrylate groups were synthesized. Dentin adhesives containing BisGMA, HEMA and the siloxane-methacrylate monomers were photo-polymerized. The experimental adhesives were compared with the control adhesive (HEMA/BisGMA 45/55 w/w) and characterized with regard to degree of conversion (DC), water miscibility of the liquid resin, water sorption and dynamic mechanical analysis (DMA). Results The experimental adhesives exhibited improved water miscibility as compared to the control. When cured in the presence of 12 wt % water to simulate the wet environment of the mouth, the SM-containing adhesives showed DC comparable to the control. The experimental adhesives showed higher rubbery modulus than the control under dry conditions. Under wet conditions, the mechanical properties of the formulations containing SM monomer with increased functionality were comparable with the control, even with more water sorption. Significance The concentration and functionality of the newly synthesized siloxane-methacrylate monomers affected the water miscibility, water sorption and mechanical properties of the adhesives. The experimental adhesives show improved water compatibility compared with the control. The mechanical properties were enhanced with an increase of the functionality of the siloxane-containing monomers. The results provide critical structure/property relationships and important information for future development of durable, versatile siloxane-containing dentin adhesives. PMID:24993811
Synthesis and evaluation of novel siloxane-methacrylate monomers used as dentin adhesives.
Ge, Xueping; Ye, Qiang; Song, Linyong; Misra, Anil; Spencer, Paulette
2014-09-01
The objectives of this study were to synthesize two new siloxane-methacrylate (SM) monomers for application in dentin adhesives and to investigate the influence of different functionality of the siloxane-containing monomers on the adhesive photopolymerization, water sorption, and mechanical properties. Two siloxane-methacrylate monomers (SM1 and SM2) with four and eight methacrylate groups were synthesized. Dentin adhesives containing BisGMA, HEMA and the siloxane-methacrylate monomers were photo-polymerized. The experimental adhesives were compared with the control adhesive (HEMA/BisGMA, 45/55, w/w) and characterized with regard to degree of conversion (DC), water miscibility of the liquid resin, water sorption and dynamic mechanical analysis (DMA). The experimental adhesives exhibited improved water miscibility as compared to the control. When cured in the presence of 12 wt% water to simulate the wet environment of the mouth, the SM-containing adhesives showed DC comparable to the control. The experimental adhesives showed higher rubbery modulus than the control under dry conditions. Under wet conditions, the mechanical properties of the formulations containing SM monomer with increased functionality were comparable with the control, even with more water sorption. The concentration and functionality of the newly synthesized siloxane-methacrylate monomers affected the water miscibility, water sorption and mechanical properties of the adhesives. The experimental adhesives show improved water compatibility compared with the control. The mechanical properties were enhanced with an increase of the functionality of the siloxane-containing monomers. The results provide critical structure/property relationships and important information for future development of durable, versatile siloxane-containing dentin adhesives. Published by Elsevier Ltd.
Amino-siloxane composition and methods of using the same
DOE Office of Scientific and Technical Information (OSTI.GOV)
O'Brien, Michael Joseph; Farnum, Rachel Lizabeth; Perry, Robert James
2016-08-30
An amino-siloxane composition is presented. The amino-siloxane composition includes structure (I): ##STR00001## wherein R.sup.1 is independently at each occurrence a C.sub.1-C.sub.5 aliphatic radical; R.sup.2 is a C.sub.3-C.sub.4 aliphatic radical; R.sup.3 is a C.sub.1-C.sub.5 aliphatic radical or R.sup.4, wherein R.sup.4 comprises structure (II): ##STR00002## and X is an electron donating group. Methods of reducing an amount of carbon dioxide in a process stream using the amino-siloxane composition are also presented.
Code of Federal Regulations, 2013 CFR
2013-07-01
... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Siloxanes and silicones, 3-[(2... Specific Chemical Substances § 721.9516 Siloxanes and silicones, 3-[(2-aminoethyl) amino]propyl Me, di-Me... silicones, 3-[(2-aminoethyl) amino]propyl Me, di-Me, reaction products with polyethylene-polypropylene...
Code of Federal Regulations, 2013 CFR
2013-07-01
... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Siloxanes and Silicones, di-Me, Me... Silicones, di-Me, Me vinyl, hydroxy-terminated, reaction products with silica. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as Siloxanes and Silicones...
Code of Federal Regulations, 2012 CFR
2012-07-01
... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Siloxanes and silicones, 3-[(2... Specific Chemical Substances § 721.9516 Siloxanes and silicones, 3-[(2-aminoethyl) amino]propyl Me, di-Me... silicones, 3-[(2-aminoethyl) amino]propyl Me, di-Me, reaction products with polyethylene-polypropylene...
Code of Federal Regulations, 2014 CFR
2014-07-01
... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Siloxanes and Silicones, di-Me, Me... Silicones, di-Me, Me vinyl, hydroxy-terminated, reaction products with silica. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as Siloxanes and Silicones...
Code of Federal Regulations, 2014 CFR
2014-07-01
... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Siloxanes and silicones, 3-[(2... Specific Chemical Substances § 721.9516 Siloxanes and silicones, 3-[(2-aminoethyl) amino]propyl Me, di-Me... silicones, 3-[(2-aminoethyl) amino]propyl Me, di-Me, reaction products with polyethylene-polypropylene...
Trapote, Arturo; García, Mariano; Prats, Daniel
2016-12-01
Siloxanes present in the biogas produced during anaerobic digestion in wastewater treatment plants (WWTPs) can damage the mechanism of cogeneration heat engines and obstruct the process of energy valorization. The objective of this research is to detect the presence of siloxanes in the biogas and evaluate a procedure for their elimination. A breakthrough curve of a synthetic decamethylcyclopentasiloxane on an experimental bed of activated carbon was modeled and the theoretical mathematical model of the adsorption process was adjusted. As a result, the constants of the model were obtained: the mass transfer constant, Henry's equilibrium constant, and the Eddy diffusion. The procedure developed allows the adsorption equilibrium of siloxanes on activated carbon to be predicted, and makes it possible to lay the basis for the design of an appropriate activated carbon module for the elimination of siloxanes in a WWTP.
Light-weight ceramic insulation
NASA Technical Reports Server (NTRS)
Hsu, Ming-Ta S. (Inventor); Chen, Timothy S. (Inventor)
2002-01-01
Ultra-high temperature, light-weight, ceramic insulation such as ceramic tile is obtained by pyrolyzing a siloxane gel derived from the reaction of at least one organo dialkoxy silane and at least one tetralkoxy silane in an acid or base liquid medium. The reaction mixture of the tetra- and dialkoxy silanes may contain also an effective amount of a mono- or trialkoxy silane to obtain the siloxane gel. The siloxane gel is dried at ambient pressures to form a siloxane ceramic precursor without significant shrinkage. The siloxane ceramic precursor is subsequently pyrolyzed, in an inert atmosphere, to form the black ceramic insulation comprising atoms of silicon, carbon and oxygen. The ceramic insulation, can be characterized as a porous, uniform ceramic tile resistant to oxidation at temperatures ranging as high as 1700.degree. C. and is particularly useful as lightweight tiles for spacecraft and other high-temperature insulation applications.
Horii, Yuichi; Kannan, Kurunthachalam
2008-11-01
The determination of organosiloxanes in consumer products is important for the evaluation and characterization of sources of human and environmental exposures. In this study, we determined concentrations of cyclic siloxanes [octamethylcyclotetrasiloxane (D(4)), decamethylcyclopentasiloxane (D(5)), dodecamethylcyclohexasiloxane (D(6))], tetradecamethylcycloheptasiloxane (D(7))] and linear siloxanes (L(4) to L(14)) in a variety of consumer products (n = 76), including hair-care products, skin lotions, body washes, cosmetics, nursing nipples (i.e., pacifiers), cookware, and household sanitation products such as cleansers and furniture polishes, using gas chromatography-mass spectrometry with selected ion monitoring. Prior to the analysis of samples, a method was developed to reduce the contamination arising from organosiloxanes present in certain gas chromatograph (GC) parts, such as the inlet septum; use of a Restek BTO septum at an inlet temperature of 200 degrees C gave the lowest background level (D(4): 0.8 pg; D(5): 0.3 pg; D(6): 0.2 pg). Concentrations of cyclic siloxanes in consumer products analyzed ranged from <0.35 to 9380 microg/g, from <0.39 to 81,800 microg/g, from <0.33 to 43,100 microg/g, and from <0.42 to 846 microg/g for D(4), D(5), D(6), and D(7), respectively. Concentrations of linear siloxanes varied from <0.059 to 73,000 microg/g. More than 50% of the samples analyzed contained D(4), D(5), or D(6). Cyclic siloxanes were predominant in most of the sample categories; D(5) was predominant in hair-care products, skin lotions, and cosmetics; D(6) or D(7) was predominant in rubber products, including nipples, cookware, and sealants. Potential daily exposure to total organosiloxanes (sum of cyclic and linear siloxanes) from the use of personal-care products by adult women in the United States has been estimated to be 307 mg. Significant positive correlations (p < 0.01) existed in our study between D(4) and D(7), D(4) and linear siloxanes, D(5) and D(6), and D(5) and linear siloxanes. The correlations can be related to the composition of organosiloxanes used in consumer products. The results of our study suggest that a wide variety of consumer products that are used on a daily basis contain cyclic and linear siloxanes and these products can contribute considerably to human exposures.
Code of Federal Regulations, 2013 CFR
2013-10-01
... returns to port and at all points in between. Real-time means as soon as possible, but at least every 4... paragraph (1) of this definition. Centralized Vessel Monitoring System (C-VMS) means a system that uses... weight, at any time, of the catch on board the vessel. Dissostichus catch document (DCD) means the...
Code of Federal Regulations, 2011 CFR
2011-10-01
... returns to port and at all points in between. Real-time means as soon as possible, but at least every 4... paragraph (1) of this definition. Centralized Vessel Monitoring System (C-VMS) means a system that uses... weight, at any time, of the catch on board the vessel. Dissostichus catch document (DCD) means the...
Code of Federal Regulations, 2010 CFR
2010-10-01
... returns to port and at all points in between. Real-time means as soon as possible, but at least every 4... paragraph (1) of this definition. Centralized Vessel Monitoring System (C-VMS) means a system that uses... weight, at any time, of the catch on board the vessel. Dissostichus catch document (DCD) means the...
Gharibi, Reza; Yeganeh, Hamid; Rezapour-Lactoee, Alireza; Hassan, Zuhair M
2015-11-04
A series of novel polyurethane/siloxane-based wound dressing membranes was prepared through sol-gel reaction of methoxysilane end-functionalized urethane prepolymers composed of castor oil and ricinoleic methyl ester as well as methoxysilane functional aniline tetramer (AT) moieties. The samples were fully characterized and their physicochemical, mechanical, electrical, and biological properties were assayed. The biological activity of these dressings against fibroblast cells and couple of microbes was also studied. It was revealed that samples that displayed electroactivity by introduction of AT moieties showed a broad range of antimicrobial activity toward different microorganisms, promising antioxidant (radical scavenging) efficiency and significant activity for stimulation of fibroblast cell growth and proliferation. Meanwhile, these samples showed appropriate tensile strength and ability for maintaining a moist environment over a wound by controlled equilibrium water absorption and water vapor transmission rate. The selected electroactive dressing was subjected to an in vivo assay using a rat animal model and the wound healing process was monitored and compared with analogous dressing without AT moieties. The recorded results showed that the electroactive dressings induced an increase in the rate of wound contraction, promoted collagen deposition, and encouraged vascularization in the wounded area. On the basis of the results of in vitro and in vivo assays, the positive influence of designed dressings for accelerated healing of a wound model was confirmed.
Code of Federal Regulations, 2010 CFR
2010-07-01
..., reaction products with 2,2,6,6-tetramethyl-4-(2-propenyloxy)piperdine. 721.6170 Section 721.6170 Protection... Siloxanes and silicones, Me hydrogen, reaction products with 2,2,6,6-tetramethyl-4-(2-propenyloxy)piperdine... identified as siloxanes and silicones, Me hydrogen, reaction products with 2,2,6,6-tetramethyl-4-(2...
Code of Federal Regulations, 2011 CFR
2011-07-01
..., reaction products with 2,2,6,6-tetramethyl-4-(2-propenyloxy)piperdine. 721.6170 Section 721.6170 Protection... Siloxanes and silicones, Me hydrogen, reaction products with 2,2,6,6-tetramethyl-4-(2-propenyloxy)piperdine... identified as siloxanes and silicones, Me hydrogen, reaction products with 2,2,6,6-tetramethyl-4-(2...
Tran, Tri Manh; Abualnaja, Khalid O; Asimakopoulos, Alexandros G; Covaci, Adrian; Gevao, Bondi; Johnson-Restrepo, Boris; Kumosani, Taha A; Malarvannan, Govindan; Minh, Tu Binh; Moon, Hyo-Bang; Nakata, Haruhiko; Sinha, Ravindra K; Kannan, Kurunthachalam
2015-05-01
Siloxanes are used widely in a variety of consumer products, including cosmetics, personal care products, medical and electrical devices, cookware, and building materials. Nevertheless, little is known on the occurrence of siloxanes in indoor dust. In this survey, five cyclic (D3-D7) and 11 linear (L4-L14) siloxanes were determined in 310 indoor dust samples collected from 12 countries. Dust samples collected from Greece contained the highest concentrations of total cyclic siloxanes (TCSi), ranging from 118 to 25,100ng/g (median: 1380), and total linear siloxanes (TLSi), ranging from 129 to 4990ng/g (median: 772). The median total siloxane (TSi) concentrations in dust samples from 12 countries were in the following decreasing order: Greece (2970ng/g), Kuwait (2400), South Korea (1810), Japan (1500), the USA (1220), China (1070), Romania (538), Colombia (230), Vietnam (206), Saudi Arabia (132), India (116), and Pakistan (68.3). TLSi concentrations as high as 42,800ng/g (Kuwait) and TCSi concentrations as high as 25,000ng/g (Greece) were found in indoor dust samples. Among the 16 siloxanes determined, decamethylcyclopentasiloxane (D5) was found at the highest concentration in dust samples from all countries, except for Japan and South Korea, with a predominance of L11; Kuwait, with L10; and Pakistan and Romania, with L12. The composition profiles of 16 siloxanes in dust samples varied by country. TCSi accounted for a major proportion of TSi concentrations in dust collected from Colombia (90%), India (80%) and Saudi Arabia (70%), whereas TLSi predominated in samples collected from Japan (89%), Kuwait (85%), and South Korea (78%). Based on the measured median TSi concentrations in indoor dust, we estimated human exposure doses through indoor dust ingestion for various age groups. The exposure doses ranged from 0.27 to 11.9ng/kg-bw/d for toddlers and 0.06 to 2.48ng/kg-bw/d for adults. Copyright © 2015 Elsevier Ltd. All rights reserved.
NASA Technical Reports Server (NTRS)
Bott, R. H.; Summers, J. D.; Arnold, C. A.; Blankenship, C. P., Jr.; Taylor, L. T.
1988-01-01
The improved properties that have been demonstrated through thermal solution imidization in the case of polyimides and poly(imide-siloxane) segmented copolymers suggests significant potential for application of these new materials. Specifically, the enhancement in solubility, moisture reduction, and processability observed through this solution technique is quite dramatic. Previous work has shown that the presence of low amounts of siloxane does not detract significantly from the lap shear strength of these materials to titanium in the case of bulk thermal imidization synthesis. In addition, the siloxane incorporation results in the added advantage of resistance to hot, wet environments. This added durability is presumably due to the hydrophobic siloxane segments preventing the uptake of water at the critical interphase between the adhesive and the adherend. This paper discusses the extension of this work to the solution imidization synthesis technique recently developed in our laboratory. Results dealing with the absolute bond strengths as well as durability and failure surface analysis will be presented.
Light-weight black ceramic insulation
NASA Technical Reports Server (NTRS)
Hsu, Ming-Ta S. (Inventor); Chen, Timothy S. (Inventor)
2003-01-01
Ultra-high temperature, light-weight, black ceramic insulation having a density ranging from about 0.12 g/cc. to 0.6 g/cc. such as ceramic tile is obtained by pyrolyzing siloxane gels derived from the reaction of at least one organo dialkoxy silane and at least one tetralkoxy silane in an acid or base liquid medium. The reaction mixture of the tetra- and dialkoxy silanes also may contain an effective amount of a mono- or trialkoxy silane to obtain the siloxane gels. The siloxane gels are dried at ambient temperatures and pressures to form siloxane ceramic precursors without significant shrinkage. The siloxane ceramic precursors are subsequently pyrolyzed, in an inert atmosphere, to form the black ceramic insulation comprising atoms of silicon, carbon and oxygen. The ceramic insulation can be characterized as a porous, uniform ceramic tile resistant to oxidation at temperatures ranging as high as 1700.degree. C., and particularly useful as lightweight tiles for spacecraft and other high-temperature insulation applications.
Formation mechanism of photo-induced nested wrinkles on siloxane-photomonomer hybrid film
DOE Office of Scientific and Technical Information (OSTI.GOV)
Suzuki, Kazumasa; International Laboratory of Materials Science and Nanotechnology; Laboratorio di Scienz
Nested wrinkle structures, hierarchical surface wrinkles of different periodicities of sub-μm and tens-μm, have been fabricated on a siloxane-photomonomer hybrid film via a photo-induced surface polymerization of acrylamide. The formation mechanism of the nested wrinkle structures is examined based on a time-dependent structure observation and chemical composition analyses. In-situ observation of the evolving surface structure showed that sub-μm scale wrinkles first formed, subsequently the tens-μm scale ones did. In-situ FT-IR analysis indicated that the nested wrinkles formation took place along with the development of siloxane network of under layer. A cross sectional observation of the film revealed that the filmmore » was composed of three layers. FT-IR spectra of the film revealed that the surface and interior layers were polyacrylamide rich layer and siloxane-polymer rich layer, respectively. The intermediate layer formed as a diffusion layer by migration of acrylamide from interior to the surface. These three layers have different chemical compositions and therefore different mechanical characteristics, which allows the wrinkle formation. Shrinkage of siloxane-polymer interior layers, as a result of polycondensation of siloxane network, induced mechanical instabilities at interlayers, to form the nested wrinkle structures.« less
Singh, Rina; Singh, Jagjit; Singh, Ramanpreet; Nanda, Sonia
2013-01-01
Objective:To determine the effect of different retraction cord medicaments on surface detail reproduction of polyvinyl siloxane impression materials and compare this effect on any two brands of commercially available polyvinyl siloxane impression materials. Material and methods: Four stainless steel dies were made according to ADA specification no.19. Three dies were treated with aluminium chloride (5%), ferric sulphate (13.3%) and epinephrine (0.1%) while the fourth one was left untreated to serve as control. Two impression materials (Dentsply and 3M ESPE) were used. Results: All the three medicaments adversely affected the surface detail reproduction of both the brands of the polyvinyl siloxane impression materials. These effects were statistically significant as compared to untreated control. The impressions of 3M ESPE brand have shown better surface detail reproduction as compared to Dentsply impression material. Conclusion: Surface detail reproduction of the polyvinyl siloxane impression materials is adversely affected by the retraction cord medicaments. The presence of moisture or any traces of the medicaments should be removed from the tooth surface to provide a dry field for the correct reproduction of the surface detail of these materials. Key words:Polyvinyl Siloxane, retraction cord medicaments, surface detail reproduction. PMID:24455069
Effect of polyvinyl siloxane impression material on the polymerization of composite resin.
Chen, Liang; Kleverlaan, Cornelis Johannes; Liang, Kunneng; Yang, Deqin
2017-04-01
Polyvinyl siloxane impression material has been widely used as a lingual matrix for rebuilding missing tooth structure with composite resin. The composite resin is light polymerized in contact with the polyvinyl siloxane impression material. However, polyvinyl siloxane impression material has been shown to interact with other dental materials. The purpose of this study was to assess the effect of polyvinyl siloxane impression materials on the polymerization of composite resins by assessing the Vickers microhardness and degree of conversion of polyvinyl siloxane. The composite resins were light polymerized in contact with 3 polyvinyl siloxane impression materials (Flexitime Easy Putty; President Light Body; Xantopren L Blue) (n=8) and in contact with a matrix strip as the control group (n=8). Vickers microhardness and degree of conversion on contact surfaces were measured to evaluate the polymerization of composite resins. The depth of the effect was assessed by Vickers microhardness on section surfaces and observed with scanning electron microscopy. The results were analyzed by 1-way analysis of variance and the post hoc Tukey honest significant differences test (α=.05). The Vickers microhardness and degree of conversion values on the contact surfaces of the experiment groups were significantly lower than those of the control group (P<.05); the Vickers microhardness values on the section surfaces indicated that there was no significant difference at the same depth of different groups (P>.05). The scanning electron microscope observation showed that an approximately 10-μm deep unpolymerized layer was found in the experimental group. Polyvinyl siloxane impression materials have an inhibitory effect on the polymerization of the composite resins, but just limited to within approximately 10 μm from the surface in contact with the impression material. Copyright © 2016 Editorial Council for the Journal of Prosthetic Dentistry. Published by Elsevier Inc. All rights reserved.
Carbon dioxide absorbent and method of using the same
Perry, Robert James [Niskayuna, NY; Lewis, Larry Neil [Scotia, NY; O'Brien, Michael Joseph [Clifton Park, NY; Soloveichik, Grigorii Lev [Latham, NY; Kniajanski, Sergei [Clifton Park, NY; Lam, Tunchiao Hubert [Clifton Park, NY; Lee, Julia Lam [Niskayuna, NY; Rubinsztajn, Malgorzata Iwona [Ballston Spa, NY
2011-10-04
In accordance with one aspect, the present invention provides an amino-siloxane composition comprising at least one of structures I, II, III, IV or V said compositions being useful for the capture of carbon dioxide from gas streams such as power plant flue gases. In addition, the present invention provides methods of preparing the amino-siloxane compositions are provided. Also provided are methods for reducing the amount of carbon dioxide in a process stream employing the amino-siloxane compositions of the invention as species which react with carbon dioxide to form an adduct with carbon dioxide. The reaction of the amino-siloxane compositions provided by the present invention with carbon dioxide is reversible and thus, the method provides for multicycle use of said compositions.
Seagraves, Nikki J.; McBride, Kim L.
2012-01-01
Maternal phenylketonuria (MPKU) is a syndrome including cardiovascular malformations (CVMs), microcephaly, intellectual impairment, and small for gestational age, caused by in-utero exposure to elevated serum phenylalanine (Phe) due to PKU in the mother. It is becoming a public health concern as more women with PKU reach child bearing age. Although a mouse model of PKU, BTBR Pahenu2, has been available for 20 years, it has not been well utilized for studying MPKU. We used this model to delineate critical parameters in Phe cardiovascular teratogenicity and study the effect of genetic background. Dosing and timing experiments were performed with the BTBR Pahenu2 mouse. A dose response curve was noted, with CVM rates at maternal serum Phe levels <360 μM (control), 360 – 600 μM (low), 600 – 900 μM (mid), and >900μM (high) of 11.86%, 16.67%, 30.86%, and 46.67% respectively. A variety of CVMs were noted on the BTBR background, including double outlet right ventricle (DORV), aortic arch artery (AAA)abnormalities, and ventricular septal defects (VSDs). Timed exposure experiments identified a teratogenic window from embryonic day 8.5-13.5, with higher rates of conotruncal and valve defects occurring in early exposure time and persistent truncus arteriosus (PTA) and aortic arch branching abnormalities occurring with late exposure. Compared to the BTBR strain, N10+ Pahenu2 congenics on the C3H/HeJ background had higher rates of CVMs in general and propensity to left ventricular outflow tract (LVOT) malformations, while the C57B/L6 background had similar CVM rates but predominately AAA abnormalities. We have delineated key parameters of Phe cardiovascular teratogenicity, demonstrated the utility of this MPKU model on different mouse strains, and shown how genetic background profoundly affects the phenotype. PMID:22951387
Wang, De-Gao; Steer, Helena; Tait, Tara; Williams, Zackery; Pacepavicius, Grazina; Young, Teresa; Ng, Timothy; Smyth, Shirley Anne; Kinsman, Laura; Alaee, Mehran
2013-10-01
A comprehensive surveillance program was conducted to determine the occurrence of three cyclic volatile methylsiloxanes (cVMS) octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) in environmental compartments impacted by wastewater effluent discharges. Eleven wastewater treatment plants (WWTPs), representative of those found in Southern Ontario and Southern Quebec, Canada, were investigated to determine levels of cVMS in their influents and effluents. In addition, receiving water and sediment impacted by WWTP effluents, and biosolid-amended soil from agricultural fields were also analyzed for a preliminary evaluation of the environmental exposure of cVMS in media impacted by wastewater effluent and solids. A newly-developed large volume injection (septumless head adapter and cooled injection system) gas chromatography - mass spectrometry method was used to avoid contamination originating from instrumental analysis. Concentrations of D4, D5, and D6 in influents to the 11 WWTPs were in the range 0.282-6.69μgL(-1), 7.75-135μgL(-1), and 1.53-26.9μgL(-1), respectively. In general, wastewater treatment showed cVMS removal rates of greater than 92%, regardless of treatment type. The D4, D5, and D6 concentration ranges in effluent were <0.009-0.045μgL(-1), <0.027-1.56μgL(-1), and <0.022-0.093μgL(-1), respectively. The concentrations in receiving water influenced by effluent, were lower compared to those in effluent in most cases, with the ranges <0.009-0.023μgL(-1), <0.027-1.48μgL(-1), and <0.022-0.151μgL(-1) for D4, D5, and D6, respectively. Sediment concentrations ranged from <0.003-0.049μgg(-1)dw, 0.011-5.84μgg(-1)dw, and 0.004-0.371μgg(-1)dw for D4, D5, and D6, respectively. The concentrations in biosolid-amended soil, having values of <0.008-0.017μgg(-1)dw, <0.007-0.221μgg(-1)dw, and <0.009-0.711μgg(-1)dw for D4, D5, and D6, respectively, were lower than those in sediment impacted by wastewater effluent in most cases. In comparison with the no-observed-effected concentrations (NOEC) and IC50 (concentration that causes 50% inhibition of the response) values, the potential risks to aquatic, sediment-dwelling, and terrestrial organisms from these reported concentrations are low. Crown Copyright © 2012. Published by Elsevier Ltd. All rights reserved.
Chen, Ying; Xu, Pengcheng; Li, Xinxin
2010-07-02
This paper presents a novel sensing layer modification technique for static micro-cantilever sensors that detect trace explosives by measuring specific adsorption-induced surface stress. For the first time, a method of directly modifying a siloxane sensing bilayer on an SiO(2) surface is proposed to replace the conventional self-assembled monolayers (SAMs) of thiols on Au to avoid the trouble from long-term unstable Au-S bonds. For modifying the long-term reliable sensing bilayer on the piezoresistor-integrated micro-cantilevers, a siloxane-head bottom layer is self-assembled directly on the SiO(2) cantilever surface, which is followed by grafting another explosive-sensing-group functionalized molecule layer on top of the siloxane layer. The siloxane-modified sensor has experimentally exhibited a highly resoluble response to 0.1 ppb TNT vapor. More importantly, the repeated detection results after 140 days show no obvious attenuation in sensing signal. Also observed experimentally, the specific adsorption of the siloxane sensing bilayer to TNT molecules causes a tensile surface stress on the cantilever. Herein the measured tensile surface stress is in contrast to the compressive surface stress normally measured from conventional cantilever sensors where the sensitive thiol-SAMs are modified on an Au surface. The reason for this newly observed phenomenon is discussed and preliminarily analyzed.
Adsorption characteristics of siloxanes in landfill gas by the adsorption equilibrium test.
Nam, Sangchul; Namkoong, Wan; Kang, Jeong-Hee; Park, Jin-Kyu; Lee, Namhoon
2013-10-01
Due to the increase in energy cost by constantly high oil prices and the obligation to reduce greenhouse effect gases, landfill gas is frequently used as an alternative energy source for producing heat and electricity. Most of landfill gas utility facilities, however, are experiencing problems controlling siloxanes from landfill gas as their catalytic oxidizers are becoming fouled by silicon dioxide dust. To evaluate adsorption characteristics of siloxanes, an adsorption equilibrium test was conducted and parameters in the Freundlich and Langmuir isotherms were analyzed. Coconut activated carbon (CA1), coal activated carbon (CA2), impregnated activated carbon (CA3), silicagel (NCA1), and activated alumina (NCA2) were used for the adsorption of the mixed siloxane which contained hexamethyldisiloxane (L2), octamethylcyclotetrasiloxane (D4), and decamethylcyclopentasiloxane (D5). L2 had higher removal efficiency in noncarbon adsorbents compared to carbon adsorbents. The application of Langmuir and Freundlich adsorption isotherm demonstrated that coconut based CA1 and CA3 provided higher adsorption capacity on L2. And CA2 and NCA1 provided higher adsorption capacity on D4 and D5. Based on the experimental results, L2, D4, and D5 were converted by adsorption and desorption in noncarbon adsorbents. Adsorption affinity of siloxane is considered to be affect by the pore size distribution of the adsorbents and by the molecular size of each siloxane. Copyright © 2013 Elsevier Ltd. All rights reserved.
Ekin, Abdullah; Webster, Dean C
2007-01-01
Libraries of siloxane-polyurethane coatings were designed, formulated, and screened using high-throughput experimentation. Four independent variables that were analyzed were the molecular weight of poly(dimethylsiloxane) (PDMS), presence or absence of poly(epsilon-caprolactone) (PCL) blocks attached to the PDMS backbone, the length of the PCL blocks, and the siloxane polymer level in the coating formulations. In addition to the siloxane libraries (3-aminopropyl-terminated PDMS and poly(epsilon-caprolactone)-poly(dimethylsiloxane)-poly(epsilon-caprolactone) (PCL-PDMS-PCL) triblock copolymers), the coating formulation included a trifunctional isocyanate crosslinker, trifunctional poly(epsilon-caprolactone) polyol, 2,4-pentanedione (pot-life extender), dibutyltin diacetate (catalyst), and a blend of solvents. The resulting coatings were analyzed for their surface energy and pseudobarnacle adhesion both before and after aging the coatings for 30 days in water. The water and methylene iodide contact angle averages increase with increasing molecular weight of PDMS. Coatings prepared from PCL-PDMS-PCL triblock copolymers have lower surface energies than coatings prepared from 3-aminopropyl-terminated PDMS; however, lower pseudobarnacle adhesion results were obtained for the coatings prepared from 3-aminopropyl-terminated PDMS than coatings prepared from PCL-PDMS-PCL triblock copolymers. The siloxane polymer level in the coating formulations does not have a significant effect on the surface energy of the coatings, but it resulted in higher pseudobarnacle adhesion.
New dielectric elastomers with improved properties for energy harvesting and actuation
NASA Astrophysics Data System (ADS)
Stiubianu, George; Bele, Adrian; Tugui, Codrin; Musteata, Valentina
2015-02-01
New materials with large value for dielectric constant were obtained by using siloxane and chemically modified lignin. The modified lignin does not act as a stiffening filler material for the siloxane but acts as bulk filler, preserving the softness and low value of Young's modulus specific for silicones. The measured values for dielectric constant compare positively with the ones for previously tested dielectric elastomers based on siloxane rubber or acrylic rubber loaded with ceramic nanoparticles. The new materials use the well-known silicone chemistry and lignin which is available worldwide in large amounts as a by-product of pulp and paper industry, making its manufacturing affordable. The prepared dielectric elastomers were tested for possible applications for wave, wind and kinetic body motion energy harvesting. Siloxane, lignin, dielectric
Pakhomova, A A; Aksel'-Rubinshteĭn, V Z; Mikos, K N; Nikitin, E I
2009-01-01
Analysis of experimental data about the quantitative and qualitative chemical make-up of air in the orbital station Mir and International space station (ISS) showed a permanent presence of silicon. The main source of silicon contaminants seems to be a variety of polymethyl siloxane liquids and siloxane coating of electronics. The article describes the volatile silicon contaminants detected in space stations air. To control concentrations of silicon, the existing air purification system needs to be augmented with carbons having the micropore entrance larger than diameters of silicon-containing molecules. It is also important to elaborate the technology of polymethyl siloxane liquids synthesis so as to reduce the amount of volatile admixtures emission and to observe rigorously the pre-flight off-gassing requirements with special concern about silicon coatings.
1979-06-01
LUOROALKYL SILOXANES AS LIQUID-JEPELLENT FABiRIC FINISHES YARUJF- THE 1OMOPOLYMERS AND /,THEIR CUPOLYMERS WITH !IxKL LALEK i.W o D DC BEST AVAILABLE...NATIONAL DEFENCE CANADA DEFENCE RESEARCH ESTABLISHMENT OTTAWA REPORT NO. 804 FLUOROALKYL SILOXANES AS LIQUID-REPELLENT FABRIC FINISHES PART II THE...cent) and cotton as finishes , and the oil and water repellency imparted to these fabrics ascertained by standard tests. In this manner it is possible
Gas production in the radiolysis of Poly(dimethysiloxanes)
NASA Astrophysics Data System (ADS)
LaVerne, Jay A.; Tratnik, Nicole A. I.; Sasgen, Andrea
2018-01-01
A variety of small poly(dimethyl siloxanes) were irradiated with γ-rays followed by the determination of the production of methane and molecular hydrogen and characterization of spectroscopic changes in the medium. The yields of methane was found to be about twice that of molecular hydrogen indicating that breakage of the C-Si bond occurs at a frequency comparable to the breakage of the C-H bond. Both yields slowly decrease with increasing molecular weight of the medium. The presence of oxygen decreases the yield of both gases suggesting radical precursors to methane and molecular hydrogen, presumably the methyl radical and H atom, respectively. Temperature gravimetric analysis and UV-visible spectroscopy both suggest the formation of higher molecular weight compounds with radiolysis, which agrees with bond loss and formation observed in infrared spectroscopy.
Food web accumulation of cyclic siloxanes in Lake Mjøsa, Norway.
Borgå, Katrine; Fjeld, Eirik; Kierkegaard, Amelie; McLachlan, Michael S
2012-06-05
The biomagnification of the cyclic volatile methyl siloxanes octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexatetrasiloxane (D6) was analyzed in the Lake Mjøsa food web in Norway from zooplankton and Mysis to planktivorous and piscivorous fish. The trophic magnification factor (TMF) for D5 was determined and compared with TMFs of several legacy contaminants: polychlorinated biphenyl (PCB) congeners 153 and 180, polybrominated diphenyl ether (PBDE) congeners 47 and 99, and p,p'-DDE. D5 showed TMF significantly greater than 1, implying food web biomagnification (TMF = 2.28, CI: 1.22-4.29). This contrasts with two studies that reported TMF < 1, which may reflect variability in TMF between food webs. The Lake Mjøsa D5 TMF was sensitive to the species included at the higher trophic level; whole food web TMF differed from TMF excluding smelt (Osmerus eperlanus) or brown trout (Salmo trutta) (TMF(-SMELT) = 1.62, CI: 0.96-2.72; TMF(-TROUT) = 3.58, CI: 1.82-7.03). For legacy contaminants (e.g., PCB-153 and PCB-180), the TMFs were less sensitive to the food web composition, and a better model fit was obtained compared to D5. The differences in biomagnification behavior between D5 and the legacy contaminants suggest that the biomagnification of D5 is being governed by species-specific properties such as biotransformation rate or tissue distribution that differ from those of legacy contaminants.
Enzymatic synthesis of lignin-siloxane hybrid functional polymers.
Prasetyo, Endry Nugroho; Kudanga, Tukayi; Fischer, Roman; Eichinger, Reinhard; Nyanhongo, Gibson S; Guebitz, Georg M
2012-02-01
This study combines the properties of siloxanes and lignin polymers to produce hybrid functional polymers that can be used as adhesives, coating materials, and/or multifunctionalized thin-coating films. Lignin-silica hybrid copolymers were synthesized by using a sol-gel process. Laccases from Trametes hirsuta were used to oxidize lignosulphonates to enhance their reactivity towards siloxanes and then were incorporated into siloxane precursors undergoing a sol-gel process. In vitro copolymerization studies using pure lignin monomers with aminosilanes or ethoxytrimethylsilane and analysis by ²⁹Si NMR spectroscopy revealed hybrid products. Except for kraft lignin, an increase in lignin concentration positively affected the tensile strength in all samples. Similarly, the viscosity generally increased in all samples with increasing lignin concentration and also affected the curing time. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Substrate-Independent Surface Energy Tuning via Siloxane Treatment for Printed Electronics.
Schlisske, Stefan; Held, Martin; Rödlmeier, Tobias; Menghi, Silvia; Fuchs, Kathleen; Ruscello, Marta; Morfa, Anthony J; Lemmer, Uli; Hernandez-Sosa, Gerardo
2018-05-29
Digital printing enables solution processing of functional materials and opens a new route to fabricate low-cost electronic devices. One crucial parameter that affects the wettability of inks for all printing techniques is the surface free energy (SFE) of the substrate. Siloxanes, with their huge variety of side chains and their ability to form self-assembled monolayers, offer exhaustive control of the substrate SFE from hydrophilic to hydrophobic. Thus, siloxane treatment is a suitable approach to adjust the substrate conditions to the desired ink, instead of optimizing the ink to an arbitrary substrate. In this work, the influence of different fluorinated and nonfluorinated siloxanes on the SFE of different substrates, such as polymers, glasses, and metals, are examined. By mixing several siloxanes, we demonstrate the fine tuning of the surface energy. The polar and dispersive components of the SFE are determined by the Owens-Wendt-Rabel-Kaelble (OWRK) method. Furthermore, the impact of the siloxanes and therefore the SFE on the pinning of droplets and wet films are assessed via dynamic contact angle measurements. SFE-optimized substrates enable tailoring the resolution of inkjet printed silver structures. A nanoparticulate silver ink was used for printing single drops, lines, and source-drain electrodes for transistors. These were examined in terms of diameter, edge quality, and functionality. We show that by adjusting the SFE of an arbitrary substrate, the printed resolution is substantially increased by minimizing the printed drop size by up to 70%.
Direct conversion of hydride- to siloxane-terminated silicon quantum dots
Anderson, Ryan T.; Zang, Xiaoning; Fernando, Roshan; ...
2016-10-20
Here, peripheral surface functionalization of hydride-terminated silicon quantum dots (SiQD) is necessary in order to minimize their oxidation/aggregation and allow for solution processability. Historically thermal hydrosilylation addition of alkenes and alkynes across the Si-H surface to form Si-C bonds has been the primary method to achieve this. Here we demonstrate a mild alternative approach to functionalize hydride-terminated SiQDs using bulky silanols in the presence of free-radical initiators to form stable siloxane (~Si-O-SiR 3) surfaces with hydrogen gas as a byproduct. This offers an alternative to existing methods of forming siloxane surfaces that require corrosive Si-Cl based chemistry with HCl byproducts.more » A 52 nm blue shift in the photoluminescent spectra of siloxane versus alkyl-functionalized SiQDs is observed that we explain using computational theory. Model compound synthesis of silane and silsesquioxane analogues is used to optimize surface chemistry and elucidate reaction mechanisms. Thorough characterization on the extent of siloxane surface coverage is provided using FTIR and XPS. As a result, TEM is used to demonstrate SiQD size and integrity after surface chemistry and product isolation.« less
Carbon dioxide absorbent and method of using the same
Perry, Robert James; O'Brien, Michael Joseph
2015-12-29
In accordance with one aspect, the present invention provides a composition which contains the amino-siloxane structures I, or III, as described herein. The composition is useful for the capture of carbon dioxide from process streams. In addition, the present invention provides methods of preparing the amino-siloxane composition. Another aspect of the present invention provides methods for reducing the amount of carbon dioxide in a process stream employing the amino-siloxane compositions of the invention, as species which react with carbon dioxide to form an adduct with carbon dioxide.
Carbon dioxide absorbent and method of using the same
Perry, Robert James; O'Brien, Michael Joseph
2014-06-10
In accordance with one aspect, the present invention provides a composition which contains the amino-siloxane structures I, or III, as described herein. The composition is useful for the capture of carbon dioxide from process streams. In addition, the present invention provides methods of preparing the amino-siloxane composition. Another aspect of the present invention provides methods for reducing the amount of carbon dioxide in a process stream employing the amino-siloxane compositions of the invention, as species which react with carbon dioxide to form an adduct with carbon dioxide.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Das, Ujjal; Zhang, Guanghui; Hu, Bo
2015-10-28
Amorphous silica (SiO 2) is commonly used as a support in heterogeneous catalysis. However, due to the structural disorder and temperature induced change of surface morphology, the structures of silica supported metal catalysts are difficult to determine. Most studies are primarily focused on understanding the interactions of different types of surface hydroxyl groups with metal ions. In comparison, the effect of siloxane ring size on the structure of silica supported metal catalysts and how it affects catalytic activity is poorly understood. Here, we have used density functional theory calculations to understand the effect of siloxane ring strain on structure andmore » activity of different monomeric Lewis acid metal sites on silica. In particular, we have found that large siloxane rings favor strong dative bonding interaction between metal ion and surface hydroxyls, leading to the formation of high-coordinate metal sites. In comparison, metal-silanol interaction is weak in small siloxane rings, resulting in low-coordinate metal sites. The physical origin of this size dependence is associated with siloxane ring strain, and, a correlation between metal-silanol interaction energy and ring strain energy has been observed. In addition to ring strain, the strength of the metal-silanol interaction also depends on the positive charge density of the cations. In fact, a correlation also exists between metal-silanol interaction energy and charge density of several first-row transition and post-transition metals. The theoretical results are compared with the EXAFS data of monomeric Zn(II) and Ga(III) ions grafted on silica. In conclusion, the molecular level insights of how metal ion coordination on silica depends on siloxane ring strain and cation charge density will be useful in the synthesis of new catalysts.« less
Elastomeric nanoparticle composites covalently bound to Al2O3/GaAs surfaces.
Song, Hyon Min; Ye, Peide D; Ivanisevic, Albena
2007-08-28
This article reports the modification of Al2O3/GaAs surfaces with multifunctional soft materials. Siloxane elastomers were covalently bound to dopamine-modified Al2O3/GaAs semiconductor surfaces using MPt (M = Fe, Ni) nanoparticles. The sizes of the monodisperse FePt and NiPt nanoparticles were less than 5 nm. The surfaces of the nanoparticles as well as the Al2O3/GaAs substrates were modified with allyl-functionalized dopamine that utilized a dihydroxy group as a strong ligand. The immobilization of the elastomers was performed via a hydrosilation reaction of the allyl-functionalized dopamines with the siloxane backbones. X-ray photoelectron spectroscopy (XPS) experiments confirmed the covalent bonding of the siloxane elastomers to the oxide layer on the semiconductor surface. Fourier transform-infrared reflection absorption spectroscopy (FT-IRRAS) measurements revealed that the allyl functional groups are bonded to the siloxane backbones. The FT-IRRAS data also showed that the density of the allyl groups on the surface was lower than that of the siloxane backbones. The mechanical properties of the surface-bound nanocomposites were tested using nanoindentation experiments. The nanoindentation data showed that the soft matrix composed of the elastomeric coating on the surfaces behaves differently from the inner, hard Al2O3/GaAs substrate.
Gamma radiation effects on siloxane-based additive manufactured structures
NASA Astrophysics Data System (ADS)
Schmalzer, Andrew M.; Cady, Carl M.; Geller, Drew; Ortiz-Acosta, Denisse; Zocco, Adam T.; Stull, Jamie; Labouriau, Andrea
2017-01-01
Siloxane-basedadditive manufactured structures prepared by the direct ink write (DIW) technology were exposed to ionizing irradiation in order to gauge radiolysis effects on structure-property relationships. These well-defined 3-D structures were subjected to moderate doses of gamma irradiation in an inert atmosphere and characterized by a suite of experimental methods. Changes in thermal, chemical, microstructure, and mechanical properties were evaluated by DSC, TGA, FT-IR, mass spectroscopy, EPR, solvent swelling, SEM, and uniaxial compressive load techniques. Our results demonstrated that 3-D structures made from aromatic-free siloxane resins exhibited hardening after being exposed to gamma radiation. This effect was accompanied by gas evolution, decreasing in crystallization levels, decreasing in solvent swelling and damage to the microstructure. Furthermore, long-lived radiation-induced radicals were not detected by EPR methods. Our results are consistent with cross-link formation being the dominant degradation mechanism over chain scission reactions. On the other hand, 3-D structures made from high phenyl content siloxane resins showed little radiation damage as evidenced by low off gassing.
Campos, A A; Nathanson, D
1999-10-01
Addition silicones (polyvinyl siloxanes) are universally accepted as accurate and stable impression materials. They have also gained popularity as interocclusal record materials. However, it has not been defined if it is possible to work with polyvinyl siloxanes without changing the recorded maxillomandibular relations. This study examined the compressibility of 2 addition silicones as interocclusal record materials, analyzing the changes of maxillomandibular relations at the condyle region when different compressive forces are used to stabilize articulated casts. Sixteen interocclusal records, obtained from the same patient (8 of each polyvinyl siloxane, Blu-Mousse, Fast Set), were interposed between the patient casts in a new measuring system obtaining 48 curves of load versus maxillomandibular positional changes in 3 axes (x, y, z). These curves were compared with curves obtained with the casts in maximum intercuspation without interocclusal records (reference curves). Analysis of variance was used to compare maxillomandibular positional changes among the 3 groups (n = 48 each): Blu-Mousse, Fast Set, and control group or maximum intercuspation without interocclusal record. There was no significant change in maxillomandibular relations when forces up to 1 kgf were applied to stabilize the casts related by means of Blu-Mousse and Fast Set addition silicone interocclusal records. It is possible to use these polyvinyl siloxanes as interocclusal record materials without changing the recorded maxillomandibular relations.
Fokkinga, Wietske A; Witter, Dick J; Bronkhorst, Ewald M; Creugers, Nico H
The aim of this study was to analyze the clinical fit of metal-frame partial removable dental prostheses (PRDPs) based on custom trays used with alginate or polyvinyl siloxane impression material. Fifth-year students of the Nijmegen Dental School made 25 correct impressions for 23 PRDPs for 21 patients using alginate, and 31 correct impressions for 30 PRDPs for 28 patients using polyvinyl siloxane. Clinical fit of the framework as a whole and of each retainer separately were evaluated by calibrated supervisors during framework try-in before (first evaluation) and after (second evaluation) possible adjustments (score 0 = poor fit, up to score 3 = good fit). Framework fit and fit of the denture base were evaluated at delivery (third evaluation). Finally, postinsertion sessions were evaluated and total number of sessions needed, sore spots, adjustments to the denture base, and reported food-impaction were recorded. No significant differences in clinical fit (of the framework as a whole, for the retainers, or for the denture base) were found between the groups in the three evaluation sessions. Differences were not found for postinsertion sessions with one exception: in the alginate group, four subjects reported food impaction, versus none in the polyvinyl siloxane group. Clinical fit of metal-frame PRDPs based on impressions with custom trays combined with alginate or polyvinyl siloxane was similar.
Copolymer sealant compositions and method for making
NASA Technical Reports Server (NTRS)
Singh, Navjot (Inventor); Leman, John Thomas (Inventor); Whitney, John M. (Inventor); Krabbenhoft, Herman Otto (Inventor)
2002-01-01
Condensation curable poly(fluoroorgano)siloxane-poly(silarylene)siloxane block copolymer compositions having a glass transition temperature not exceeding about -54.degree. C. and excellent solvent resistance have been found useful as sealants. Polyalkoxysilylorgano compounds, such as 1,4-bis[trimethoxysilyl(ethyl)]benzene have been found to be effective as cross-linkers.
Copolymer sealant compositions and method for making
NASA Technical Reports Server (NTRS)
Singh, Navjot (Inventor); Leman, John Thomas (Inventor); Whitney, John M. (Inventor); Krabbenhoft, Herman Otto (Inventor)
2004-01-01
Condensation curable poly(fluoroorgano)siloxane-poly(silarylene)siloxane block copolymer compositions having a glass transition temperature not exceeding about -54.degree. C. and excellent solvent resistance have been found useful as sealants. Polyalkoxysilylorgano compounds, such as 1,4-bis[trimethoxysilyl(ethyl)]benzene have been found to be effective as cross-linkers.
Copolymer sealant compositions and method for making
NASA Technical Reports Server (NTRS)
Singh, Navjot (Inventor); Leman, John Thomas (Inventor); Whitney, John M. (Inventor); Krabbenhoft, Herman Otto (Inventor)
2003-01-01
Condensation curable poly(fluoroorgano)siloxane-poly(silarylene)siloxane block copolymer compositions having a glass transition temperature not exceeding about -54.degree. C. and excellent solvent resistance have been found useful as sealants. Polyalkoxysilylorgano compounds, such as 1,4-bis[trimethoxysilyl(ethyl)]benzene have been found to be effective as cross-linkers.
Microstructural Organization of Elastomeric Polyurethanes with Siloxane-Containing Soft Segments
NASA Astrophysics Data System (ADS)
Choi, Taeyi; Weklser, Jadwiga; Padsalgikar, Ajay; Runt, James
2011-03-01
In the present study, we investigate the microstructure of two series of segmented polyurethanes (PUs) containing siloxane-based soft segments and the same hard segments, the latter synthesized from diphenylmethane diisocyanate and butanediol. The first series is synthesized using a hydroxy-terminated polydimethylsiloxane macrodiol and varying hard segment contents. The second series are derived from an oligomeric diol containing both siloxane and aliphatic carbonate species. Hard domain morphologies were characterized using tapping mode atomic force microscopy and quantitative analysis of hard/soft segment demixing was conducted using small-angle X-ray scattering. The phase transitions of all materials were investigated using DSC and dynamic mechanical analysis, and hydrogen bonding by FTIR spectroscopy.
Ultra-high molecular weight silphenylene-siloxane polymers
NASA Technical Reports Server (NTRS)
Patterson, W. J.; Hundley, N. H.; Ludwick, L. M.
1984-01-01
Silphenylene-siloxane copolymers with molecular weights above one million were prepared using a two stage polymerization technique. The technique was successfully scaled up to produce 50 grams of this high polymer in a single run. The reactive monomer approach was also investigated using the following aminosilanes: bis(dimethylamino)dimethylsilane, N,N-bis(pyrrolidinyl)dimethylsilane and N,N-bis(gamma-butyrolactam)dimethylsilane). Thermal analyses were performed in both air and nitrogen. The experimental polymers decomposed at 540 to 562 C, as opposed to 408 to 426 C for commercial silicones. Differential scanning calorimetry showed a glass transition (Tg) at -50 to -55 C for the silphenylene-siloxane copolymer while the commercial silicones had Tg's at -96 to -112 C.
Gu, Qun; David, Frank; Lynen, Frédéric; Vanormelingen, Pieter; Vyverman, Wim; Rumpel, Klaus; Xu, Guowang; Sandra, Pat
2011-05-20
Ionic liquid stationary phases were tested for one dimensional gas chromatography-mass spectrometry (GC-MS) and comprehensive two dimensional gas chromatography (GC×GC) of fatty acid methyl esters from algae. In comparison with polyethylene glycol and cyanopropyl substituted polar stationary phases, ionic liquid stationary phases SLB-IL 82 and SLB-IL 100 showed comparable resolution, but lower column bleeding with MS detection, resulting in better sensitivity. The selectivity and polarity of the ionic liquid phases are similar to a highly polar biscyanopropyl-silicone phase (e.g. HP-88). In GC×GC, using an apolar polydimethyl siloxane×polar ionic liquid column combination, an excellent group-type separation of fatty acids with different carbon numbers and number of unsaturations was obtained, providing information that is complementary to GC-MS identification. Copyright © 2011 Elsevier B.V. All rights reserved.
Zapadlo, Michal; Krupčík, Ján; Kovalczuk, Tomáš; Májek, Pavel; Spánik, Ivan; Armstrong, Daniel W; Sandra, Pat
2011-02-04
A total of 196 out of 209 polychlorobiphenyl (PCB) congeners were resolved using GC×GC-TOFMS with a non-polar/ionic liquid column series consisting of poly(50%-n-octyl-50%-methyl)siloxane and (1,12-di(tripropylphosphonium)dodecane bis(trifluoromethansulfonyl)amide) in the first and second dimension, respectively. It has been found that 13 PCB congeners overlap in five doublets (CB12+CB13, CB62+CB75, CB70+CB76, CB97+CB125 and CB153+CB168) and one triplet (CB90+CB101+CB113). All toxic, "dioxin like" congeners were separated with no interferences from any PCB congener. The 109 PCBs present in Aroclor 1242 and the 82 PCBs present in Aroclor 1260 were resolved GC×GC-TOFMS analysis on this column set. Copyright © 2010 Elsevier B.V. All rights reserved.
Light sensitive polymer obtained by dispersion of azo-functionalized POSS nanoparticles
NASA Astrophysics Data System (ADS)
Miniewicz, A.; Tomkowicz, M.; Karpinski, P.; Sznitko, L.; Mossety-Leszczak, B.; Dutkiewicz, M.
2015-07-01
Hybrid inorganic-organic nanoparticles based on cubic siloxane cage (RSiO3/2)8, known as polyhedral oligosilsesquioxane (POSS), have been functionalized by eight groups of azo-benzene mesogens and dispersed in poly(methyl methacrylate) PMMA matrix. Presence of azo-benzene units adds an important light-driven functionality to the system due to their photoisomerization resulting in refractive index and/or absorption changes of the whole system. The polymer films containing various concentrations of azo-POSS nanoparticles show remarkable changes of surface morphology being either transparent (at low POSS concentration) or highly scattering (at high POSS concentration) for visible light. Surface structures were examined by optical microscopy as well as by atomic force microscopy (AFM). Results of photoinduced alignment are discussed in the framework of light-induced modification of the aliphatic chains containing azo-benzene photoisomerizing moieties and self-organization process.
The Art of Silicones: Bringing Siloxane Chemistry to the Undergraduate Curriculum
ERIC Educational Resources Information Center
Longenberger, Taylor B.; Ryan, Kaleigh M.; Bender, William Y.; Krumpfer, Anna-Katharina; Krumpfer, Joseph W.
2017-01-01
Siloxane polymers and silicone materials are major components in most people's daily lives and are important in a wide variety of applications. However, despite their undeniable importance, they are often overlooked in the traditional undergraduate education, as they do not fall neatly into the traditional categories of organic or inorganic…
Preparation and characterization of siloxane-containing thermoplastic polyimides
NASA Technical Reports Server (NTRS)
Maudgal, S.; St Clair, T. L.
1984-01-01
Copolyimides and homopolyimides of bis(gamma-aminopropyl)tetramethyldisiloxane and 3,3'-diaminobenzophenone have been prepared with benzophenonetetracarboxylic dianhydride. The properties of the copolyimides were compared with those of the homopolyimides to assess the effect of incorporation of siloxane groups in the backbone. Applications of the polymers as adhesives and mouldings are discussed.
Macro and micro wettability of hydrophobic siloxane films with hierarchical surface roughness
NASA Astrophysics Data System (ADS)
Terpilowski, Konrad; Goncharuk, Olena; Gun’ko, Vladimir M.
2018-07-01
A method has been proposed to control the macro- and micro-wetting properties of hydrophobic surfaces through changes in the roughness due to modifying siloxane films with silica microparticles (MP). An experimental and theoretical analysis of macro- and micro-wettability dependence on the roughness of a film surface was carried out by combination of SEM and XPS methods with evaluation of equilibrium contact angles from Tadmor’s equation. SEM images (environmental mode) allowed characterizing the mosaic hydrophobicity/hydrophilicity of the siloxane film surface. Hydrophobic siloxane films filled with silica MP were synthesized on the plasma activated and non-activated glass substrates by the sol-gel dip-coating method using tetraethylorthosilicate based precursor compositions with subsequent reaction with hexamethyldisilazane. The values of water contact angles higher than 150° indicating a superhydrophobic effect were observed for films with combining nano- and micro-hierarchical roughness. Moreover, considering wettability on the micro scale the hybrid effect was discovered and confirmed by the SEM and XPS studies showing the presence of not only hydrophobic but also hydrophilic surface domains.
Novel Low-Temperature Poss-Containing Siloxane Elastomers
NASA Technical Reports Server (NTRS)
Belcher, Marcus A.; Hinkley, Jeffrey A.; Kiri, Neha N.; Lillehei, Peter T.
2008-01-01
One route to increased aircraft performance is through the use of flexible, shape-changeable aerodynamics effectors. However, state of the art materials are not flexible or durable enough over the required broad temperature range. Mixed siloxanes were crosslinked by polyhedral oligomeric silsesquioxanes (POSS) producing novel materials that remained flexible and elastic from -55 to 94 C. POSS molecules were chemically modified to generate homogeneous distributions within the siloxane matrix. High resolution scanning electron microscope (HRSEM) images indicated homogenous POSS distribution up to 0.8 wt %. Above the solubility limit, POSS aggregates could be seen both macroscopically and via SEM (approx.60-120 nm). Tensile tests were performed to determine Young s modulus, tensile strength, and elongation at break over the range of temperatures associated with transonic aircraft use (-55 to 94 C; -65 to 200 F). The siloxane materials developed here maintained flexibility at -55 C, where previous candidate materials failed. At room temperature, films could be elongated up to 250 % before rupturing. At -55 and 94 C, however, films could be elongated up to 400 % and 125 %, respectively.
Fuel Flexibility: Landfill Gas Contaminant Mitigation for Power Generation
DOE Office of Scientific and Technical Information (OSTI.GOV)
Storey, John Morse; Theiss, Timothy J; Kass, Michael D
This research project focused on the mitigation of silica damage to engine-based renewable landfill gas energy systems. Characterization of the landfill gas siloxane contamination, combined with characterization of the silica deposits in engines, led to development of two new mitigation strategies. The first involved a novel method for removing the siloxanes and other heavy contaminants from the landfill gas prior to use by the engines. The second strategy sought to interrupt the formation of hard silica deposits in the engine itself, based on inspection of failed landfill gas engine parts. In addition to mitigation, the project had a third taskmore » to develop a robust sensor for siloxanes that could be used to control existing and/or future removal processes.« less
Thiol-Ene functionalized siloxanes for use as elastomeric dental impression materials
Cole, Megan A.; Jankousky, Katherine C.; Bowman, Christopher N.
2014-01-01
Objectives Thiol- and allyl-functionalized siloxane oligomers are synthesized and evaluated for use as a radical-mediated, rapid set elastomeric dental impression material. Thiol-ene siloxane formulations are crosslinked using a redox-initiated polymerization scheme, and the mechanical properties of the thiol-ene network are manipulated through the incorporation of varying degrees of plasticizer and kaolin filler. Formulations with medium and light body consistencies are further evaluated for their ability to accurately replicate features on both the gross and microscopic levels. We hypothesize that thiol-ene functionalized siloxane systems will exhibit faster setting times and greater detail reproduction than commercially available polyvinylsiloxane (PVS) materials of comparable consistencies. Methods Thiol-ene functionalized siloxane mixtures formulated with varying levels of redox initiators, plasticizer, and kaolin filler are made and evaluated for their polymerization speed (FTIR), consistency (ISO4823.9.2), and surface energy (goniometer). Feature replication is evaluated quantitatively by SEM. The Tg, storage modulus, and creep behavior are determined by DMA. Results Increasing redox initiation rate increases the polymerization rate but at high levels also limits working time. Combining 0.86 wt% oxidizing agent with up to 5 wt% plasticizer gave a working time of 3 min and a setting time of 2 min. The selected medium and light body thiol-ene formulations also achieved greater qualitative detail reproduction than the commercial material and reproduced micrometer patterns with 98% accuracy. Significance Improving detail reproduction and setting speed is a primary focus of dental impression material design and synthesis. Radical-mediated polymerizations, particularly thiol-ene reactions, are recognized for their speed, reduced shrinkage, and ‘click’ nature. PMID:24553250
Friesen, Dwayne T.; Obligin, Alan S.
1989-01-01
Composite cellulosic semipermeable membranes are disclosed which are the covalently bonded reaction product of an asymmetric cellulosic semipermeable membrane and a polysiloxane containing reactive functional groups. The two reactants chemically bond by ether, ester, amide or acrylate linkages to form a siloxane-grafted cellulosic membrane having superior selectivity and flux stability. Selectivity may be enhanced by wetting the surface with a swelling agent such as water.
1987-07-16
inorganic plastics since the siloxanes . They have great potential and may in time prove to be even more useful than the polysiloxanes since many of these...important new class of seni-inorganic plastics since the siloxanes . They have great potential and may in time prove to be even more useful than the... biomedical qualities and useful engineering material parameters, toxicological, corrosion and fire resistance characteristics place many of the
Friesen, D.T.; Obligin, A.S.
1989-10-31
Composite cellulosic semipermeable membranes are disclosed which are the covalently bonded reaction product of an asymmetric cellulosic semipermeable membrane and a polysiloxane containing reactive functional group. The two reactants chemically bond by ether, ester, amide or acrylate linkages to form a siloxane-grafted cellulosic membrane having superior selectivity and flux stability. Selectivity may be enhanced by wetting the surface with a swelling agent such as water.
Synthesis and Thermal Stability of Novel Poly(M-Carborane-Siloxanes) with Various Pendant Groups
NASA Astrophysics Data System (ADS)
Yang, Xiaoxue; Zhao, Yanyan; Wang, Cuicui; Zhang, Xiaoa; Jiang, Shengling; Lyu, Yafei
2017-10-01
Poly(m-carborane-siloxanes) with various pendant groups (P15-P46) were synthesized via polycondensation of m-carborane-containing disilanols (1-4) and highly active bisureidosilanes (5 and 6). The obtained polymers exhibit controlled molecular weight by carefully adjusting the monomer ratio. Standard spectroscopic techniques including FTIR and NMR were utilized to characterize these polymers and satisfactory results were obtained. TGA analysis indicated that the thermal cyclization of polysiloxanes under nitrogen was greatly postponed by the incorporated m-carborane cage, since the siloxane bonds within the main chain were strengthened by the inductive effect of the latter. DSC and FTIR results confirmed that both siloxane unit and carborane cage were oxidized at elevated temperature under air, which contributed to the transformation of the polymers into the mixture of SiO2 and B2O3. Therefore, high char yield was obtained. Besides, the electronic effect of pendant groups greatly influenced the degradation behavior of m-carborane-containing polysiloxanes, having nothing to do with their position. The initial degradation temperature (T d5) increases with varying substituent in the order: CH2CH2CF3 < CH3 ≈ Ph < CH=CH2.
Cyclic volatile methylsiloxanes in fish from the Baltic Sea.
Kierkegaard, Amelie; Bignert, Anders; McLachlan, Michael S
2013-10-01
Laboratory studies suggest that the cyclic volatile methylsiloxanes (cVMS) octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) will persist in the aquatic environment and bioaccumulate in fish. Here these cVMS were measured in herring collected in the Swedish waters of the Baltic Sea and the North Sea and in grey seals from the Baltic Proper. D4, D5, and D6 were present in herring muscle at concentrations around 10, 200, and 40ngg(-1) lipid weight, respectively. The ratio of these concentrations was similar to the relative magnitude of estimated emissions to water, suggesting that the efficiency of overall transfer through the environment and food web was similar (within a factor 2-3) for the three chemicals. The concentrations of D5 and D6 were similar in herring caught in the highly populated Baltic Proper and in the less populated Bothnian Sea and Bothnian Bay. The D4 concentrations were lower at the most remote northern station, suggesting that D4 is less persistent than D5 and D6. Herring from the North Sea had lower levels of all three chemicals. The concentrations of D4, D5 and D6 in grey seal blubber were lower than the lipid normalized concentrations in herring, indicating that they do not biomagnify in grey seals. Copyright © 2012 Elsevier Ltd. All rights reserved.
Maternal caffeine consumption and risk of cardiovascular malformations.
Browne, Marilyn L; Bell, Erin M; Druschel, Charlotte M; Gensburg, Lenore J; Mitchell, Allen A; Lin, Angela E; Romitti, Paul A; Correa, Adolfo
2007-07-01
The physiologic effects and common use of caffeine during pregnancy call for examination of maternal caffeine consumption and risk of birth defects. Epidemiologic studies have yielded mixed results, but such studies have grouped etiologically different defects and have not evaluated effect modification. The large sample size and precise case classification of the National Birth Defects Prevention Study allowed us to examine caffeine consumption and specific cardiovascular malformation (CVM) case groups. We studied consumption of caffeinated coffee, tea, soda, and chocolate to estimate total caffeine intake and separately examined exposure to each caffeinated beverage. Smoking, alcohol, vasoactive medications, folic acid supplement use, and infant gender were evaluated for effect modification. Maternal interview reports for 4,196 CVM case infants overall and 3,957 control infants were analyzed. We did not identify any significant positive associations between maternal caffeine consumption and CVMs. For tetralogy of Fallot, nonsignificant elevations in risk were observed for moderate (but not high) caffeine intake overall and among nonsmokers (ORs of 1.3 to 1.5). Risk estimates for both smoking and consuming caffeine were less than the sum of the excess risks for each exposure. We observed an inverse trend between coffee intake and risk of atrial septal defect; however, this single significant pattern of association might have been a chance finding. Our study found no evidence for an appreciable teratogenic effect of caffeine with regard to CVMs. (c) 2007 Wiley-Liss, Inc.
Kim, Yong Ho; Lim, Young-Woo; Kim, Yun Hyeok; Bae, Byeong-Soo
2016-04-06
We report vinyl-phenyl siloxane hybrid material (VPH) that can be used as a matrix for copper-clad laminates (CCLs) for high-frequency applications. The CCLs, with a VPH matrix fabricated via radical polymerization of resin blend consisting of sol-gel-derived linear vinyl oligosiloxane and bulky siloxane monomer, phenyltris(trimethylsiloxy)silane, achieve low dielectric constant (Dk) and dissipation factor (Df). The CCLs with the VPH matrix exhibit excellent dielectric performance (Dk = 2.75, Df = 0.0015 at 1 GHz) with stability in wide frequency range (1 MHz to 10 GHz) and at high temperature (up to 275 °C). Also, the VPH shows good flame resistance without any additives. These results suggest the potential of the VPH for use in high-speed IC boards.
Catalysts and Initiators as Instruments Controlling Structure of Polymers with Inorganic Backbone.
1991-05-02
lipophobic, electron reach/poor, mesogenic, bioactive , etc. Most modifications have been performed on polyphosphazenes (nucleophilic displacement of...chlorines) and on partially hydrogenated siloxanes (hydrosilylation). Modifications of polysilanes is also known. In this aiticle the main emphasis will...groups6 ,7 . Poly(dimethylsiloxane) is probably the only siloxane polymer which does not form a mesophase and has only one first order thermal
NASA Astrophysics Data System (ADS)
Gardella, Joseph A.; Mahoney, Christine M.
2004-06-01
While many XPS and SIMS studies of polymers have detected and quantified segregation of low surface energy blocks or components in copolymers and polymer blends [D. Briggs, in: D.R. Clarke, S. Suresh, I.M. Ward (Eds.), Surface Analysis of Polymers by XPS and Static SIMS, Cambridge University Press, Cambridge, 1998 (Chapter 5).], this paper reports ToF-SIMS studies of direct measurement of the segment length distribution at the surface of siloxane copolymers. These data allow insight into the segregation of particular portions of the oligomeric distribution; specifically, in this study, longer PDMS oligomers segregated at the expense of shorter PDMS chains. We have reported XPS analysis of competitive segregation effects for short PDMS chains [Macromolecules 35 (13) (2002) 5256]. In this study, a series of poly(ureaurethane)-poly(dimethylsiloxane) (PUU-PDMS) copolymers have been synthesized containing varying ratios of G-3 and G-9 (G- X describes the average segment length of the PDMS added), while maintaining a constant overall siloxane weight percentage (10, 30, and 60%). These copolymers were utilized as model systems to study the preferential segregation of certain siloxane segment lengths to the surface over others. ToF-SIMS analysis of PUU-PDMS copolymers has yielded high-mass range copolymer fragmentation patterns containing intact PDMS segments. For the first time, this information is utilized to determine PDMS segment length distributions at the copolymer surface as compared to the bulk. The results show that longer siloxane segment lengths are preferentially segregating to the surface over shorter chain lengths. These results also show the importance of ToF-SIMS and mass spectrometry in the development of new materials containing low molecular weight amino-propyl-terminated siloxanes.
Raich-Montiu, J; Ribas-Font, C; de Arespacochaga, N; Roig-Torres, E; Broto-Puig, F; Crest, M; Bouchy, L; Cortina, J L
2014-02-17
Siloxanes and trimethylsilanol belong to a family of organic silicone compounds that are currently used extensively in industry. Those that are prone to volatilisation become minor compounds in biogas adversely affecting energetic applications. However, non-standard analytical methodologies are available to analyse biogas-based gaseous matrixes. To this end, different sampling techniques (adsorbent tubes, impingers and tedlar bags) were compared using two different configurations: sampling directly from the biogas source or from a 200 L tedlar bag filled with biogas and homogenised. No significant differences were apparent between the two sampling configurations. The adsorbent tubes performed better than the tedlar bags and impingers, particularly for quantifying low concentrations. A method for the speciation of silicon compounds in biogas was developed using gas chromatography coupled with mass spectrometry working in dual scan/single ion monitoring mode. The optimised conditions could separate and quantify eight siloxane compounds (L2, L3, L4, L5, D3, D4, D5 and D6) and trimethylsilanol within fourteen minutes. Biogas from five waste water treatment plants located in Spain, France and England was sampled and analysed using the developed methodology. The siloxane concentrations in the biogas samples were influenced by the anaerobic digestion temperature, as well as the nature and composition of the sewage inlet. Siloxanes D4 and D5 were the most abundant, ranging in concentration from 1.5 to 10.1 and 10.8 to 124.0 mg Nm(-3), respectively, and exceeding the tolerance limit of most energy conversion systems. Copyright © 2013 Elsevier B.V. All rights reserved.
Mitigating the effect of siloxanes on internal combustion engines using landfill gasses
Besmann, Theodore M
2015-01-06
A waste gas combustion method that includes providing a combustible fuel source, in which the combustible fuel source is composed of at least methane and siloxane gas. A sodium source or magnesium source is mixed with the combustible fuel source. Combustion of the siloxane gas of the combustible fuel source produces a silicon containing product. The sodium source or magnesium source reacts with the silicon containing product to provide a sodium containing glass or sodium containing silicate, or a magnesium containing silicate. By producing the sodium containing glass or sodium containing silicate, or the magnesium containing silicate, or magnesium source for precipitating particulate silica instead of hard coating, the method may reduce or eliminate the formation of silica deposits within the combustion chamber and the exhaust components of the internal combustion engine.
Mitigating the effect of siloxanes on internal combustion engines using landfill gasses
Besmann, Theodore M
2014-01-21
A waste gas combustion method that includes providing a combustible fuel source, in which the combustible fuel source is composed of at least methane and siloxane gas. A sodium source or magnesium source is mixed with the combustible fuel source. Combustion of the siloxane gas of the combustible fuel source produces a silicon containing product. The sodium source or magnesium source reacts with the silicon containing product to provide a sodium containing glass or sodium containing silicate, or a magnesium containing silicate. By producing the sodium containing glass or sodium containing silicate, or the magnesium containing silicate, or magnesium source for precipitating particulate silica instead of hard coating, the method may reduce or eliminate the formation of silica deposits within the combustion chamber and the exhaust components of the internal combustion engine.
Physical Aging Studies of Styrene-Butadiene and Carbonate-Siloxane Block Copolymers
1979-11-19
Carbonate-Siloxane Block Copolymers, ,-- by Martin Tant Garth . D D C Prepared for Publication r - r-on n[? in the JAN Journal of Applied Polymer Science B...revereie ifI nocesy and Identify by black mumibo,) Polymer glasses Non equilibrium glasses Stress relaxation Block copolymers 20. AOSTRACT (Continwaon...copolymers in material applications. -2- Introduction The physical aging phenomenon in glassy polymers has drawn considerable interest within the
DOE Office of Scientific and Technical Information (OSTI.GOV)
Vetter, L. de; Cnudde, V.; Masschaele, B.
This article explores the potential of a scanning electron microscope with an energy dispersive X-ray spectrometer in combination with a new non-destructive 3D visualization technique, X-ray micro-computed tomography, as detection methods for siloxanes/silanes mixtures applied as wood preservatives. In order to have a higher contrast, bromine functional silane was added to the mixture. Scots pine and beech samples were dipped or impregnated with the mixture and subsequently scanned. Both silicon and bromine were easily detectable with both techniques. Dipped siloxanes/silanes covered the cell walls partly in beech and the lumen partly or completely in Scots pine. Impregnated siloxanes/silanes could bemore » found in the cell walls of both wood species. From the results, it can be concluded that, under the circumstances as described in the article, impregnation with a siloxane is necessary to have cell wall penetration. The combination of scanning electron microscopy, energy dispersive X-ray spectroscopy and micro-computed tomography can offer important information concerning the localization of certain products inside wood. While the last of these can monitor changes in 3D, the other two techniques can provide detailed 2D information. Both techniques are complementary and provide important extra information.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Schweigkofler, M.; Niessner, R.
1999-10-15
Biogases such as landfill gas and sewage gas undergo a combustion process which is generating electric energy. Since several trace compounds such as siloxanes (also halogenated and sulfur compounds) are known to cause severe problems to these gas combustion engines, they are of particular interest. In this work, a new technique for sampling, identification, and quantification of siloxanes and volatile organic carbon (VOC) in landfill gas and sewage gas is presented. After sample collection using evacuated stainless steel canisters biogas was analyzed by gas chromatography-mass spectrometry/atomic emission spectroscopy (GC-MS/AES). Using gas canisters, the sampling process was simplified (no vacuum pumpmore » needed), and multiple analysis was possible. The simultaneous application of MSD and AED allowed a rapid screening of silicon compounds in the complex biogases. Individual substances were identified independently both by MSD analysis and by determination of their elemental constitution. Quantification of trace compounds was achieved using a 30 component external standard containing siloxanes, organochlorine and organosulfur compounds, alkanes, terpenes, and aromatic compounds. Precision, linearity, and detection limits have been studied. In real samples, concentrations of silicon containing compounds (trimethylsilanol, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasilioxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane) in the mg/m{sub 3} range have been observed.« less
Migration behaviour of silicone moulds in contact with different foodstuffs.
Helling, Ruediger; Kutschbach, Katja; Joachim Simat, Thomas
2010-03-01
Various foodstuffs were prepared in silicone baking moulds and analyzed for siloxane migration using a previously developed and validated (1)H-NMR method. Meat loaf significantly exceeded the overall migration limit of 60 mg kg(-1) (10 mg sdm(-1)) in the first and third experiment. The highest siloxane migration found in a meat loaf after preparation in a commercial mould was 177 mg kg(-1). In contrast, milk-based food showed very low or non-detectable migration (<2.4 mg kg(-1)), even containing high fat levels. Similar results were achieved using 50% ethanol as the simulant for milk-based products, as defined in the Plastics Directive 2007/19/EEC. After solvent extraction of the moulds in simulating long-term usage, no further migration into the food was detectable, indicating that there is no significant formation of low molecular weight, potentially migrating siloxanes from the elastomer. During repeated usage, the moulds showed a high uptake of fat: up to 8.0 g fat per kg elastomer. Proper tempering of the moulds had a major influence on the migration properties of siloxanes into different foodstuffs. Non-tempered moulds with a high level of volatile organic compounds (1.1%) were shown to have considerably higher migration than the equivalent tempered moulds.
Hydrogen peroxide mechanosynthesis in siloxane-hydrogel contact lenses.
Tavazzi, Silvia; Ferraro, Lorenzo; Cozza, Federica; Pastori, Valentina; Lecchi, Marzia; Farris, Stefano; Borghesi, Alessandro
2014-11-26
Drug-loaded contact lenses are emerging as the preferred treatment method for several ocular diseases, and efforts are being directed to promote extended and controlled delivery. One strategy is based on delivery induced by environmental triggers. One of these triggers can be hydrogen peroxide, since many platforms based on drug-loaded nanoparticles were demonstrated to be hydrogen-peroxide responsive. This is particularly interesting when hydrogen peroxide is the result of a specific pathophysiological condition. Otherwise, an alternative route to induce drug delivery is here proposed, namely the mechano-synthesis. The present work represents the proof-of-concept of the mechanosynthesis of hydrogen peroxide in siloxane-hydrogel contact lenses as a consequence of the cleavage of siloxane bonds at the interface between the polymer and water in aqueous phase. Their spongy morphology makes contact lenses promising systems for mechanical-to-chemical energy conversion, since the amount of hydrogen peroxide is expected to scale with the interfacial area between the polymer and water. The eyelid pressure during wear is sufficient to induce the hydrogen peroxide synthesis with concentrations which are biocompatible and suitable to trigger the drug release through hydrogen-peroxide-responsive platforms. For possible delivery on demand, the integration of piezoelectric polymers in the siloxane-hydrogel contact lenses could be designed, whose mechanical deformation could be induced by an applied wireless-controlled voltage.
{sup 6}LiF oleic acid capped nanoparticles entrapment in siloxanes for thermal neutron detection
DOE Office of Scientific and Technical Information (OSTI.GOV)
Carturan, S., E-mail: sara.carturan@lnl.infn.it; Maggioni, G., E-mail: Gianluigi.maggioni@lnl.infn.it; INFN, Laboratori Nazionali di Legnaro, Viale dell’Università 2, 35020 Legnaro
2016-07-07
The good light output of siloxane based scintillators as displayed under γ-rays and α particles has been exploited here to obtain clear and reliable response toward thermal neutrons. Sensitization towards thermal neutrons has been pursued by adding {sup 6}LiF, in form of nanoparticles. Aiming at the enhancement of compatibility between the inorganic nanoparticles and the low polarity, siloxane based surrounding medium, oleic acid-capped {sup 6}LiF nanoparticles have been synthesized by thermal decomposition of Li trifluoroacetate. Thin pellets siloxane scintillator maintained their optical transmittance up to weight load of 2% of {sup 6}Li. Thin samples with increasing {sup 6}Li concentration andmore » thicker ones with fixed {sup 6}Li amount have been prepared and tested with several sources (α, γ-rays, moderated neutrons). Light output as high as 80% of EJ212 under α irradiation was measured with thin samples, and negligible changes have been observed as a result of {sup 6}LiF addition. In case of thick samples, severe light loss has been observed, as induced by opacity. Nevertheless, thermal neutrons detection has been assessed and the data have been compared with GS20, based on Li glass, taken as a reference material.« less
Mechanisms associated with the high adsorption of dibenzo-p-dioxin from water by smectite clays.
Liu, Cun; Li, Hui; Teppen, Brian J; Johnston, Cliff T; Boyd, Stephen A
2009-04-15
Clay minerals may be an important unrecognized sorptive phase for dioxins in soils and clay deposits. Smectites, especially Cs-saponite, effectively adsorbed dibenzo-p-dioxin (DD) from water, reaching 0.8% (wt/wt). Adsorption was promoted by exchangeable cations with low hydration energies, and negative charge in the smectite arising from the tetrahedral siloxane sheets. X-ray diffraction measurements revealed that as DD loading increased to > or =8000 mg/kg the clay basal spacing increased abruptly from 12.3 to 15.2 A demonstrating DD intercalation. The 12.3 A spacing provides an interlayer distance that closely matches the molecular thickness of DD. In this configuration DD is essentially dehydrated as it interacts with the opposing hydrophobic siloxane sheets and with coplanar Cs+ via one of the dioxin ring oxygens. Ab initio calculations suggest that geometrical structures form at higher loadings in which intercalated DD molecules adopt a butterfly geometry sandwiched between dehydrated interlayer Cs+ and the siloxane surface, consistent with the 15.2 A spacing, wherein Cs+ interacts with dioxin ring oxygens and benzene ring pi-electrons. Fourier transformation infrared measurements confirm that adsorbed DD is present in orientations that are not parallel with the interlayer planar siloxane surfaces of smectite.
Surface confined ionic liquid as a stationary phase for HPLC
DOE Office of Scientific and Technical Information (OSTI.GOV)
Wang, Qian; Baker, Gary A; Baker, Sheila N
Trimethoxysilane ionosilane derivatives of room temperature ionic liquids based on alkylimidazolium bromides were synthesized for attachment to silica support material. The derivatives 1-methyl-3-(trimethoxysilylpropyl)imidazolium bromide and 1-butyl-3-(trimethoxysilylpropyl)imidazolium bromide were used to modify the surface of 3 {micro}m diameter silica particles to act as the stationary phase for HPLC. The modified particles were characterized by thermogravimetric analysis (TGA) and {sup 13}C and {sup 29}Si NMR spectroscopies. The surface modification procedure rendered particles with a surface coverage of 0.84 {micro}mol m{sup -2} for the alkylimidazolium bromide. The ionic liquid moiety was predominantly attached to the silica surface through two siloxane bonds of themore » ionosilane derivative (63%). Columns packed with the modified silica material were tested under HPLC conditions. Preliminary evaluation of the stationary phase for HPLC was performed using aromatic carboxylic acids as model compounds. The separation mechanism appears to involve multiple interactions including ion exchange, hydrophobic interaction, and other electrostatic interactions.« less
NASA Technical Reports Server (NTRS)
Nakayama, M.; Morita, H.; Tokuoka, Y.; Izumi, T.; Fukuda, K.; Kubota, Y.
1984-01-01
The magnetic layer of a magnetic record support is coated with a thin film of a polymer with a siloxane bond. The magnetic layer consists of a thin film obtained by vacuum metallization, cathode sputtering or dispersion of a ferromagnetic metal powder in a binder. The polymer with a siloxane bond is produced by the polymerization of an organic silicon compound which inherently contains or is able to form this bond. Polymerization is preferably performed by plasma polymerization.
Antonetti, Claudia; Licursi, Domenico; Raspolli Galletti, Anna Maria; Martinelli, Marco; Tellini, Filippo; Valentini, Giorgio; Gambineri, Francesca
2016-09-01
The removal of polychlorinated biphenyls (PCBs) both from siloxane transformer oil and hydrocarbon engine oil was investigated through the application of microwave (MW) irradiation and a reaction system based on polyethyleneglycol (PEG) and potassium hydroxide. The influence of the main reaction parameters (MW irradiation time, molecular weight of PEG, amount of added reactants and temperature) on the dechlorination behavior was studied. Promising performances were reached, allowing about 50% of dechlorination under the best experimental conditions, together time and energy saving compared to conventional heating systems. Moreover, an interesting dechlorination degree (up to 32%) was achieved for siloxane transformer oil when MW irradiation was employed as the unique driving force. To the best of our knowledge, this is the first time in which MW irradiation is tested as the single driving force for the dechlorination of these two types of PCB-contaminated oils. Copyright © 2016 Elsevier Ltd. All rights reserved.
Non-toxic liquid scintillators with high light output based on phenyl-substituted siloxanes
NASA Astrophysics Data System (ADS)
Dalla Palma, M.; Carturan, S. M.; Degerlier, M.; Marchi, T.; Cinausero, M.; Gramegna, F.; Quaranta, A.
2015-04-01
The work describes the development of a new class of liquid scintillators based on polysiloxane liquid compounds. These materials are characterized by low toxicity, chemical inertness, very low volatility and low flammability, allowing their use without concerns even at high temperatures in vacuum. In this view different polysiloxane based liquids have been tested, with variable content and distribution of phenyl lateral substituents and added with suitable dyes, namely 2,5-diphenyloxazole (PPO) and Lumogen Violet (LV). Absorption and fluorescence spectroscopy have been used in order to study the emission feature of the various compounds and to investigate the spectral matching between siloxane solvents and dissolved primary dyes. Scintillation efficiency towards 60Co and 137Cs gamma rays, relative to commercial liquid scintillator (EJ-309), has been measured and the results have been related to the energy transfer and energy migration mechanism from monomer and excimer forming sites in liquid siloxanes.
Method for forming porous sintered bodies with controlled pore structure
Whinnery, LeRoy Louis; Nichols, Monte Carl
2000-01-01
The present invention is based, in part, on a method for combining a mixture of hydroxide and hydride functional siloxanes to form a polysiloxane polymer foam, that leaves no residue (zero char yield) upon thermal decomposition, with ceramic and/or metal powders and appropriate catalysts to produce porous foam structures having compositions, densities, porosities and structures not previously attainable. The siloxanes are mixed with the ceramic and/or metal powder, wherein the powder has a particle size of about 400 .mu.m or less, a catalyst is added causing the siloxanes to foam and crosslink, thereby forming a polysiloxane polymer foam having the metal or ceramic powder dispersed therein. The polymer foam is heated to thermally decompose the polymer foam and sinter the powder particles together. Because the system is completely nonaqueous, this method further provides for incorporating reactive metals such as magnesium and aluminum, which can be further processed, into the foam structure.
Organosiloxane working fluids for the liquid droplet radiator
NASA Technical Reports Server (NTRS)
Buch, R. R.; Huntress, A. R.
1985-01-01
Siloxane-based working fluids for advanced space radiators requiring direct fluid exposure to the space environment are evaluated. Isolation of five candidate fluids by vacuum distillation from existing siloxane polymers is discussed. The five fluids recovered include a polydimethylsiloxane, three phenyl-containing siloxanes, and a methylhexylsiloxane. Vapor pressures and viscosities for the five fluids are reported over the temperature range of 250 to 400 K. Use of thermal-gravimetric analysis to reliably estimate vapor pressures of 10 to the -8 power Pascals is described. Polydimethylsiloxane (PDMS) and polymethylphenylsiloxane (PMPS) are selected from the five candidate fluids based on favorable vapor pressure and viscosity, as well as perceived stability in low-Earth orbit environments. Characterization of these fluids by infrared spectroscopy, Si-29 NMR, gel-permeation chromatography, and liquid chromatography is presented. Both fluids consist of narrow molecular weight distributions, with average molecular weights of about 2500 for PDMS and 1300 for PMPS.
VMCast: A VM-Assisted Stability Enhancing Solution for Tree-Based Overlay Multicast
Gu, Weidong; Zhang, Xinchang; Gong, Bin; Zhang, Wei; Wang, Lu
2015-01-01
Tree-based overlay multicast is an effective group communication method for media streaming applications. However, a group member’s departure causes all of its descendants to be disconnected from the multicast tree for some time, which results in poor performance. The above problem is difficult to be addressed because overlay multicast tree is intrinsically instable. In this paper, we proposed a novel stability enhancing solution, VMCast, for tree-based overlay multicast. This solution uses two types of on-demand cloud virtual machines (VMs), i.e., multicast VMs (MVMs) and compensation VMs (CVMs). MVMs are used to disseminate the multicast data, whereas CVMs are used to offer streaming compensation. The used VMs in the same cloud datacenter constitute a VM cluster. Each VM cluster is responsible for a service domain (VMSD), and each group member belongs to a specific VMSD. The data source delivers the multicast data to MVMs through a reliable path, and MVMs further disseminate the data to group members along domain overlay multicast trees. The above approach structurally improves the stability of the overlay multicast tree. We further utilized CVM-based streaming compensation to enhance the stability of the data distribution in the VMSDs. VMCast can be used as an extension to existing tree-based overlay multicast solutions, to provide better services for media streaming applications. We applied VMCast to two application instances (i.e., HMTP and HCcast). The results show that it can obviously enhance the stability of the data distribution. PMID:26562152
VMCast: A VM-Assisted Stability Enhancing Solution for Tree-Based Overlay Multicast.
Gu, Weidong; Zhang, Xinchang; Gong, Bin; Zhang, Wei; Wang, Lu
2015-01-01
Tree-based overlay multicast is an effective group communication method for media streaming applications. However, a group member's departure causes all of its descendants to be disconnected from the multicast tree for some time, which results in poor performance. The above problem is difficult to be addressed because overlay multicast tree is intrinsically instable. In this paper, we proposed a novel stability enhancing solution, VMCast, for tree-based overlay multicast. This solution uses two types of on-demand cloud virtual machines (VMs), i.e., multicast VMs (MVMs) and compensation VMs (CVMs). MVMs are used to disseminate the multicast data, whereas CVMs are used to offer streaming compensation. The used VMs in the same cloud datacenter constitute a VM cluster. Each VM cluster is responsible for a service domain (VMSD), and each group member belongs to a specific VMSD. The data source delivers the multicast data to MVMs through a reliable path, and MVMs further disseminate the data to group members along domain overlay multicast trees. The above approach structurally improves the stability of the overlay multicast tree. We further utilized CVM-based streaming compensation to enhance the stability of the data distribution in the VMSDs. VMCast can be used as an extension to existing tree-based overlay multicast solutions, to provide better services for media streaming applications. We applied VMCast to two application instances (i.e., HMTP and HCcast). The results show that it can obviously enhance the stability of the data distribution.
Environmentally stable polymers and coatings for space application: CH-5, supplement 10
NASA Technical Reports Server (NTRS)
Sykes, G.
1986-01-01
High molecular weight, randomly coupled poly(imide siloxane) soluble block copolymers were synthesized from bis(amino propyl) polydimethylsiloxane equilibrates of various molecular weights, aromatic metalinked diamines, and 3,3'-4,4'-benzophenone tetracarboxylic dianhydride (BTDA). Two synthetic procedures were successfully used to synthesize the poly(amic acid siloxane) intermediates. For both synthetic procedures, a cosolvent system was employed to achieve complete solvation of all components throughout the polymerization. Physical property characterization is continuing.
Polyvinyl siloxane: novel material for external nasal splinting.
Jayakumar, N K; Rathnaprabhu, V; Ramesh, S; Parameswaran, A
2016-01-01
External nasal splinting is performed routinely after nasal bone fracture reductions, osteotomies, and rhinoplasties. Materials commonly used include plaster of Paris (POP), thermoplastic splints, self-adhesive padded aluminium splints, and Orthoplast, among many others. The disadvantages of these materials are described in this paper, and polyvinyl siloxane is recommended as an effective and more readily available alternative material to counter these pitfalls. Copyright © 2015 International Association of Oral and Maxillofacial Surgeons. Published by Elsevier Ltd. All rights reserved.
Lynam, Emily C; Xie, Yan; Loli, Bree; Dargaville, Tim R; Leavesley, David I; George, Graeme A; Upton, Zee
2010-11-01
The formation of hypertrophic scars (HSF) is a frequent medical outcome of wound repair and often requires further therapy with treatments such as silicone gel sheets (SGS) or apoptosis-inducing agents, including bleomycin. Although widely used, knowledge regarding SGS and their mode of action is limited. Preliminary research has shown that small amounts of amphiphilic silicone present in SGS have the ability to move into skin during treatment. We demonstrate herein that a commercially available analogue of these amphiphilic siloxane species, the rake copolymer GP226, decreases collagen synthesis on exposure to cultures of fibroblasts derived from HSF. By size exclusion chromatography, GP226 was found to be a mixture of siloxane species, containing five fractions of different molecular weight. By studies of collagen production, cell viability and proliferation, it was revealed that a low molecular weight fraction (fraction IV) was the most active, reducing the number of viable cells present after treatment and thereby reducing collagen production as a result. On exposure of fraction IV to human keratinocytes, viability and proliferation were also significantly affected. HSF undergoing apoptosis after application of fraction IV were also detected via real-time microscopy and by using the TUNEL assay. Taken together, these data suggests that these amphiphilic siloxanes could be potential non-invasive substitutes to apoptotic-inducing chemical agents that are currently used as scar treatments.
Accuracy of impressions with different impression materials in angulated implants.
Reddy, S; Prasad, K; Vakil, H; Jain, A; Chowdhary, R
2013-01-01
To evaluate the dimensional accuracy of the resultant (duplicative) casts made from two different impression materials (polyvinyl siloxane and polyether) in parallel and angulated implants. Three definitive master casts (control groups) were fabricated in dental stone with three implants, placed at equi-distance. In first group (control), all three implants were placed parallel to each other and perpendicular to the plane of the cast. In the second and third group (control), all three implants were placed at 10° and 15 o angulation respectively to the long axis of the cast, tilting towards the centre. Impressions were made with polyvinyl siloxane and polyether impression materials in a special tray, using a open tray impression technique from the master casts. These impressions were poured to obtain test casts. Three reference distances were evaluated on each test cast by using a profile projector and compared with control groups to determine the effect of combined interaction of implant angulation and impression materials on the accuracy of implant resultant cast. Statistical analysis revealed no significant difference in dimensional accuracy of the resultant casts made from two different impression materials (polyvinyl siloxane and polyether) by closed tray impression technique in parallel and angulated implants. On the basis of the results of this study, the use of both the impression materials i.e., polyether and polyvinyl siloxane impression is recommended for impression making in parallel as well as angulated implants.
Structural Characterization of POSS Siloxane Dimer and Trimer (PREPRINT)
2005-11-14
68.49 (s, 1 Si); -109.77 (s, 1 Si). Elemental analysis found (theoretical): %C 50.12 (50.11); %H 7.88 (7.71). HPLC showed a single peak. Synthesis...s, 1 Si); -68.88 (s, 1 Si); -110.09 (s, 1 Si). Elemental analysis found (theoretical): %C 51.37 (51.22); %H 7.96 (7.88). HPLC showed a single...when tethered or blended into polydimethylsiloxane . Attempts to model siloxanes28-30 are not new. Sun and Rigby31 were the first to develop a
Chemical treatment for silica-containing glass surfaces
Grabbe, Alexis; Michalske, Terry Arthur; Smith, William Larry
1999-01-01
Dehydroxylated, silica-containing, glass surfaces are known to be at least partially terminated by strained siloxane rings. According to the invention, a surface of this kind is exposed to a selected silane compound or mixture of silane compounds under reaction-promoting conditions. The ensuing reaction results in opening of the strained siloxane rings, and termination of surface atoms by chemical species, such as organic or organosilicon species, having desirable properties. These species can be chosen to provide qualities such as hydrophobicity, or improved coupling to a polymeric coating.
Chemical treatment for silica-containing glass surfaces
Grabbe, Alexis; Michalske, Terry Arthur; Smith, William Larry
1998-01-01
Dehydroxylated, silica-containing, glass surfaces are known to be at least partially terminated by strained siloxane rings. According to the invention, a surface of this kind is exposed to a selected silane compound or mixture of silane compounds under reaction-promoting conditions. The ensuing reaction results in opening of the strained siloxane rings, and termination of surface atoms by chemical species, such as organic or organosilicon species, having desirable properties. These species can be chosen to provide qualities such as hydrophobicity, or improved coupling to a polymeric coating.
Chemical treatment for silica-containing glass surfaces
Grabbe, Alexis; Michalske, Terry Arthur; Smith, William Larry
1999-01-01
Dehydroxylated, silica-containing, glass surfaces are known to be at least partially terminated by strained siloxane rings. According to the invention, a surface of this kind is exposed to a selected silane compound or mixture of silane compounds under reaction-promoting conditons. The ensuing reaction results in opening of the strained siloxane rings, and termination of surface atoms by chemical species, such as organic or organosilicon species, having desirable properties. These species can be chosen to provide qualities such as hydrophobicity, or improved coupling to a polymeric coating.
1987-03-30
TFP) siloxane and of ATBN and CTBN rubber modified epoxies were previously reported,,[1]. There was no significant evidence that the low surface energy...siloxane- modified epoxies reduced friction compared with the unmodified epoxy or the ATBN and CTBN modified epoxies. The reduction in wear noted for...is for the control, but their elastic moduli are lower. The CTBN samples from the previous work also had higher wear rates at the 5 percent level. It
Structure/Property Relationships of Siloxane-Based Liquid Crystalline Materials
1992-05-01
482 (1989). () Gierlotka, S., Przedmojski, J., and Pura, B ., Liq. Cryst.,, 1989). 45 (101) Leadbetter, A.i., Gaughan, J.P., Kelly, B ., Gray. G.W...FUNDING NUMBERSSTRUCTURE/PROPERTY RELATIONSHIPS OF SILOXANE-BASED P: 612 LIQUID CRYSTALLINE MATERIALS PR: 624022 TA: 04 6 AUTHOR(S) W: 0 B unning, T.J...Klei, H.E.; Koberstein, J.T.; W. 0 Samulski, E.T.; Adams, 51.1.; Crane, R.L. 7i PERFORMINGT ORGANIZATION NAME(S) AND ADDRESS(ES) B PERFORMING
Zapadlo, Michal; Krupcík, Ján; Májek, Pavel; Armstrong, Daniel W; Sandra, Pat
2010-09-10
The orthogonality of three columns coupled in two series was studied for the congener specific comprehensive two-dimensional GC separation of polychlorinated biphenyls (PCBs). A non-polar capillary column coated with poly(5%-phenyl-95%-methyl)siloxane was used as the first ((1)D) column in both series. A polar capillary column coated with 70% cyanopropyl-polysilphenylene-siloxane or a capillary column coated with the ionic liquid 1,12-di(tripropylphosphonium)dodecane bis(trifluoromethane-sulfonyl)imide were used as the second ((2)D) columns. Nine multi-congener standard PCB solutions containing subsets of all native 209 PCBs, a mixture of 209 PCBs as well as Aroclor 1242 and 1260 formulations were used to study the orthogonality of both column series. Retention times of the corresponding PCB congeners on (1)D and (2)D columns were used to construct retention time dependences (apex plots) for assessing orthogonality of both columns coupled in series. For a visual assessment of the peak density of PCBs congeners on a retention plane, 2D images were compared. The degree of orthogonality of both column series was, along the visual assessment of distribution of PCBs on the retention plane, evaluated also by Pearson's correlation coefficient, which was found by correlation of retention times t(R,i,2D) and t(R,i,1D) of corresponding PCB congeners on both column series. It was demonstrated that the apolar+ionic liquid column series is almost orthogonal both for the 2D separation of PCBs present in Aroclor 1242 and 1260 formulations as well as for the separation of all of 209 PCBs. All toxic, dioxin-like PCBs, with the exception of PCB 118 that overlaps with PCB 106, were resolved by the apolar/ionic liquid series while on the apolar/polar column series three toxic PCBs overlapped (105+127, 81+148 and 118+106). Copyright 2010 Elsevier B.V. All rights reserved.
The non-modulated transfer of total effluent for serially coupled columns in gas chromatography.
Krupcík, Ján; Mydlová-Memersheimerová, Janka; Májek, Pavel; Zapadlo, Michal; Sandra, Pat
2010-03-12
The non-modulated transfer (NMT) of the total effluent of the separation of polychlorinated biphenyls (PCBs) on two columns coupled in series has been studied. A non-polar poly(5%-phenyl-95%-methyl)siloxane column (40 m x 100 microm x 0.1 microm) and a polar 70%-cyanopropyl-polysilphenylene-siloxane column (4 m x 0.1 mm x 0.1 microm) were used as (1)D and (2)D columns, respectively. The effluents from both the (1)D column and the (1)D+(2)D column series were monitored independently by two FIDs. Data from the (1)D and (1)D+(2)D integration reports were used to evaluate the NMT experiment. (1)D retention times, t(R,i,D1), were directly accessible from (1)D integration report while (2)D retention times, t(R,i,B), were calculated for all corresponding peak pairs from (1)D and (1)D+(2)D integration reports as a difference t(R,i,D2)=t(R,i,D1+D2)-t(R,i,D1). Search for corresponding peaks of PCB congeners in the (1)D and (1)D+(2)D chromatograms is elucidated in detail on standard PCB samples and on PCB congeners present in the technical formulation Arochlor 1242. Both retention times (t(R,i,D1) and t(R,i,D2)) as well as peak widths at half height (w(h,i)) and peak heights (h(i)) obtained from integration reports were used to construct 2D and 3D images for PCB NMT separations on serially coupled columns. The performance of the NMT procedure is illustrated by the separation of (i) standard PCB solutions, (ii) a mixture of the 209 PCBs, and (iii) a mixture of Arochlor 1242 and hydrocarbons on the DB-5+BPX-70 column series. Copyright (c) 2010 Elsevier B.V. All rights reserved.
Shoeib, Mahiba; Schuster, Jasmin; Rauert, Cassandra; Su, Ky; Smyth, Shirley-Anne; Harner, Tom
2016-11-01
The potential of wastewater treatment plants (WWTPs) to act as sources of poly and perfluoroalkyl substances (PFASs), volatile methyl siloxanes (VMSs) and organic UV-filters to the atmosphere was investigated. Target compounds included: PFASs (fluorotelomer alcohols (FTOHs), perfluorooctane sulfonamides/sulfonamidoethanols (FOSAs/FOSEs), perfluroalkyl sulfonic acids (PFSAs) and perfluroalkyl carboxylic acids (PFCAs)), cyclic VMSs (D3 to D6), linear VMSs (L3 to L5) and eight UV-filters. Emissions to air were assessed at eight WWTPs using paired sorbent-impregnated polyurethane foam passive air samplers, deployed during summer 2013 and winter 2014. Samplers were deployed on-site above the active tank and off-site as a reference. Several types of WWTPs were investigated: secondary activated sludge in urban areas (UR-AS), secondary extended aeration in towns (TW-EA) and facultative lagoons in rural areas (RU-LG). The concentrations of target compounds in air were ∼1.7-35 times higher on-site compared to the corresponding off-site location. Highest concentrations in air were observed at UR-AS sites while the lowest were at RU-LG. Higher air concentrations (∼2-9 times) were observed on-site during summer compared to winter, possibly reflecting enhanced volatilization due to higher wastewater temperatures or differences in influent wastewater concentrations. A significant positive correlation was obtained between concentrations in air and WWTP characteristics (influent flow rate and population in the catchment of the WWTP); whereas a weak negative correlation was obtained with hydraulic retention time. Emissions to air were estimated using a simplified dispersion model. Highest emissions to air were seen at the UR-AS locations. Emissions to air (g/year/tank) were highest for VMSs (5000-112,000) followed by UV-filters (16-2000) then ΣPFASs (10-110). Copyright © 2016. Published by Elsevier Ltd.
New Control Over Silicone Synthesis using SiH Chemistry: The Piers-Rubinsztajn Reaction.
Brook, Michael A
2018-06-18
There is a strong imperative to synthesize polymers with highly controlled structures and narrow property ranges. Silicone polymers do not lend themselves to this paradigm because acids or bases lead to siloxane equilibration and loss of structure. By contrast, elegant levels of control are possible when using the Piers-Rubinsztajn reaction and analogues, in which the hydrophobic, strong Lewis acid B(C 6 F 5 ) 3 activates SiH groups, permitting the synthesis of precise siloxanes under mild conditions in high yield; siloxane decomposition processes are slow under these conditions. A broad range of oxygen nucleophiles including alkoxysilanes, silanols, phenols, and aryl alkyl ethers participate in the reaction to create elastomers, foams and green composites, for example, derived from lignin. In addition, the process permits the synthesis of monofunctional dendrons that can be assembled into larger entities including highly branched silicones and dendrimers either using the Piers-Rubinsztajn process alone, or in combination with hydrosilylation or other orthogonal reactions. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
Cesur, E; Altug, A T; Toygar-Memikoglu, U; Gumru-Celikel, D; Tagrikulu, B; Erbay, E
2018-05-01
The aim of this case-control study was to assess sella turcica area and skeletal maturity in children with unilateral cleft lip and palate (UCLP) and compare with those of non-cleft children. A total of 85 UCLP patients aged 7.5-17.08 years (Group 1: age 7-11 years, Group 2: age 11-14 years and Group 3: age 14-18 years) were compared with 85 control subjects without clefts who were divided into similar age groups. Hand-wrist radiographs and cervical vertebra maturation stages (CVMS) were used to evaluate growth. Lateral cephalograms were traced, and reference points of sella were determined. Sella turcica area was measured using a digital planimeter. Comparison of overall growth on hand-wrist radiographs revealed no significant difference between cleft and non-cleft subjects. However, according to the chronological age groups, Group 1-UCLP showed statistically significant delay in skeletal maturation when compared with the age-matched control subjects (P = .05). This difference was due to the delay among male subjects (P = .05). As for CVMS, more significant maturation delay was observed in Group 1-UCLP (P = .001) and was attributable to both male and female subjects (P = .05). Comparison of sella turcica area showed no significant difference between UCLP patients and controls. Although children with CLP showed significant delay in growth when they are younger compared with the non-cleft children, sella turcica area measurements were similar for individuals in both groups. © 2018 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.
Margin adaptation of indirect composite inlays fabricated on flexible dies.
Price, R B; Gerrow, J D
2000-03-01
Indirect composite restorations can be made in 1 appointment using a flexible die. Interactions between different impression materials and flexible die materials may affect the accuracy of fit and margin adaptation of the restoration. This study compared the margin adaptation of composite inlays made using the following 5 impression/flexible die material combinations; condensation silicone/polyvinyl siloxane (CS/PVS), wash viscosity polyvinyl siloxane/medium or heavy viscosity polyvinyl siloxane (PVS/PVS), irreversible hydrocolloid impression/medium viscosity polyvinyl siloxane (IH/PVS), wash viscosity polyvinyl siloxane impression/polyether (PVS/PE), with composite inlays made using a control system of a wash viscosity polyvinyl siloxane impression and a type IV stone die. For each test and control system, 10 impressions were made of a class II composite inlay preparation in a metal master die. One die was made from each impression and one composite inlay was made and finished on each die (a total of 60 inlays). Inlays were placed on the master die and the margin opening at the buccal, distal, and gingival sites was recorded with a measuring microscope (x40 magnification). The overall mean +/- SD margin openings of inlays made from the systems were as follows: PVS wash/PVS heavy viscosity 149.5 +/- 107. 4 microm; PVS wash/PVS medium viscosity 87.4 +/- 63.0 microm; IH/PVS medium viscosity 76.7 +/- 48.9 microm; CS/PVS 73.3 +/- 48.7 microm, PVS wash viscosity/PE 64.0 +/- 44.3 microm, PVS wash viscosity/stone 53.9 +/- 48.3 microm. Composite inlays made using the PVS wash viscosity/PVS heavy viscosity system had significantly larger distal, gingival, and overall mean margin openings than all other inlays (ANOVA and Fisher PLSD test; P =.05). The separating medium required between some impression and die materials did not work consistently. Composite inlays fabricated on dies made of material different than the impression material had mean buccal, distal, gingival, and overall margin openings < or =100 microm. Composite inlays made on the CS/PVS, IH/PVS medium viscosity, PVS wash viscosity/PE flexible dies, and control PVS wash viscosity/stone dies had statistically similar (P =.05) mean buccal, distal, gingival, and overall mean margin openings that were < or =100 microm. Composite inlays made on dies that were made of the same type of material as the impression material (PVS/PVS) had mean gingival margin openings >100 microm that were significantly larger than all other systems tested (P =.05).
Liu, Richard Y; Bae, Minwoo; Buchwald, Stephen L
2018-02-07
Metal-catalyzed silylative dehydration of primary amides is an economical approach to the synthesis of nitriles. We report a copper-hydride(CuH)-catalyzed process that avoids a typically challenging 1,2-siloxane elimination step, thereby dramatically increasing the rate of the overall transformation relative to alternative metal-catalyzed systems. This new reaction proceeds at ambient temperature, tolerates a variety of metal-, acid-, or base-sensitive functional groups, and can be performed using a simple ligand, inexpensive siloxanes, and low catalyst loading.
Method for chemical surface modification of fumed silica particles
Grabbe, Alexis; Michalske, Terry Arthur; Smith, William Larry
1999-01-01
Dehydroxylated, silica-containing, glass surfaces are known to be at least partially terminated by strained siloxane rings. According to the invention, a surface of this kind is exposed to a selected silane compound or mixture of silane compounds under reaction-promoting conditions. The ensuing reaction results in opening of the strained siloxane rings, and termination of surface atoms by chemical species, such as organic or organosilicon species, having desirable properties. These species can be chosen to provide qualities such as hydrophobicity, or improved coupling to a polymeric coating.
NASA Technical Reports Server (NTRS)
Crivello, James V. (Inventor)
1996-01-01
A process for the selective monoadditon of an olefin or acetylene to a siloxane which contains two reactive Si--H bonds to produce a product in which only one of the two Si--H functions has added across the olefin or acetylene is disclosed. A process for making unsymmetrical siloxanes from symmetrical dihydrosiloxanes and products of both of these processes are also disclosed. Products are represented by the formula I in which R.sup.1 and R.sup.4 are different: ##STR1##.
Morphology and Surface Energy of a Si Containing Semifluorinated Di-block Copolymer Thin Films.
NASA Astrophysics Data System (ADS)
Shrestha, Umesh; Clarson, Stephen; Perahia, Dvora
2013-03-01
The structure and composition of an interface influence stability, adhesiveness and response to external stimuli of thin polymeric films. Incorporation of fluorine affects interfacial energy as well as thermal and chemical stability of the layers. The incompatibility between the fluorinated and non-fluorinated blocks induces segregation that leads to long range correlations where the tendency of the fluorine to migrate to interfaces impacts the surface tension of the films. Concurrently Si in a polymeric backbone enhances the flexibility of polymeric chains. Our previous studies of poly trifluoro propyl methyl siloxane-polystyrene thin films with SiF fraction 0.03-0.5 as a function of temperature have shown that the SiF block drives layering parallel to the surface of the diblock. Here in we report the structure and interfacial energies of SiF-PS in the plane of the films, as a function of the volume fraction of the SiF block obtained from Atomic Force microscopy and contact angle measurement studies. This work is supported by NSF DMR - 0907390
Concentration and Velocity Measurements of Both Phases in Liquid-Solid Slurries
NASA Astrophysics Data System (ADS)
Altobelli, Stephen; Hill, Kimberly; Caprihan, Arvind
2007-03-01
Natural and industrial slurry flows abound. They are difficult to calculate and to measure. We demonstrate a simple technique for studying steady slurries. We previously used time-of-flight techniques to study pressure driven slurry flow in pipes. Only the continuous phase velocity and concentration fields were measured. The discrete phase concentration was inferred. In slurries composed of spherical, oil-filled pills and poly-methyl-siloxane oils, we were able to use inversion nulling to measure the concentration and velocity fields of both phases. Pills are available in 1-5mm diameter and silicone oils are available in a wide range of viscosities, so a range of flows can be studied. We demonstrated the technique in horizontal, rotating cylinder flows. We combined two tried and true methods to do these experiments. The first used the difference in T1 to select between phases. The second used gradient waveforms with controlled first moments to produce velocity dependent phase shifts. One novel processing method was developed that allows us to use static continuous phase measurements to reference both the continuous and discrete phase velocity images. ?
Magnetophoretic manipulation in microsystem using carbonyl iron-polydimethylsiloxane microstructures
Faivre, Magalie; Gelszinnis, Renaud; Degouttes, Jérôme; Terrier, Nicolas; Rivière, Charlotte; Ferrigno, Rosaria; Deman, Anne-Laure
2014-01-01
This paper reports the use of a recent composite material, noted hereafter i-PDMS, made of carbonyl iron microparticles mixed in a PolyDiMethylSiloxane (PDMS) matrix, for magnetophoretic functions such as capture and separation of magnetic species. We demonstrated that this composite which combine the advantages of both components, can locally generate high gradients of magnetic field when placed between two permanent magnets. After evaluating the magnetic susceptibility of the material as a function of the doping ratio, we investigated the molding resolution offered by i-PDMS to obtain microstructures of various sizes and shapes. Then, we implemented 500 μm i-PDMS microstructures in a microfluidic channel and studied the influence of flow rate on the deviation and trapping of superparamagnetic beads flowing at the neighborhood of the composite material. We characterized the attraction of the magnetic composite by measuring the distance from the i-PDMS microstructure, at which the beads are either deviated or captured. Finally, we demonstrated the interest of i-PDMS to perform magnetophoretic functions in microsystems for biological applications by performing capture of magnetically labeled cells. PMID:25332740
Monomolecular Siloxane Film as a Model of Single Site Catalysts
Martynowycz, Michael W.; Hu, Bo; Kuzmenko, Ivan; ...
2016-09-06
Achieving structurally well-defined catalytic species requires a fundamental understanding of surface chemistry. Detailed structural characterization of the catalyst binding sites in situ, such as single site catalysts on silica supports, is technically challenging or even unattainable. Octadecyltrioxysilane (OTOS) monolayers formed from octadecyltrimethoxysilane (OTMS) at the air-liquid interface after hydrolysis and condensation at low pH were chosen as a model system of surface binding sites in silica-supported Zn 2+ catalysts. We characterize the system by grazing incidence X-ray diffraction, X-ray reflectivity (XR), and X-ray fluorescence spectroscopy (XFS). Previous X-ray and infrared surface studies of OTMS/OTOS films at the airliquid interface proposedmore » the formation of polymer OTOS structures. According to our analysis, polymer formation is inconsistent with the X-ray observations and structural properties of siloxanes; it is energetically unfavorable and thus highly unlikely. We suggest an alternative mechanism of hydrolysis/condensation in OTMS leading to the formation of structurally allowed cyclic trimers with the six-membered siloxane rings, which explain well both the X-ray and infrared results. XR and XFS consistently demonstrate that tetrahedral [Zn(NH 3) 4] 2+ ions bind to hydroxyl groups of the film at a stoichiometric ratio of OTOS:Zn ~ 2:1. The high binding affinity of zinc ions to OTOS trimers suggests that the six-membered siloxane rings are binding locations for single site Zn/SiO 2 catalysts. Finally, our results show that OTOS monolayers may serve as a platform for studying silica surface chemistry or hydroxyl-mediated reactions.« less
Yoshikawa, Masashi; Tamura, Yasuhiro; Wakabayashi, Ryutaro; Tamai, Misa; Shimojima, Atsushi; Kuroda, Kazuyuki
2017-11-06
The concept of protecting groups and leaving groups in organic synthesis was applied to the synthesis of siloxane-based molecules. Alkoxy-functionalized siloxane oligomers composed of SiO 4 , RSiO 3 , or R 2 SiO 2 units were chosen as targets (R: functional groups, such as Me and Ph). Herein we describe a novel synthesis of alkoxysiloxane oligomers based on the substitution reaction of trimethylsilyl (TMS) groups with alkoxysilyl groups. Oligosiloxanes possessing TMS groups were reacted with alkoxychlorosilane in the presence of BiCl 3 as a catalyst. TMS groups were substituted with alkoxysilyl groups, leading to the synthesis of alkoxysiloxane oligomers. Siloxane oligomers composed of RSiO 3 and R 2 SiO 2 units were synthesized more efficiently than those composed of SiO 4 units, suggesting that the steric hindrance around the TMS groups of the oligosiloxanes makes a difference in the degree of substitution. This reaction uses TMS groups as both protecting and leaving groups for SiOH/SiO - groups. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
Sevimoğlu, Orhan; Tansel, Berrin
2013-01-01
Performances of gas engines operated with landfill gas (LFG) are affected by the impurities in the LFG, reducing the economic viability of energy recovery. The purpose of this study was to characterize the trace compounds in the LFG at the Odayeri Landfill, Istanbul, Turkey which is used for energy recovery. Composite gas samples were collected and analyzed for trace compounds (hydrocarbons, siloxanes, and volatile halogenated hydrocarbons) over a 3-year period. Trace compounds entering the gas engines, their impact on the engine performance were evaluated. The operational problems included deposit formation in the combustion chamber, turbocharger, and intercooler of engine before the scheduled maintenance times. High levels of hydrogen sulfide, as well as chlorinated and fluorinated compounds cause corrosion of the engine parts and decrease life of the engine oils. Persistence of siloxanes results in deposit formation, increasing engine maintenance costs. Pretreatment of LFG is necessary to protect the engines at the waste-to-energy facilities with persistence levels of siloxanes and volatile halogenated hydrocarbons. Copyright © 2012 Elsevier Ltd. All rights reserved.
Surita, Sharon C; Tansel, Berrin
2014-01-15
Siloxane use in consumer products (i.e., fabrics, paper, concrete, wood, adhesive surfaces) has significantly increased in recent years due to their excellent water repelling and antimicrobial characteristics. The objectives of this study were to evaluate the release mechanisms of two siloxane compounds, octamethylcyclotetrasiloxane (D4) and decamethylcyclopentasiloxane (D5), which have been detected both at landfills and wastewater treatment plants, estimate persistence times in different media, and project release quantities over time in relation to their increasing use. Analyses were conducted based on fate and transport mechanisms after siloxanes enter waste streams. Due to their high volatility, the majority of D4 and D5 end up in the biogas during decomposition. D5 is about ten times more likely to partition into the solid phase (i.e., soil, biosolids). D5 concentrations in the wastewater influent and biogas are about 16 times and 18 times higher respectively, in comparison to the detected levels of D4. © 2013 Elsevier B.V. All rights reserved.
Coupled aging effects in nanofiber-reinforced siloxane foams
Labouriau, Andrea; Robison, Tom; Geller, Drew Adam; ...
2018-01-11
Here, this study investigates the combined effects of ionizing radiation and thermal treatments on the aging of siloxane foams containing small amounts of carbon nanofibers. Our siloxane foams were exposed to accelerated aging conditions for more than two years, resulting in very low dose rates. In addition, foams were aged under compressive load to evaluate the strength of the porous microstructure. Samples were characterized by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (NMR), Mössbauer, mass spectroscopy, electron paramagnetic resonance spectroscopy (EPR), solvent swelling, imaging techniques, uniaxial compressive load testing and tearmore » testing. No significant changes in thermal stability or chemistry of the accelerated aged foam were observed, although gas evolution was detected. Changes in crystallization levels at low temperatures, microstructure, and mechanical properties were observed for foams with and without carbon nanofibers. In particular, foams aged under compressive load showed irreversible deformation of the porous microstructure. This study demonstrates that aging effects were enhanced when thermal and radiolysis were coupled together and that the addition of carbon nanofibers did not improve aging effects.« less
NASA Astrophysics Data System (ADS)
Cai, Dengke; Neyer, Andreas; Kuckuk, Rüdiger; Heise, H. Michael
2010-07-01
Special siloxane polymers have been produced via an addition reaction from commercially available two-component addition materials by thermal curing. Polydimethylsiloxane (PDMS) based polymers have already been used in the optical communication field, where passive polymer multimode waveguides are required for short-distance datacom optical applications. For such purpose, materials with low intrinsic absorption losses within the spectral region of 600-900 nm wavelengths are essential. For vibrational absorption band assignments, especially in the visible and short-wave near-infrared region, the mid-infrared and Raman spectra were investigated for fundamental vibrations of the siloxane materials, shedding light onto the chemistry before and after material polymerization. Within the near-infrared and long-wave visible spectral range, vibrational C sbnd H stretching overtone and combination bands dominate the spectra, rendering an optical characterization of core and clad materials. Such knowledge also provides information for the synthesis and optical characterization, e.g., of deuterated derivatives with less intrinsic absorption losses from molecular vibrations compared to the siloxane materials studied.
Coupled aging effects in nanofiber-reinforced siloxane foams
DOE Office of Scientific and Technical Information (OSTI.GOV)
Labouriau, Andrea; Robison, Tom; Geller, Drew Adam
Here, this study investigates the combined effects of ionizing radiation and thermal treatments on the aging of siloxane foams containing small amounts of carbon nanofibers. Our siloxane foams were exposed to accelerated aging conditions for more than two years, resulting in very low dose rates. In addition, foams were aged under compressive load to evaluate the strength of the porous microstructure. Samples were characterized by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (NMR), Mössbauer, mass spectroscopy, electron paramagnetic resonance spectroscopy (EPR), solvent swelling, imaging techniques, uniaxial compressive load testing and tearmore » testing. No significant changes in thermal stability or chemistry of the accelerated aged foam were observed, although gas evolution was detected. Changes in crystallization levels at low temperatures, microstructure, and mechanical properties were observed for foams with and without carbon nanofibers. In particular, foams aged under compressive load showed irreversible deformation of the porous microstructure. This study demonstrates that aging effects were enhanced when thermal and radiolysis were coupled together and that the addition of carbon nanofibers did not improve aging effects.« less
Refractory Oxidative-Resistant Ceramic Carbon Insulation
NASA Technical Reports Server (NTRS)
Leiser, Daniel B. (Inventor); Hsu, Ming-Ta S. (Inventor); Chen, Timothy S. (Inventor)
2001-01-01
High-temperature, lightweight, ceramic carbon insulation is prepared by coating or impregnating a porous carbon substrate with a siloxane gel derived from the reaction of an organodialkoxy silane and an organotrialkoxy silane in an acid or base medium in the presence of the carbon substrate. The siloxane gel is subsequently dried on the carbon substrate to form a ceramic carbon precursor. The carbon precursor is pyrolyzed, in an inert atmosphere, to form the ceramic insulation containing carbon, silicon, and oxygen. The carbon insulation is characterized as a porous, fibrous, carbon ceramic tile which is particularly useful as lightweight tiles for spacecraft.
Babcock, W.C.; Friesen, D.T.
1988-11-01
Novel semipermeable membranes and thin film composite (TFC) gas separation membranes useful in the separation of oxygen, nitrogen, hydrogen, water vapor, methane, carbon dioxide, hydrogen sulfide, lower hydrocarbons, and other gases are disclosed. The novel semipermeable membranes comprise the polycondensation reaction product of two complementary polyfunctional compounds, each having at least two functional groups that are mutually reactive in a condensation polymerization reaction, and at least one of which is selected from siloxanes, alkoxsilyls and aryloxysilyls. The TFC membrane comprises a microporous polymeric support, the surface of which has the novel semipermeable film formed thereon, preferably by interfacial polymerization.
Babcock, Walter C.; Friesen, Dwayne T.
1988-01-01
Novel semiperimeable membranes and thin film composite (TFC) gas separation membranes useful in the separation of oxygen, nitrogen, hydrogen, water vapor, methane, carbon dioxide, hydrogen sulfide, lower hydrocarbons, and other gases are disclosed. The novel semipermeable membranes comprise the polycondensation reaction product of two complementary polyfunctional compounds, each having at least two functional groups that are mutually reactive in a condensation polymerization reaction, and at least one of which is selected from siloxanes, alkoxsilyls and aryloxysilyls. The TFC membrane comprises a microporous polymeric support, the surface of which has the novel semipermeable film formed thereon, preferably by interfacial polymerization.
Inflammatory responses and side effects generated by several adjuvant-containing vaccines in turbot.
Noia, M; Domínguez, B; Leiro, J; Blanco-Méndez, J; Luzardo-Álvarez, A; Lamas, J
2014-05-01
Several of the adjuvants used in fish vaccines cause adhesions in internal organs when they are injected intraperitoneally. We describe the damage caused by vaccines containing different adjuvants in the turbot Scophthalmus maximus and show that internal adhesions can be greatly reduced by injecting the fish in a specific way. Injection of fish with the needle directed towards the anterior part of the peritoneal cavity induced formation of a single cell-vaccine mass (CVM) that became attached to the parietal peritoneum. However, injection of the fish with the needle pointing in the opposite direction generated many small CVM that became attached to the visceral and parietal peritoneum and in some cases caused internal adhesions. We describe the structural and cellular changes in the adjuvant-induced CVMs. The CVMs mainly comprised neutrophils and macrophages, although most of the former underwent apoptosis, which was particularly evident from day 3 post-injection. The apoptotic cells were phagocytosed by macrophages, which were the dominant cell type from the first days onwards. All of the vaccines induced angiogenesis in the area of contact between the CVM and the mesothelium. Vaccines containing oil-based adjuvants or microspheres induced the formation of granulomas in the CVM; however, no granulomas were observed in the CVM induced by vaccines containing aluminium hydroxide or Matrix-Q(®) as adjuvants. All of the vaccines induced strong migration of cells to the peritoneal cavity. Although some of these cells remained unattached in the peritoneal cavity, most of them formed part of the CVM. We also observed migration of the cells from the peritoneal cavity to lymphoid organs, indicating bidirectional traffic of cells between the inflamed areas and these organs. Copyright © 2014 Elsevier Ltd. All rights reserved.
NASA Astrophysics Data System (ADS)
Ren, Wanting
2007-12-01
Soft materials have attracted much scientific and technical interest in recent years. In this thesis, attention has been placed on the underpinning relations between molecular structure and properties of one type of soft matter---main chain liquid crystalline elastomers (MCLCEs), which may have application as shape memory or as auxetic materials. In this work, a number of siloxane-based MCLCEs and their linear polymer analogues (MCLCEs) with chemical variations were synthesized and examined. Among these chemical variations, rigid p-phenylene transverse rod and flat-shaped anthraquinone (AQ) mesogenic monomers were specifically incorporated. Thermal and X-ray analysis found a smectic C phase in most of our MCLCEs, which was induced by the strong self-segregation of siloxane spacers, hydrocarbon spacers and mesogenic rods. The smectic C mesophase of the parent LCE was not grossly affected by terphenyl transverse rods. Mechanical studies of MCLCEs indicated the typical three-region stress-strain curve and a polydomain-to-monodomain transition. Strain recovery experiments of MCLCEs showed a significant dependence of strain retentions on the initial strains but not on the chemical variations, such as the crosslinker content and the lateral substituents on mesogenic rods. The MCLCE with p-phenylene transverse rod showed a highly ordered smectic A mesophase at room temperature with high stiffness. Mechanical properties of MCLCEs with AQ monomers exhibit a strong dependence on the specific combination of hydrocarbon spacer and siloxane spacer, which also strongly affect the formation of pi-pi stacking between AQ units. Poisson's ratio measurement over a wide strain range found distinct trends of Poisson's ratio as a function of the crosslinker content as well as terphenyl transverse rod loadings in its parent MCLCEs.
Skartland, Liv Kjersti; Mjøs, Svein A; Grung, Bjørn
2011-09-23
The retention behavior of components analyzed by chromatography varies with instrumental settings. Being able to predict how changes in these settings alter the elution pattern is useful, both with regards to component identification, as well as with regards to optimization of the chromatographic system. In this work, it is shown how experimental designs can be used for this purpose. Different experimental designs for response surface modeling of the separation of fatty acid methyl esters (FAME) as function of chromatographic conditions in GC have been evaluated. Full factorial, central composite, Doehlert and Box-Behnken designs were applied. A mixture of 38 FAMEs was separated on a polar cyanopropyl substituted polysilphenylene-siloxane phase capillary column. The temperature gradient, the start temperature of the gradient, and the carrier gas velocity were varied in the experiments. The modeled responses, as functions of chromatographic conditions, were retention time, retention indices, peak widths, separation efficiency and resolution between selected peak pairs. The designs that allowed inclusion of quadratic terms among the predictors performed significantly better than factorial design. Box-Behnken design provided the best results for prediction of retention, but the differences between the central composite, Doehlert and Box-Behnken designs were small. Retention indices could be modeled with much better accuracy than retention times. However, because the errors of predicted tR of closely eluting peaks were highly correlated, models of resolution (Rs) that were based on retention time had errors in the same range as corresponding models based on ECL. Copyright © 2011 Elsevier B.V. All rights reserved.
Formulation/cure technology for ultrahigh molecular weight silphenylene-siloxane polymers
NASA Technical Reports Server (NTRS)
Hundley, N. H.; Patterson, W. J.
1985-01-01
Molecular weights above one million were achieved for methylvinylsilphenylene-siloxane terpolymers using a two-stage polymerization technique which was successfully scaled up to 200 grams. The resulting polymer was vulcanized by two different formulations and compared to an identically formulated commercial methylvinyl silicone on the basis of ultimate strength, Young's modulus, percent elongation at failure, and tear strength. Relative thermal/oxidative stabilities of the elastomers were assessed by gradient and isothermal thermogravimetric analyses performed in both air and nitrogen. The experimental elastomer exhibited enhanced thermal/oxidative stability and possed equivalent or superior mechanical properties. The effect of variations in prepolymer molecular weight on mechanical properties was also investigated.
Surface wettability enhancement of silicone hydrogel lenses by processing with polar plastic molds.
Lai, Y C; Friends, G D
1997-06-05
In the quest for hydrogel contact lenses with improved extended wear capability, the use of siloxane moieties in the lens materials was investigated. However, the introduction of hydrophobic siloxane groups gave rise to wettability and lipidlike deposit problems. It was found that when polysiloxane-based compositions for hydrogels were processed with polar plastic molds, such as those fabricated from an acrylonitrile-based polymer, the hydrogel lenses fabricated were wettable, with minimized lipidlike deposits. These findings were supported by the wettability of silicone hydrogel films, silicon, and nitrogen element contents near lens surfaces, as well as the results from clinical assessment of silicone hydrogel lenses.
Smoldering and Flame Resistant Textiles via Conformal Barrier Formation.
Zammarano, Mauro; Cazzetta, Valeria; Nazaré, Shonali; Shields, J Randy; Kim, Yeon Seok; Hoffman, Kathleen M; Maffezzoli, Alfonso; Davis, Rick
2016-12-07
A durable and flexible silicone-based backcoating (halogen free) is applied to the backside of an otherwise smoldering-prone and flammable fabric. When exposed to fire, cyclic siloxanes (produced by thermal decomposition of the backcoating) diffuse through the fabric in the gas phase. The following oxidation of the cyclic siloxanes forms a highly conformal and thermally stable coating that fully embeds all individual fibers and shields them from heat and oxidation. As a result, the combustion of the fabric is prevented. This is a novel fire retardant mechanism that discloses a powerful approach towards textiles and multifunctional flexible materials with combined smoldering/flaming ignition resistance and fire-barrier properties.
NASA Astrophysics Data System (ADS)
Ambati, Jyothirmai
This dissertation presents studies of the synthetic processes and applications of siloxane-based materials. Kinetic investigations of bridged organoalkoxysilanes that are precursors to organic-inorganic hybrid polysilsesquioxanes are a primary focus. Quick gelation despite extensive cyclization is found during the polymerization of bridged silane precursors except for silanes with certain short bridges. This work is an attempt to characterize and understand some of the distinct features of bridged silanes using experimental characterization, kinetic modeling and simulation. In addition to this, the dissertation shows how the properties of siloxane-materials can be engineered for drug delivery and adsorption. The phase behavior of polymerizing mixtures is first investigated to identify the solutions that favor kinetic characterization. Microphase separation is found to cause gradual loss of NMR signal for certain initial compositions. Distortionless Enhancement by Polarization Transfer 29Si NMR is employed to identify the products of polymerization of some short-bridged silanes under no signal loss conditions. This technique requires knowing indirect 29Si-1H scalar coupling constants which sometimes cannot be measured due to second-order effects. However, the B3LYP density functional method with 6-31G basis set is found to predict accurate 29Si- 1H coupling constants of organoalkoxysilanes and siloxanes. The scalar coupling constants thus estimated are employed to resolve non-trivial coupled NMR spectra and quantitative kinetic modeling is performed using the DEPT Si NMR transients. In order to investigate the role of the organic bridging group, the structural evolution of bridged and non-bridged silanes are compared using Monte Carlo simulations. Kinetic and simulation models suggest that cyclization plays a key role right from the onset of polymerization for bridged silanes even more than in non-bridged silanes. The simulations indicate that the carbosiloxane rings formed from short-bridged precursors slow down but do not prevent gelation. The tuning of siloxane-based materials for adsorption technologies are also discussed here. In the first example, antioxidant enzyme loading is investigated as a means to reduce oxidative stress generated by silica nanoparticle drug carriers. Materials are engineered for promising enzyme loading and protection from proteolysis. Second, the potential of copper sulfate impregnation to enhance adsorption of ammonia by silica is explored by molecular simulation. KEYWORDS: Sol-gel Polymerization, Kinetic Investigation, Si NMR, Bridged Silanes, DFT Calculations.
From the shop to the drain - Volatile methylsiloxanes in cosmetics and personal care products.
Capela, Daniela; Alves, Arminda; Homem, Vera; Santos, Lúcia
2016-01-01
Organosiloxanes are widely used in the formulation of a broad range of cosmetic and personal care products (PCPs), including creams and lotions, bath soaps, shampoo and hair care products to soften, smooth, and moisten. In fact, the intensive and widespread use of organosiloxanes combined with their lipophilic nature, makes them interesting targets for future research, particularly in the toxicology area. This study focused on determining the concentration levels of these compounds in the bestselling brands of PCPs in the Oporto region (Portugal), allowing the estimation of dermal and inhalation exposure to siloxanes and the evaluation of the quantities released to the environment "down-the-drain" and to air. To accomplish this task, a QuEChERS technique ("Quick, Easy, Cheap, Effective, Rugged, and Safe") was employed to extract the siloxanes from the target PCPs, which has never been tested before. The resulting extract was analysed by gas chromatography-mass spectrometry (GC-MS). The limits of detection varied between 0.17 (L2) and 3.75ngg(-1) (L5), being much lower than any values reported in the literature for this kind of products. In general, satisfactory precision (<10%) and accuracy values (average recovery of 84%) were obtained. 123 PCPs were analysed (moisturizers, deodorants, body and hair washes, toilet soaps, toothpastes and shaving products) and volatile methylsiloxanes were detected in 96% of the samples, in concentrations between 0.003μgg(-1) and 1203μgg(-1). Shampoo exhibited the highest concentration for cyclic and aftershaves for linear siloxanes. Combining these results with the daily usage amounts, an average daily dermal exposure of 25.04μgkgbw(-1)day(-1) for adults and 0.35μgkgbw(-1)day(-1) for baby/children was estimated. The main contributors for adult dermal exposure were body moisturizers, followed by facial creams and aftershaves, while for babies/children were body moisturizers, followed by shower gel and shampoo. Similarly, the average daily inhalation exposure was also estimated. Values of 1.56μgkgbw(-1)day(-1) for adults and 0.03μgkgbw(-1)day(-1) for babies/children were calculated. An estimate of the siloxanes amount released "down-the-drain" into the sewage systems through the use of toiletries was also performed. An emission per capita between 49.25 and 9574μgday(-1) (mean: 1817μgday(-1)) is expected and shampoo and shower gel presented the higher mean total values (1008μgday(-1) and 473.3μgday(-1), respectively). In the worst-case scenario, D5 and D3 were the predominant siloxanes in the effluents with 3336μgday(-1) and 3789μgday(-1), respectively. Regarding the air emissions per capita, values between 8.33 and 6109μgday(-1) (mean: 1607μgday(-1)) are expected and D5 and D6 were the predominant siloxanes. Copyright © 2016 Elsevier Ltd. All rights reserved.
Synthesis of lipase-catalysed silicone-polyesters and silicone-polyamides at elevated temperatures.
Frampton, Mark B; Zelisko, Paul M
2013-10-18
More and more enzymes are being explored as alternatives to conventional catalysts in chemical reactions. To utilize these biocatalysts to their fullest, it is incumbent on researchers to gain a complete understanding of the reaction conditions that particular enzymes will tolerate. To this end siloxane-containing polyesters and polyamides have been produced via N435-mediated catalysis at temperatures well above the normal denaturation temperature for free CalB. Low molecular weight disiloxane-based acceptors release the enzyme from its acylated state with equal proficiency while longer chain siloxanes favours polyester synthesis. The thermal tolerance of the enzyme catalyst is increased using longer chain diesters and generally more hydrophobic substrates.
Papadopoulos, P; Floudas, G; Schnell, I; Lieberwirth, I; Nguyen, T Q; Klok, H-A
2006-02-01
The structure and the associated dynamics of a series of poly(gamma-benzyl-L-glutamate)-b-poly(dimethyl siloxane)-b-poly(gamma-benzyl-L-glutamate) (PBLG-b-PDMS-b-PBLG) triblock copolymers were investigated using small- and wide-angle X-ray scattering, NMR, transmission electron microscopy, and dielectric spectroscopy, respectively. The structural analysis revealed phase separation in the case of the longer blocks with defected alpha-helical segments embedded within the block copolymer nanodomains. The alpha-helical persistence length was found to depend on the degree of segregation; thermodynamic confinement and chain stretching results in the partial annihilation of helical defects.
Dandeniyage, Loshini S; Adhikari, Raju; Bown, Mark; Shanks, Robert; Adhikari, Benu; Easton, Christopher D; Gengenbach, Thomas R; Cookson, David; Gunatillake, Pathiraja A
2018-03-04
A series of siloxane poly(urethane-urea) (SiPUU) were developed by incorporating a macrodiol linked with a diisocyanate to enhance mixing of hard and soft segments (SS). The effect of this modification on morphology, surface properties, surface elemental composition, and creep resistance was investigated. The linked macrodiol was prepared by reacting α,ω-bis(6-hydroxyethoxypropyl) poly(dimethylsiloxane)(PDMS) or poly(hexamethylene oxide) (PHMO) with either 4,4'-methylenediphenyl diisocyanate (MDI), hexamethylene diisocyanate (HDI), or isophorone diisocyanate (IPDI). SiPUU with PHMO-MDI-PHMO and PHMO-IPDI-PHMO linked macrodiols showed enhanced creep resistance and recovery when compared with a commercial biostable polyurethane, Elast-Eon™ 2A. Small and wide-angle X-ray scattering data were consistent with significant increase of hydrogen bonding between hard and SS with linked-macrodiols, which improved SiPUU's tensile stress and tear strengths. These SiPUU were hydrophobic with contact angle higher than 101° and they had low water uptake (0.7%·w/w of dry mass). They also had much higher siloxane concentration on the surface compared to that in the bulk. © 2018 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 2018. © 2018 Wiley Periodicals, Inc.
Dandeniyage, Loshini S; Gunatillake, Pathiraja A; Adhikari, Raju; Bown, Mark; Shanks, Robert; Adhikari, Benu
2017-08-31
Mixed macrodiol based siloxane poly(urethane-urea)s (SiPUU) having number average molecular weights in the range 87-129 kDa/mol were synthesized to give elastomers with high tensile and tear strengths required to fabricate artificial heart valves. Polar functional groups were introduced into the soft segment to improve the poor segmental compatibility of siloxane polyurethanes. This was achieved by linking α,ω-bis(6-hydroxyethoxypropyl) poly(dimethylsiloxane) (PDMS) or poly(hexamethylene oxide) (PHMO) macrodiols with either 4,4'-methylenediphenyl diisocyanate (MDI), hexamethylene diisocyanate (HDI) or isophorone diisocyanate (IPDI) prior to polyurethane synthesis. The hard segment was composed of MDI, and a 1:1 mixture of 1,3-bis(4-hydroxybutyl)-1,1,3,3-tetramethyldisiloxane and 1,2-ethylene diamine. We report the effect of urethane linkers in soft segments on properties of the SiPUU. PHMO linked with either MDI or IPDI produced SiPUU with the highest tensile and tear strengths. Linking PDMS hardly affected the tensile strength; however, the tear strength was improved. The stress-strain curves showed no plastic deformation region typically observed for conventional polyurethanes indicating good creep resistance. © 2017 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 2017. © 2017 Wiley Periodicals, Inc.
Oh, Heung-Il; Ye, Sang-Ho; Johnson, Carl A.; Woolley, Joshua R.; Federspiel, William J.; Wagner, William R.
2011-01-01
Hollow fiber membrane (HFM)-based artificial lungs can require a large blood-contacting membrane surface area to provide adequate gas exchange. However, such a large surface area presents significant challenges to hemocompatibility. One method to improve carbon dioxide (CO2) transfer efficiency might be to immobilize carbonic anhydrase (CA) onto the surface of conventional HFMs. By catalyzing the dehydration of bicarbonate in blood, CA has been shown to facilitate diffusion of CO2 toward the fiber membranes. This study evaluated the impact of surface modifying a commercially available microporous HFM-based artificial lung on fiber blood biocompatibility. A commercial poly(propylene) Celgard HFM surface was coated with a siloxane, grafted with amine groups, and then attached with CA which has been shown to facilitate diffusion of CO2 toward the fiber membranes. Results following acute ovine blood contact indicated no significant reduction in platelet deposition or activation with the siloxane coating or the siloxane coating with grafted amines relative to base HFMs. However,HFMs with attached CA showed a significant reduction in both platelet deposition and activation compared with all other fiber types. These findings, along with the improved CO2 transfer observed in CA modified fibers, suggest that its incorporation into HFM design may potentiate the design of a smaller, more biocompatible HFM-based artificial lung. PMID:20633159
Chen, Shiguo; Chen, Shaojun; Jiang, Song; Mo, Yangmiao; Luo, Junxuan; Tang, Jiaoning; Ge, Zaochuan
2011-07-01
Antibacterial agents receive a great deal of attention around the world due to the interesting academic problems of how to combat bacteria and of the beneficial health, social and economic effects of successful agents. Scientists are actively developing new antibacterial agents for biomaterial applications. This paper reports the novel antibacterial agent siloxane sulfopropylbetaine (SSPB), which contains reactive alkoxysilane groups. The structure and properties of SSPB were systematically investigated, with the results showing that SSPB contains both quaternary ammonium compounds and reactive siloxane groups. SSPB has good antibacterial activity against both Escherichia coli (E. coli, 8099) and Staphylococcus aureus (S. aureus, ATCC 6538). The minimal inhibition concentration is 70 μmol/ml SSPB against both E. coli and S. aureus. In addition, the SSPB antibacterial agent can be used in both weak acid and weak alkaline environments, functioning within the wide pH range of 4.0-9.0. The SSPB-modified glass surface killed 99.96% of both S. aureus and E. coli organisms within 24 h. No significant decrease was observed in this antibacterial activity after 20 washes. Moreover, SSPB does not induce a skin reaction and is nontoxic to animals. Thus, SSPB is an ideal candidate for future applications as a safe, environmentally friendly antibacterial agent. Copyright © 2011 Elsevier B.V. All rights reserved.
NASA Astrophysics Data System (ADS)
Ryan, Catherine; Alcock, Emma; Buttimer, Finbarr; Schmidt, Michael; Clarke, David; Pemble, Martyn; Bardosova, Maria
2017-12-01
We present a study of a range of cross-linked chitosan composites with potential antimicrobial applications. They were formed by cross-linking chitosan and siloxane networks and by introducing silver and gold nanoparticles (NPs). The aim was to investigate whether adding the metal NPs to the chitosan-siloxane composite would lead to a material with enhanced antimicrobial ability as compared to chitosan itself. The composites were synthesised in hydrogel form with the metal NPs embedded in the cross-linked chitosan network. Spectroscopic and microscopic techniques were employed to investigate the structural properties of the composite and the tensile strength of the structures was measured. It was found that the addition of metal NPs did not influence the mechanical strength of the composite. A crystal violet attachment assay results displayed a significant reduction in the attachment of E. coli to the cross-linked chitosan surfaces. Release profile tests suggest that the metal NPs do not contribute to the overall antimicrobial activity under neutral conditions. The contribution to the mechanical and antimicrobial properties from cross-linking with siloxane is significant, giving rise to a versatile, durable, antimicrobial material suitable for thin film formation, wound dressings or the coating of various surfaces where robustness and antimicrobial control are required.
Ryan, Catherine; Alcock, Emma; Buttimer, Finbarr; Schmidt, Michael; Clarke, David; Pemble, Martyn; Bardosova, Maria
2017-01-01
Abstract We present a study of a range of cross-linked chitosan composites with potential antimicrobial applications. They were formed by cross-linking chitosan and siloxane networks and by introducing silver and gold nanoparticles (NPs). The aim was to investigate whether adding the metal NPs to the chitosan-siloxane composite would lead to a material with enhanced antimicrobial ability as compared to chitosan itself. The composites were synthesised in hydrogel form with the metal NPs embedded in the cross-linked chitosan network. Spectroscopic and microscopic techniques were employed to investigate the structural properties of the composite and the tensile strength of the structures was measured. It was found that the addition of metal NPs did not influence the mechanical strength of the composite. A crystal violet attachment assay results displayed a significant reduction in the attachment of E. coli to the cross-linked chitosan surfaces. Release profile tests suggest that the metal NPs do not contribute to the overall antimicrobial activity under neutral conditions. The contribution to the mechanical and antimicrobial properties from cross-linking with siloxane is significant, giving rise to a versatile, durable, antimicrobial material suitable for thin film formation, wound dressings or the coating of various surfaces where robustness and antimicrobial control are required. PMID:28804527
Ryan, Catherine; Alcock, Emma; Buttimer, Finbarr; Schmidt, Michael; Clarke, David; Pemble, Martyn; Bardosova, Maria
2017-01-01
We present a study of a range of cross-linked chitosan composites with potential antimicrobial applications. They were formed by cross-linking chitosan and siloxane networks and by introducing silver and gold nanoparticles (NPs). The aim was to investigate whether adding the metal NPs to the chitosan-siloxane composite would lead to a material with enhanced antimicrobial ability as compared to chitosan itself. The composites were synthesised in hydrogel form with the metal NPs embedded in the cross-linked chitosan network. Spectroscopic and microscopic techniques were employed to investigate the structural properties of the composite and the tensile strength of the structures was measured. It was found that the addition of metal NPs did not influence the mechanical strength of the composite. A crystal violet attachment assay results displayed a significant reduction in the attachment of E. coli to the cross-linked chitosan surfaces. Release profile tests suggest that the metal NPs do not contribute to the overall antimicrobial activity under neutral conditions. The contribution to the mechanical and antimicrobial properties from cross-linking with siloxane is significant, giving rise to a versatile, durable, antimicrobial material suitable for thin film formation, wound dressings or the coating of various surfaces where robustness and antimicrobial control are required.
Staircase polymetalsilicon nanocomplexes - Polymetalphenyl siloxanes: Structure and properties
NASA Astrophysics Data System (ADS)
Shapkin, N. P.; Balanov, M. I.; Razov, V. I.; Gardionov, S. V.; Mayorov, V. Yu; Tokar, E. A.; Papynov, E. K.; Korochentsev, V. V.; Leont'ev, L. B.; Slobodyuk, A. B.; Modin, E. B.
2018-03-01
Polyphenyl siloxanes containing chromium, iron, and aluminum in the backbone chain have been synthesized. The structure of the obtained staircase nano-metal complexes has been studied by the methods of XRD analysis and IR, 29Si and 27Al NMR, and XPS spectroscopy and scanning electron microscopy. Physical-chemical characteristics of these compounds have been investigated by the positron annihilation spectroscopy (PAS) and low-temperature nitrogen adsorption. The data of X-ray diffraction analysis (XRD) enabled us to calculate the size and volume of coherent scattering regions (CSR) and the cross-section area of the polymer chains. By means of the PAS method, the specific volumes of positron (Ve+) and positronium (Vps) "traps" have been calculated. The data of 29Si NMR spectroscopy have shown the presence of T2 and T3 fragments in the structure. As was shown on the basis of the data of 27Al NMR and XPS spectroscopy, tetrahedral (66%) and octahedral surroundings of the metal atom were realized in the backbone chain. The obtained data were used to describe a spatial layered structure of phenyl siloxanes containing trivalent metals. The electron microscopy of nanocomplexes revealed the presence of spherical particles, whose size changes in cases of chromium, iron, and aluminum. Using the data of low-temperature nitrogen adsorption, it was assumed that the specific surface area was filled with a layer of compacted spherical particles, whereas the layer thickness was determined, in its turn, by the specific polarizing potential (SPP) calculated as a ratio of the polarizing potential (PP) to the volume of voids between coherent scattering regions. Similar dependence is observed between the layer thickness and the specific polarizing potential calculated as a ratio of the polarizing potential to the positronium "trap" volume. A direct dependence between the thickness of the spherical particles layer and the specific polarizing potential has been demonstrated. The assumption on a fractal structure of spherical particles was made. Tribotechnical properties of the motor oil with metal siloxane additives have been studied.
The role of temperature in forming sol-gel biocomposites containing polydopamine.
Dyke, Jason Christopher; Hu, Huamin; Lee, Dong Joon; Ko, Ching-Chang; You, Wei
2014-11-28
To further improve the physical strength and biomedical applicability of bioceramicsbuilt on hydroxyapatite-gelatin (HAp-Gel) and siloxane sol-gel reactions, we incorporated mussel adhesive inspired polydopamine (PD) into our original composite based on HAp-Gel cross-linked with siloxane. Surprisingly, with the addition of PD, we observed that the processing conditions and temperatures play an important role in the structure and performance of these materials. A systematic study to investigate this temperature dependence behavior discloses that the rate of crosslinking of silane during the sol-gel process is significantly influenced by the temperature, whereas the polymerization of the dopamine only shows minor temperature dependence. With this discovery, we report an innovative thermal process for the design and application of these biocomposites.
The role of temperature in forming sol-gel biocomposites containing polydopamine
Dyke, Jason Christopher; Hu, Huamin; Lee, Dong Joon; Ko, Ching-Chang; You, Wei
2014-01-01
To further improve the physical strength and biomedical applicability of bioceramicsbuilt on hydroxyapatite-gelatin (HAp-Gel) and siloxane sol-gel reactions, we incorporated mussel adhesive inspired polydopamine (PD) into our original composite based on HAp-Gel cross-linked with siloxane. Surprisingly, with the addition of PD, we observed that the processing conditions and temperatures play an important role in the structure and performance of these materials. A systematic study to investigate this temperature dependence behavior discloses that the rate of crosslinking of silane during the sol-gel process is significantly influenced by the temperature, whereas the polymerization of the dopamine only shows minor temperature dependence. With this discovery, we report an innovative thermal process for the design and application of these biocomposites. PMID:25485111
Transparent and robust siloxane-based hybrid lamella film as a water vapor barrier coating.
Tokudome, Yasuaki; Hara, Takaaki; Abe, Risa; Takahashi, Masahide
2014-11-12
Water vapor barriers are important in various application fields, such as food packaging and sealants in electronic devices. Polymer/clay composites are well-studied water vapor barrier materials, but their transparency and mechanical strength degrade with increasing clay loading. Herein, we demonstrate films with good water vapor barrier properties, high transparency, and mechanical/thermal stability. Water vapor barrier films were prepared by the solution crystallization of siloxane hybrid lamellae. The films consist of highly crystallized organic/inorganic hybrid lamellae, which provide high transparency, hardness, and thermal stability and inhibit the permeation of water vapor. The water permeability of a 6 μm thick hybrid film is comparable to that of a 200 μm thick silicon rubber film.
NASA Technical Reports Server (NTRS)
Mcgrath, J. E.
1982-01-01
The radiation degradation of poly(arylene ether sulfones) and related materials is studied. These basic studies are important both as a means to developing stronger, more stable matrix resins for composite materials, as well as to improve the data base in regard to chemical structure-physical property relationships. Thirty homo and copolymers were synthesized, at least partially characterized and, in several cases suitable film casting techniques were developed. Four samples were chosen for initial radiation degradation. Poly(dimethyl siloxane) soft bocks/segments can preferentially migrate to the surface of copolymer films. Since siloxanes are utilized as thermal control coatings, this form of 'molecular' coating is of interest. The chemistry for preparing such copolymers with any of the polymers described was demonstrated.
Estephan, Zaki G; Hariri, Hanaa H; Schlenoff, Joseph B
2013-02-26
Stable aqueous dispersions of superparamagnetic iron oxide nanoparticles were synthesized in one step in the presence of a zwitterionic siloxane as the stabilizing/capping/solubilizing ligand. The hydrodynamic diameter of the particles was tuned by controlling the concentration of zwitterion siloxane, which ultimately yielded monodisperse nanoparticles small enough for renal filtration (<6 nm diameter). The zwitterated nanoparticles were readily dispersed and stable in aqueous media in the pH range 6-9 but exhibited lower magnetization values than nonzwitterated materials due to amorphous content and spin canting, typical for particles of such size. Turbidimetry and light scattering studies revealed no interaction between the particles and proteins, suggesting the materials will circulate well in vivo.
Laser Processed Condensing Heat Exchanger Technology Development
NASA Technical Reports Server (NTRS)
Hansen, Scott; Wright, Sarah; Wallace, Sarah; Hamilton, Tanner; Dennis, Alexander; Zuhlke, Craig; Roth, Nick; Sanders, John
2017-01-01
The reliance on non-permanent coatings in Condensing Heat Exchanger (CHX) designs is a significant technical issue to be solved before long-duration spaceflight can occur. Therefore, high reliability CHXs have been identified by the Evolvable Mars Campaign (EMC) as critical technologies needed to move beyond low earth orbit. The Laser Processed Condensing Heat Exchanger project aims to solve these problems through the use of femtosecond laser processed surfaces, which have unique wetting properties and potentially exhibit anti-microbial growth properties. These surfaces were investigated to identify if they would be suitable candidates for a replacement CHX surface. Among the areas researched in this project include microbial growth testing, siloxane flow testing in which laser processed surfaces were exposed to siloxanes in an air stream, and manufacturability.
Yamaguchi, Hiroyuki; Takezawa, Toshiaki
2018-05-29
A collagen vitrigel membrane (CVM) we developed can function as both a scaffold for cells and a pathway for chemicals. To extrapolate the corneal permeability of chemicals in vivo, we proposed six corneal models using the CVM. Thin and thick CVMs were utilized as models for Bowman's membrane (BM) and an acellular-stroma (AS), respectively. Models for a corneal epithelium (CEpi), a corneal epithelium-acellular stroma (CEpi-AS), a corneal epithelium-endothelium (CEpi-Endo) and a corneal epithelium-acellular stroma-endothelium (CEpi-AS-Endo) were fabricated by culturing corneal epithelial cells and/or corneal endothelial cells on the surface of CVMs. Subsequently, the permeability coefficient (P app ) value of each model was calculated using five chemicals with different molecular radii; cyanocobalamin and four FITC-dextrans (FD-4, FD-10, FD-20 and FD-40). The slopes of P app versus molecular radii of those chemicals in the both BM and AS models were almost similar to data using an excised rabbit corneal stroma. The ratios of P app values in models for BM, CEpi and CEpi-Endo against those in data using an excised rabbit cornea were calculated as 75.4, 6.4 and 4.5-folds for FD-4 and 38.7, 10.0 and 4.2-folds for FD-10, respectively. Similarly, those in models for AS, CEpi-AS and CEpi-AS-Endo were calculated as 26.1, 2.5 and 0.6-folds for FD-4 and 26.1, 1.5 and 0.6-folds for FD-10, respectively. These results suggest that the CEpi-AS-Endo model with both the barrier function of corneal cell layers and the diffusion capacity of chemicals in thick CVM is most appropriate for extrapolating the corneal permeability of chemicals in vivo . The American Society for Pharmacology and Experimental Therapeutics.
Litsas, George; Lucchese, Alessandra
2016-01-01
Purpose: To investigate the relationship between dental, chronological, and cervical vertebral maturation growth in the peak growth period, as well as to study the association between the dental calcification phases and the skeletal maturity stages during the same growth period. Methods: Subjects were selected from orthodontic pre-treatment cohorts consisting of 420 subjects where 255 were identified and enrolled into the study, comprising 145 girls and 110 boys. The lateral cephalometric and panoramic radiographs were examined from the archives of the Department of Orthodontics, Aristotle University of Thessaloniki, Greece. Dental age was assessed according to the method of Demirjian, and skeletal maturation according to the Cervical Vertebral Maturation Method. Statistical elaboration included Spearman Brown formula, descriptive statistics, Pearson’s correlation coefficient and regression analysis, paired samples t-test, and Spearman’s rho correlation coefficient. Results: Chronological and dental age showed a high correlation for both gender(r =0.741 for boys, r = 0.770 for girls, p<0.001). The strongest correlation was for the CVM Stage IV for both males (r=0.554) and females (r=0.68). The lowest correlation was for the CVM Stage III in males (r=0.433, p<0.001) and for the CVM Stage II in females (r=0.393, p>0.001). The t-test revealed statistically significant differences between these variables (p<0.001) during the peak period. A statistically significant correlation (p<0.001) between tooth calcification and CVM stages was determined. The second molars showed the highest correlation with CVM stages (CVMS) (r= 0.65 for boys, r = 0.72 for girls). Conclusion: Dental age was more advanced than chronological for both boys and girls for all CVMS. During the peak period these differences were more pronounced. Moreover, all correlations between skeletal and dental stages were statistically significant. The second molars showed the highest correlation whereas the canines showed the lowest correlation for both gender. PMID:27335610
Lajolo, Carlo; Giuliani, Michele; Cordaro, Massimo; Marigo, Luca; Marcelli, Antonio; Fiorillo, Fabio; Pascali, Vincenzo L; Oliva, Antonio
2013-10-01
Chronological age (CA) plays a fundamental role in forensic dentistry (i.e. personal identification and evaluation of imputability). Even though several studies outlined the association between biological and chronological age, there is still great variability in the estimates. The aim of this study was to determine the possible correlation between biological and CA age through the use of two new radiographic indexes (Oro-Cervical Radiographic Simplified Score - OCRSS and Oro-Cervical Radiographic Simplified Score Without Wisdom Teeth - OCRSSWWT) that are based on the oro-cervical area. Sixty Italian Caucasian individuals were divided into 3 groups according to their CA: Group 1: CAG 1 = 8-14 yr; Group 2: CAG 2 = 14-18 yr; Group 3: CAG 3 = 18-25 yr; panorexes and standardised cephalograms were evaluated according Demirjian's Method for dental age calculation (DM), Cervical Vertebral Maturation method for skeletal age calculation (CVMS) and Third Molar Development for age estimation (TMD). The stages of each method were simplified in order to generate OCRSS, which summarized the simplified scores of the three methods, and OCRSSWWT, which summarized the simplified DM and CVMS scores. There was a significant correlation between OCRSS and CAGs (Slope = 0.954, p < 0.001, R-squared = 0.79) and between OCRSSWWT and CAGs (Slope = 0.863, p < 0.001, R-squared = 0.776). Even though the indexes, especially OCRSS, appear to be highly reliable, growth variability among individuals can deeply influence the anatomical changes from childhood to adulthood. A multi-disciplinary approach that considers many different biomarkers could help make radiological age determination more reliable when it is used to predict CA. Copyright © 2013 Elsevier Ltd and Faculty of Forensic and Legal Medicine. All rights reserved.
Sampling Artifacts from Conductive Silicone Tubing
DOE Office of Scientific and Technical Information (OSTI.GOV)
Timko, Michael T.; Yu, Zhenhong; Kroll, Jesse
2009-05-15
We report evidence that carbon impregnated conductive silicone tubing used in aerosol sampling systems can introduce two types of experimental artifacts: 1) silicon tubing dynamically absorbs carbon dioxide gas, requiring greater than 5 minutes to reach equilibrium and 2) silicone tubing emits organic contaminants containing siloxane that adsorb onto particles traveling through it and onto downstream quartz fiber filters. The consequence can be substantial for engine exhaust measurements as both artifacts directly impact calculations of particulate mass-based emission indices. The emission of contaminants from the silicone tubing can result in overestimation of organic particle mass concentrations based on real-time aerosolmore » mass spectrometry and the off-line thermal analysis of quartz filters. The adsorption of siloxane contaminants can affect the surface properties of aerosol particles; we observed a marked reduction in the water-affinity of soot particles passed through conductive silicone tubing. These combined observations suggest that the silicone tubing artifacts may have wide consequence for the aerosol community and should, therefore, be used with caution. Gentle heating, physical and chemical properties of the particle carriers, exposure to solvents, and tubing age may influence siloxane uptake. The amount of contamination is expected to increase as the tubing surface area increases and as the particle surface area increases. The effect is observed at ambient temperature and enhanced by mild heating (<100 oC). Further evaluation is warranted.« less
Boron filled siloxane polymers for radiation shielding
NASA Astrophysics Data System (ADS)
Labouriau, Andrea; Robison, Tom; Shonrock, Clinton; Simmonds, Steve; Cox, Brad; Pacheco, Adam; Cady, Carl
2018-03-01
The purpose of the present work was to evaluate changes to structure-property relationships of 10B filled siloxane-based polymers when exposed to nuclear reactor radiation. Highly filled polysiloxanes were synthesized with the intent of fabricating materials that could shield high neutron fluences. The newly formulated materials consisted of cross-linked poly-diphenyl-methylsiloxane filled with natural boron and carbon nanofibers. This polymer was chosen because of its good thermal and chemical stabilities, as well as resistance to ionizing radiation thanks to the presence of aromatic groups in the siloxane backbone. Highly isotopically enriched 10B filler was used to provide an efficient neutron radiation shield, and carbon nanofibers were added to improve mechanical strength. This novel polymeric material was exposed in the Annular Core Research Reactor (ACRR) at Sandia National Labs to five different neutron/gamma fluxes consisting of very high neutron fluences within very short time periods. Thermocouples placed on the specimens recorded in-situ temperature changes during radiation exposure, which agreed well with those obtained from our MCNP simulations. Changes in the microstructural, thermal, chemical, and mechanical properties were evaluated by SEM, DSC, TGA, FT-IR NMR, solvent swelling, and uniaxial compressive load measurements. Our results demonstrate that these newly formulated materials are well-suitable to be used in applications that require exposure to different types of ionizing conditions that take place simultaneously.
Helling, Ruediger; Mieth, Anja; Altmann, Stefan; Simat, Thomas Joachim
2009-03-01
Different silicone baking moulds (37 samples) were characterized with respect to potential migrating substances using 1H-NMR, RP-HPLC-UV/ELSD and GC techniques. In all cases cyclic organosiloxane oligomers with the formula [Si(CH3)2-O]n were identified (n = 6 ... 50). Additionally, linear, partly hydroxyl-terminated organosiloxanes HO-[Si(CH3)2-O]n-H (n = 7 ... 20) were found in 13 samples. No substances other than siloxanes could be detected, meaning the migrants mainly consist of organopolysiloxanes. Based on this knowledge, a 1H-NMR quantification method for siloxanes was established for the analysis of both simulants and foodstuffs. Validation of the 1H-NMR method gave suitable performance characteristics: limit of detection 8.7 mg kg(-1) oil, coefficient of variation 7.8% (at a level of 1.0 mg kg(-1) food). Migration studies were carried out with simulants (olive oil, isooctane, ethanol (95%), Tenax) as well as preparation of different cakes. From the 1st to 10th experiment, siloxane migration into cakes only slightly decreased, with a significant dependence on fat content. Migration never exceeded a level of 21 mg kg(-1) (3 mg dm(-2)) and was, therefore, well below the overall migration limit of 60 mg kg(-1) (10 mg dm(-2)). However, migration behaviour into simulants differed completely from these results.
Boron Filled Siloxane Polymers for Radiation Shielding
Labouriau, Andrea; Robison, Tom; Shonrock, Clinton Otto; ...
2017-09-01
The purpose of the present work was to evaluate changes to structure-property relationships of 10B filled siloxane-based polymers when exposed to nuclear reactor radiation. Highly filled polysiloxanes were synthesized with the intent of fabricating materials that could shield high neutron fluences. The newly formulated materials consisted of cross-linked poly-diphenyl-methylsiloxane filled with natural boron and carbon nanofibers. This polymer was chosen because of its good thermal and chemical stabilities, as well as resistance to ionizing radiation thanks to the presence of aromatic groups in the siloxane backbone. Highly isotopically enriched 10B filler was used to provide an efficient neutron radiation shield,more » and carbon nanofibers were added to improve mechanical strength. This novel polymeric material was exposed in the Annular Core Research Reactor (ACRR) at Sandia National Labs to five different neutron/gamma fluxes consisting of very high neutron fluences within very short time periods. Thermocouples placed on the specimens recorded in-situ temperature changes during radiation exposure, which agreed well with those obtained from our MCNP simulations. Changes in the microstructural, thermal, chemical, and mechanical properties were evaluated by SEM, DSC, TGA, FT-IR NMR, solvent swelling, and uniaxial compressive load measurements. In conclusion, our results demonstrate that these newly formulated materials are well-suitable to be used in applications that require exposure to different types of ionizing conditions that take place simultaneously.« less
Boron Filled Siloxane Polymers for Radiation Shielding
DOE Office of Scientific and Technical Information (OSTI.GOV)
Labouriau, Andrea; Robison, Tom; Shonrock, Clinton Otto
The purpose of the present work was to evaluate changes to structure-property relationships of 10B filled siloxane-based polymers when exposed to nuclear reactor radiation. Highly filled polysiloxanes were synthesized with the intent of fabricating materials that could shield high neutron fluences. The newly formulated materials consisted of cross-linked poly-diphenyl-methylsiloxane filled with natural boron and carbon nanofibers. This polymer was chosen because of its good thermal and chemical stabilities, as well as resistance to ionizing radiation thanks to the presence of aromatic groups in the siloxane backbone. Highly isotopically enriched 10B filler was used to provide an efficient neutron radiation shield,more » and carbon nanofibers were added to improve mechanical strength. This novel polymeric material was exposed in the Annular Core Research Reactor (ACRR) at Sandia National Labs to five different neutron/gamma fluxes consisting of very high neutron fluences within very short time periods. Thermocouples placed on the specimens recorded in-situ temperature changes during radiation exposure, which agreed well with those obtained from our MCNP simulations. Changes in the microstructural, thermal, chemical, and mechanical properties were evaluated by SEM, DSC, TGA, FT-IR NMR, solvent swelling, and uniaxial compressive load measurements. In conclusion, our results demonstrate that these newly formulated materials are well-suitable to be used in applications that require exposure to different types of ionizing conditions that take place simultaneously.« less
Effect of Silicone on the Collagen Fibrillogenesis and Stability
Kadziński, Leszek; Prokopowicz, Magdalena; Jakóbkiewicz-Banecka, Joanna; Gabig-Cimińska, Magdalena; Łukasiak, Jerzy; Banecki, Bogdan
2015-01-01
Collagen, the most abundant protein in mammals, is able to form fibrils, which have central role in tissue repair, fibrosis, and tumor invasion. As a component of skin, tendons, and cartilages, this protein contacts with any implanted materials. An inherent problem associated with implanted prostheses is their propensity to be coated with host proteins shortly after implantation. Also, silicone implants undergoing relatively long periods of contact with blood can lead to formation of thrombi and emboli. In this paper, we demonstrate the existence of interactions between siloxanes and collagen. Low-molecular-weight cyclic siloxane (hexamethylcyclotrisiloxane—D3) and polydimethylsiloxanes (PDMS) forming linear chains, ranging in viscosity from 20 to 12,000 cSt, were analyzed. We show that D3 as well as short-chain PDMS interact with collagen, resulting in a decrease in fibrillogenesis. However, loss of collagen native structure does not occur because of these interactions. Rather, collagen seems to be sequestered in its native form in an interlayer formed by collagen–siloxane complexes. On the other hand, silicone molecules with longer chains (i.e., PDMS with viscosity of 1000 and 12,000 cSt, the highest viscosity analyzed here) demonstrate little interaction with this protein and do not seem to affect collagen activity. © 2015 Wiley Periodicals, Inc. and the American Pharmacists Association J Pharm Sci 104:1275–1281, 2015 PMID:25589402
NASA Astrophysics Data System (ADS)
Sreenilayam, S. P.; Rodriguez-Lojo, D.; Panov, V. P.; Swaminathan, V.; Vij, J. K.; Panarin, Yu. P.; Gorecka, E.; Panov, A.; Stevenson, P. J.
2017-10-01
Calamitic liquid crystals based on 5-phenyl-pyrimidine derivatives have been designed, synthesized, and characterized. The 5-phenyl pyrimidine core was functionalized with a chiral (R,R)-2,3-epoxyhexoxy chain on one side and either siloxane or perfluoro terminated chains on the opposite side. The one involving a perfluorinated chain shows Sm A* phase over a wide temperature range of 82 °C, whereas the siloxane analog exhibits both Sm A* and Sm C* phases over a broad range of temperatures, and a weak first-order Sm A*-Sm C* transition is observed. For the siloxane analog, the reduction factor for the layer shrinkage R (relative to its thickness at the Sm A*-Sm C* transition temperature, TAC) is ˜0.373 , and layer shrinkage is 1.7% at a temperature of 13 °C below the TAC. This compound is considered to have "de Vries smectic" characteristics with the de Vries coefficient CdeVries of ˜0.86 on the scale of zero (maximum-layer shrinkage) to 1 (zero-layer shrinkage). A three-parameter mean-field model is introduced for the orientational distribution function (ODF) to reproduce the electro-optic properties. This model explains the experimental results and leads to the ODF, which exhibits a crossover from the sugar-loaf to diffuse-cone ODF some 3 °C above TAC.
Mahurin, Shannon Mark; Sokolov, Alexei P.; Saito, Tomonori; ...
2016-07-06
Here, the vinyl addition polymerization of norbornylbased monomers bearing polar functional groups is often problematic, leading to low molecular weight polymers in poor yield. Herein, we provide proof-of-principle evidence that addition-type homopolymers of siloxane substituted norbornyl-based monomers may be readily synthesized using the catalyst trans-[Ni(C 6F 5) 2(SbPh 3) 2]. Polymerizations using this catalyst reached moderate to high conversion in just 5 min of polymerization and produced siloxanesubstituted polymers with molecular weights exceeding 100 kg/mol. These polymers showed excellent thermal stability (T d ≥ 362 °C) and were cast into membranes that displayed high CO 2 permeability and enhanced COmore » 2/N 2 selectivity as compared to related materials.« less
High-throughput methods for characterizing the mechanical properties of coatings
NASA Astrophysics Data System (ADS)
Siripirom, Chavanin
The characterization of mechanical properties in a combinatorial and high-throughput workflow has been a bottleneck that reduced the speed of the materials development process. High-throughput characterization of the mechanical properties was applied in this research in order to reduce the amount of sample handling and to accelerate the output. A puncture tester was designed and built to evaluate the toughness of materials using an innovative template design coupled with automation. The test is in the form of a circular free-film indentation. A single template contains 12 samples which are tested in a rapid serial approach. Next, the operational principles of a novel parallel dynamic mechanical-thermal analysis instrument were analyzed in detail for potential sources of errors. The test uses a model of a circular bilayer fixed-edge plate deformation. A total of 96 samples can be analyzed simultaneously which provides a tremendous increase in efficiency compared with a conventional dynamic test. The modulus values determined by the system had considerable variation. The errors were observed and improvements to the system were made. A finite element analysis was used to analyze the accuracy given by the closed-form solution with respect to testing geometries, such as thicknesses of the samples. A good control of the thickness of the sample was proven to be crucial to the accuracy and precision of the output. Then, the attempt to correlate the high-throughput experiments and conventional coating testing methods was made. Automated nanoindentation in dynamic mode was found to provide information on the near-surface modulus and could potentially correlate with the pendulum hardness test using the loss tangent component. Lastly, surface characterization of stratified siloxane-polyurethane coatings was carried out with X-ray photoelectron spectroscopy, Rutherford backscattering spectroscopy, transmission electron microscopy, and nanoindentation. The siloxane component segregates to the surface during curing. The distribution of siloxane as a function of thickness into the sample showed differences depending on the formulation parameters. The coatings which had higher siloxane content near the surface were those coatings found to perform well in field tests.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Bockstaller, Michael
The low thermal conductivity of state-of-the-art polymer encapsulants (k ~ 0.15 Wm-1K-1) limits the efficiency and power density of current phosphor conversion light emitting diodes (pc-LEDs). The technical objective of this project was to demonstrate synthesis and processing schemes for the fabrication of polymer hybrid encapsulants with a thermal conductivity exceeding k = 0.4 Wm-1K-1 for LED applications. The ‘hybrid polymer’ approach encompasses the dispersion of high thermal conductivity particle fillers (zinc oxide, ZnO as well as the alpha-polymorph of alumina, Al2O3) within a polysiloxane matrix (poly(dimethylsiloxane), PDMS as well as poly(phenyl methyl siloxane), PPMS) to increase the thermal conductivitymore » while maintaining optical transparency and photothermal stability at levels consistent with LED applications. To accomplish this goal, a novel synthesis method for the fabrication of nanosized ZnO particles was developed and a novel surface chemistry was established to modify the surface of zinc oxide particle fillers and thus to enable their dispersion in poly(dimethyl siloxane) (PDMS) matrix polymers. Molecular dynamics and Mie simulations were used to optimize ligand structure and to enable the concurrent mixing of particles in PDMS/PPMS embedding media while also minimizing the thermal boundary resistance as well as optical scattering of particle fillers. Using this approach the synthesis of PDMS/ZnO hybrid encapsulants exhibiting a thermal conductivity of 0.64 Wm-1K-1 and optical transparency > 0.7 mm-1 was demonstrated. A forming process based on micromolding was developed to demonstrate the forming of particle filled PDMS into film and lens shapes. Photothermal stability testing revealed stability of the materials for approximately 4000 min when exposed to blue light LED (450 nm, 30 W/cm2). One postgraduate and seven graduate students were supported by the project. The research performed within this project led to fifteen publications in peer-reviewed journals and one patent application. The grant stimulated a multi-investigator research collaborations among seven investigators at Carnegie Mellon University to address the challenge of encapsulants in pc-LED applications. The grant also catalyzed the future collaboration between researchers at Carnegie Mellon University and OSRAM Sylvania to address challenges associated with the use if polymers in LED applications.« less
NASA Astrophysics Data System (ADS)
Balciunas, Evaldas; Jonusauskas, Linas; Valuckas, Vytautas; Baltriukiene, Daiva; Bukelskiene, Virginija; Gadonas, Roaldas; Malinauskas, Mangirdas
2012-06-01
In this work, a combination of Direct Laser Writing (DLW), PoliDiMethylSiloxane (PDMS) soft lithography and UV lithography was used to create cm- scale microstructured polymer scaolds for cell culture experiments out of dierent biocompatible materials: novel hybrid organic-inorganic SZ2080, PDMS elastomer, biodegradable PEG- DA-258 and SU-8. Rabbit muscle-derived stem cells were seeded on the fabricated dierent periodicity scaolds to evaluate if the relief surface had any eect on cell proliferation. An array of microlenses was fabricated using DLW out of SZ2080 and replicated in PDMS and PEG-DA-258, showing good potential applicability of the used techniques in many other elds like micro- and nano- uidics, photonics, and MicroElectroMechanical Systems (MEMS). The synergetic employment of three dierent fabrication techniques allowed to produce desired objects with low cost, high throughput and precision as well as use materials that are dicult to process by other means (PDMS and PEG-DA-258). DLW is a relatively slow fabrication method, since the object has to be written point-by-point. By applying PDMS soft lithography, we were enabled to replicate laser-fabricated scaolds for stem cell growth and micro-optical elements for lab-on-a-chip applications with high speed, low cost and good reproducible quality.
Rueggeberg, Frederick A.; Niu, Li-na; Mettenberg, Donald; Yiu, Cynthia K. Y.; Blizzard, John D.; Wu, Christine D.; Mao, Jing; Drisko, Connie L.; Pashley, David H.; Tay, Franklin R.
2012-01-01
Global increase in patients seeking orthodontic treatment creates a demand for the use of acrylic resins in removable appliances and retainers. Orthodontic removable appliance wearers have a higher risk of oral infections that are caused by the formation of bacterial and fungal biofilms on the appliance surface. Here, we present the synthetic route for an antibacterial and antifungal organically-modified silicate (ORMOSIL) that has multiple methacryloloxy functionalities attached to a siloxane backbone (quaternary ammonium methacryloxy silicate, or QAMS). By dissolving the water-insoluble, rubbery ORMOSIL in methyl methacrylate, QAMS may be copolymerized with polymethyl methacrylate, and covalently incorporated in the pressure-processed acrylic resin. The latter demonstrated a predominantly contact-killing effect on Streptococcus mutans ATCC 36558 and Actinomyces naselundii ATCC 12104 biofilms, while inhibiting adhesion of Candida albicans ATCC 90028 on the acrylic surface. Apart from its favorable antimicrobial activities, QAMS-containing acrylic resins exhibited decreased water wettability and improved toughness, without adversely affecting the flexural strength and modulus, water sorption and solubility, when compared with QAMS-free acrylic resin. The covalently bound, antimicrobial orthodontic acrylic resin with improved toughness represents advancement over other experimental antimicrobial acrylic resin formulations, in its potential to simultaneously prevent oral infections during appliance wear, and improve the fracture resistance of those appliances. PMID:22870322
Stretching Micropatterned Cells on a PDMS Membrane
Carpi, Nicolas; Piel, Matthieu
2014-01-01
Mechanical forces exerted on cells and/or tissues play a major role in numerous processes. We have developed a device to stretch cells plated on a PolyDiMethylSiloxane (PDMS) membrane, compatible with imaging. This technique is reproducible and versatile. The PDMS membrane can be micropatterned in order to confine cells or tissues to a specific geometry. The first step is to print micropatterns onto the PDMS membrane with a deep UV technique. The PDMS membrane is then mounted on a mechanical stretcher. A chamber is bound on top of the membrane with biocompatible grease to allow gliding during the stretch. The cells are seeded and allowed to spread for several hours on the micropatterns. The sample can be stretched and unstretched multiple times with the use of a micrometric screw. It takes less than a minute to apply the stretch to its full extent (around 30%). The technique presented here does not include a motorized device, which is necessary for applying repeated stretch cycles quickly and/or computer controlled stretching, but this can be implemented. Stretching of cells or tissue can be of interest for questions related to cell forces, cell response to mechanical stress or tissue morphogenesis. This video presentation will show how to avoid typical problems that might arise when doing this type of seemingly simple experiment. PMID:24514571
Rauert, Cassandra; Harner, Tom; Schuster, Jasmin K; Eng, Anita; Fillmann, Gilberto; Castillo, Luisa Eugenia; Fentanes, Oscar; Villa Ibarra, Martín; Miglioranza, Karina S B; Moreno Rivadeneira, Isabel; Pozo, Karla; Aristizábal Zuluaga, Beatriz Helena
2018-06-15
A special initiative was run by the Global Atmospheric Passive Sampling (GAPS) Network to provide atmospheric data on a range of emerging chemicals of concern and candidate and new persistent organic pollutants in the Group of Latin America and Caribbean (GRULAC) region. Regional-scale data for a range of flame retardants (FRs) including polybrominated diphenyl ethers (PBDEs), organophosphate esters (OPEs), and a range of alternative FRs (novel FRs) are reported over 2 years of sampling with low detection frequencies of the novel FRs. Atmospheric concentrations of the OPEs were an order of magnitude higher than all other FRs, with similar profiles at all sites. Regional-scale background concentrations of the poly- and perfluoroalkyl substances (PFAS), including the neutral PFAS (n-PFAS) and perfluoroalkyl acids (PFAAs), and the volatile methyl siloxanes (VMS) are also reported. Ethyl perfluorooctane sulfonamide (EtFOSA) was detected at highly elevated concentrations in Brazil and Colombia, in line with the use of the pesticide sulfluramid in this region. Similar concentrations of the perfluoroalkyl sulfonates (PFAS) were detected throughout the GRULAC region regardless of location type, and the VMS concentrations in air increased with the population density of sampling locations. This is the first report of atmospheric concentrations of the PFAAs and VMS from this region.
Preparation and characterization of a siloxane containing bismaleimide
NASA Technical Reports Server (NTRS)
Maudgal, S.; St. Clair, T. L.
1984-01-01
A novel siloxane containing bismaleimide has been prepared by reacting maleic anhydride, benzophenonetetracarboxylic dianhydride and bis(gamma-aminopropyl)tetramethyldisiloxane. Characterization of this monomer was done by comparing its nuclear magnetic resonance spectrum (NMR) to those of model compounds. Solubility of the prepolymer was tested in amide, chlorinated and ether solvents. Films were cast from solution as well as by melt processing and a cure cycle was determined. Infrared spectrum (IR) of the resulting film was obtained. Thermal polymerization was investigated by differential scanning calorimetry (DSC). Thermal properties of the cured resin were followed by means of thermogravimetric analysis (TGA), torsional braid analysis (TBA) and dynamic mechanical analysis (DMA). Thermomechanical analysis (TMA) was used to study the effect of postcure on the glass transition temperature (Tg) of the resin. Adhesive strength of the resin was obtained at ambient temperature.
Effect of Ambient Temperature on Hydrophobic Recovery Behavior of Silicone Rubber Composites
NASA Astrophysics Data System (ADS)
Peng, Xiangyang; Li, Zijian; Zheng, Feng; Zhang, Ni; Huang, Zhen; Fang, Pengfei
A series of silicone rubber samples with different cyclosiloxanes contents have been successfully prepared, and their hydrophobic recovery behaviors and mechanism were investigated in detail. The gas chromatography-mass spectroscopy technique after Soxhlet extraction was utilized to examine the low molecular weight siloxanes in the sample, SEM was used to observe the surface morphology of the silicone rubber influenced by plasma treatment, and contact angle measurement was applied to probe the hydrophobic recovery of the sample surface after plasma treatment at different storage temperatures. The storage time-dependent contact angle of water can be well fitted by the diffusion model calculated from Fick’s second law. The results imply that the hydrophobic recovery of silicone rubber is related to the diffusion of low molecular weight siloxanes, while larger content or higher temperature can induce faster hydrophobic recovery.
Liquid-phase-deposited siloxane-based capping layers for silicon solar cells
DOE Office of Scientific and Technical Information (OSTI.GOV)
Veith-Wolf, Boris; Wang, Jianhui; Hannu-Kuure, Milja
2015-02-02
We apply non-vacuum processing to deposit dielectric capping layers on top of ultrathin atomic-layer-deposited aluminum oxide (AlO{sub x}) films, used for the rear surface passivation of high-efficiency crystalline silicon solar cells. We examine various siloxane-based liquid-phase-deposited (LPD) materials. Our optimized AlO{sub x}/LPD stacks show an excellent thermal and chemical stability against aluminum metal paste, as demonstrated by measured surface recombination velocities below 10 cm/s on 1.3 Ωcm p-type silicon wafers after firing in a belt-line furnace with screen-printed aluminum paste on top. Implementation of the optimized LPD layers into an industrial-type screen-printing solar cell process results in energy conversion efficiencies ofmore » up to 19.8% on p-type Czochralski silicon.« less
High performance hydrophobic solvent, carbon dioxide capture
Nulwala, Hunaid; Luebke, David
2017-05-09
Methods and compositions useful, for example, for physical solvent carbon capture. A method comprising: contacting at least one first composition comprising carbon dioxide with at least one second composition to at least partially dissolve the carbon dioxide of the first composition in the second composition, wherein the second composition comprises at least one siloxane compound which is covalently modified with at least one non-siloxane group comprising at least one heteroatom. Polydimethylsiloxane (PDMS) materials and ethylene-glycol based materials have high carbon dioxide solubility but suffer from various problems. PDMS is hydrophobic but suffers from low selectivity. Ethylene-glycol based systems have good solubility and selectivity, but suffer from high affinity to water. Solvents were developed which keep the desired combinations of properties, and result in a simplified, overall process for carbon dioxide removal from a mixed gas stream.
Li, Cuiping; Li, Xueyuan; Duan, Xuelan; Li, Guangjie; Wang, Jiaqiang
2014-12-15
Halloysite nanotube supported Ag nanoparticles heteroarchitectures have been prepared through a very simple electroless plating method. Robust Ag nanocrystals can be reproducibly fabricated by soaking halloysite nanotubes in ethanolic solutions of AgNO3 and butylamine. By simply adjusting the molar ratio of AgNO3 and butylamine, Ag nanoparticles with tunable size and quantity on halloysite nanotube are achieved. It reveals that the Ag nanoparticles are well-dispersed on the surface of halloysite nanotubes. The halloysite nanotube supported Ag nanoparticles heteroarchitectures can serve as active catalysts for the polymerization of an alkylsilane C18H37SiH3 with water to form silanol/siloxane composite microspheres and exhibit interesting superhydrophobicity ascribed to the micro/nanobinary structure. Copyright © 2014 Elsevier Inc. All rights reserved.
Van Moorsel, Guillaume
2005-01-01
Libraries often do not know how clients value their product/ service offerings. Yet at a time when the mounting costs for library support are increasingly difficult to justify to the parent institution, the library's ability to gauge the value of its offerings to clients has never been more critical. Client Value Models (CVMs) establish a common definition of value elements-or a "value vocabulary"-for libraries and their clients, thereby providing a basis upon which to make rational planning decisions regarding product/service acquisition and development. The CVM concept is borrowed from business and industry, but its application has a natural fit in libraries. This article offers a theoretical consideration and practical illustration of CVM application in libraries.
Lee, B B; Baumgartner, I; Berlien, H P; Bianchini, G; Burrows, P; Do, Y S; Ivancev, K; Kool, L S; Laredo, J; Loose, D A; Lopez-Gutierrez, J C; Mattassi, R; Parsi, K; Rimon, U; Rosenblatt, M; Shortell, C; Simkin, R; Stillo, F; Villavicencio, L; Yakes, W
2013-02-01
Arterio-venous malformations (AVMs) are congenital vascular malformations (CVMs) that result from birth defects involving the vessels of both arterial and venous origins, resulting in direct communications between the different size vessels or a meshwork of primitive reticular networks of dysplastic minute vessels which have failed to mature to become 'capillary' vessels termed "nidus". These lesions are defined by shunting of high velocity, low resistance flow from the arterial vasculature into the venous system in a variety of fistulous conditions. A systematic classification system developed by various groups of experts (Hamburg classification, ISSVA classification, Schobinger classification, angiographic classification of AVMs,) has resulted in a better understanding of the biology and natural history of these lesions and improved management of CVMs and AVMs. The Hamburg classification, based on the embryological differentiation between extratruncular and truncular type of lesions, allows the determination of the potential of progression and recurrence of these lesions. The majority of all AVMs are extra-truncular lesions with persistent proliferative potential, whereas truncular AVM lesions are exceedingly rare. Regardless of the type, AV shunting may ultimately result in significant anatomical, pathophysiological and hemodynamic consequences. Therefore, despite their relative rarity (10-20% of all CVMs), AVMs remain the most challenging and potentially limb or life-threatening form of vascular anomalies. The initial diagnosis and assessment may be facilitated by non- to minimally invasive investigations such as duplex ultrasound, magnetic resonance imaging (MRI), MR angiography (MRA), computerized tomography (CT) and CT angiography (CTA). Arteriography remains the diagnostic gold standard, and is required for planning subsequent treatment. A multidisciplinary team approach should be utilized to integrate surgical and non-surgical interventions for optimum care. Currently available treatments are associated with significant risk of complications and morbidity. However, an early aggressive approach to elimiate the nidus (if present) may be undertaken if the benefits exceed the risks. Trans-arterial coil embolization or ligation of feeding arteries where the nidus is left intact, are incorrect approaches and may result in proliferation of the lesion. Furthermore, such procedures would prevent future endovascular access to the lesions via the arterial route. Surgically inaccessible, infiltrating, extra-truncular AVMs can be treated with endovascular therapy as an independent modality. Among various embolo-sclerotherapy agents, ethanol sclerotherapy produces the best long term outcomes with minimum recurrence. However, this procedure requires extensive training and sufficient experience to minimize complications and associated morbidity. For the surgically accessible lesions, surgical resection may be the treatment of choice with a chance of optimal control. Preoperative sclerotherapy or embolization may supplement the subsequent surgical excision by reducing the morbidity (e.g. operative bleeding) and defining the lesion borders. Such a combined approach may provide an excellent potential for a curative result. Conclusion. AVMs are high flow congenital vascular malformations that may occur in any part of the body. The clinical presentation depends on the extent and size of the lesion and can range from an asymptomatic birthmark to congestive heart failure. Detailed investigations including duplex ultrasound, MRI/MRA and CT/CTA are required to develop an appropriate treatment plan. Appropriate management is best achieved via a multi-disciplinary approach and interventions should be undertaken by appropriately trained physicians.
Composite Materials for Hazard Mitigation of Reactive Metal Hydrides.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Pratt, Joseph William; Cordaro, Joseph Gabriel; Sartor, George B.
2012-02-01
In an attempt to mitigate the hazards associated with storing large quantities of reactive metal hydrides, polymer composite materials were synthesized and tested under simulated usage and accident conditions. The composites were made by polymerizing vinyl monomers using free-radical polymerization chemistry, in the presence of the metal hydride. Composites with vinyl-containing siloxane oligomers were also polymerized with and without added styrene and divinyl benzene. Hydrogen capacity measurements revealed that addition of the polymer to the metal hydride reduced the inherent hydrogen storage capacity of the material. The composites were found to be initially effective at reducing the amount of heatmore » released during oxidation. However, upon cycling the composites, the mitigating behavior was lost. While the polymer composites we investigated have mitigating potential and are physically robust, they undergo a chemical change upon cycling that makes them subsequently ineffective at mitigating heat release upon oxidation of the metal hydride. Acknowledgements The authors would like to thank the following people who participated in this project: Ned Stetson (U.S. Department of Energy) for sponsorship and support of the project. Ken Stewart (Sandia) for building the flow-through calorimeter and cycling test stations. Isidro Ruvalcaba, Jr. (Sandia) for qualitative experiments on the interaction of sodium alanate with water. Terry Johnson (Sandia) for sharing his expertise and knowledge of metal hydrides, and sodium alanate in particular. Marcina Moreno (Sandia) for programmatic assistance. John Khalil (United Technologies Research Corp) for insight into the hazards of reactive metal hydrides and real-world accident scenario experiments. Summary In an attempt to mitigate and/or manage hazards associated with storing bulk quantities of reactive metal hydrides, polymer composite materials (a mixture of a mitigating polymer and a metal hydride) were synthesized and tested under simulated usage and accident conditions. Mitigating the hazards associated with reactive metal hydrides during an accident while finding a way to keep the original capability of the active material intact during normal use has been the focus of this work. These composites were made by polymerizing vinyl monomers using free-radical polymerization chemistry, in the presence of the metal hydride, in this case a prepared sodium alanate (chosen as a representative reactive metal hydride). It was found that the polymerization of styrene and divinyl benzene could be initiated using AIBN in toluene at 70°C. The resulting composite materials can be either hard or brittle solids depending on the cross-linking density. Thermal decomposition of these styrene-based composite materials is lower than neat polystyrene indicating that the chemical nature of the polymer is affected by the formation of the composite. The char-forming nature of cross-linked polystyrene is low and therefore, not an ideal polymer for hazard mitigation. To obtain composite materials containing a polymer with higher char-forming potential, siloxane-based monomers were investigated. Four vinyl-containing siloxane oligomers were polymerized with and without added styrene and divinyl benzene. Like the styrene materials, these composite materials exhibited thermal decomposition behavior significantly different than the neat polymers. Specifically, the thermal decomposition temperature was shifted approximately 100 °C lower than the neat polymer signifying a major chemical change to the polymer network. Thermal analysis of the cycled samples was performed on the siloxane-based composite materials. It was found that after 30 cycles the siloxane-containing polymer composite material has similar TGA/DSC-MS traces as the virgin composite material indicating that the polymer is physically intact upon cycling. Hydrogen capacity measurements revealed that addition of the polymer to the metal hydride in the form of a composite material reduced the inherent hydrogen storage capacity of the material. This reduction in capacity was observed to be independent of the amount of charge/discharge cycles except for the composites containing siloxane, which showed less of an impact on hydrogen storage capacity as it was cycled further. While the reason for this is not clear, it may be due to a chemically stabilizing effect of the siloxane on the metal hydride. Flow-through calorimetry was used to characterize the mitigating effectiveness of the different composites relative to the neat (no polymer) material. The composites were found to be initially effective at reducing the amount of heat released during oxidation, and the best performing material was the siloxane-containing composite which reduced the heat release to less than 50% of the value of the neat material. However, upon cycling the composites, all mitigating behavior was lost. The combined results of the flow-through calorimetry, hydrogen capacity, and thermogravimetric analysis tests lead to the proposed conclusion that while the polymer composites have mitigating potential and are physically robust under cycling, they undergo a chemical change upon cycling that makes them ineffective at mitigating heat release upon oxidation of the metal hydride.« less
Fire behavior of transformer dielectric insulating fluids
DOT National Transportation Integrated Search
1980-01-31
This report presents results for the fire behavior of pure and askarel-contaminated fluids which are candidates for use as railroad transformer dielectric insulating fluids. In the study a hydrocarbon and a dimethyl-siloxane fluid were examined. The ...
Wear effects on microscopic morphology and hyaluronan uptake in siloxane-hydrogel contact lenses.
Tavazzi, Silvia; Tonveronachi, Martina; Fagnola, Matteo; Cozza, Federica; Ferraro, Lorenzo; Borghesi, Alessandro; Ascagni, Miriam; Farris, Stefano
2015-07-01
The purpose of this study was a comparison between new and worn siloxane-hydrogel contact lenses in terms of microscopic structure, surface morphology, and loading of hyaluronan. The analyses were performed by scanning electron microscopy, with the support of the freeze-drying technique, and by fluorescence confocal microscopy. Along the depth profile of new lenses, a thin porous top layer was observed, which corresponds to the region of hyaluronan penetration inside well-defined channels. The time evolution was followed from one day to two weeks of daily wear, when a completely different scenario was found. Clear experimental evidence of a buggy surface was observed with several crests and regions of swelling, which could be filled by the hyaluronan solution. The modifications are attributed to the progressive relaxation of the structure of the polymeric network. © 2014 Wiley Periodicals, Inc.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Dobrzyńska-Mizera, Monika, E-mail: monika.dobrzynska-mizera@doctorate.put.poznan.pl; Sterzyński, Tomasz; Dutkiewicz, Michał
Composites based on polypropylene (iPP) modified with a sorbitol derivative (NX8000) and siloxane-silsesquioxane resin (SiOPh) containing maleated polypropylene (MAPP) as compatibilizer were prepared by melt extrusion. Calorimetric investigations were carried out using differential scanning calorimetry (DSC), whereas the morphological and mechanical properties were investigated by scanning electron microscopy (SEM) and static tensile tests. DSC measurements revealed no influence of SiOPh and a slight effect of MAPP addition on the crystallization kinetics of polypropylene. Additionally, the introduction of MAPP into the iPP+NX8000+SiOPh composites increased plastic properties of the samples. All the above was attributed to the compatibilizing effect of MAPP whichmore » improved interfacial adhesion between iPP, NX8000 and SiOPh. This phenomenon was also confirmed by the SEM images illustrating more homogenous distribution of the filler in the compatibilized samples.« less
NASA Astrophysics Data System (ADS)
Dobrzyńska-Mizera, Monika; Dutkiewicz, Michał; Sterzyński, Tomasz; Di Lorenzo, Maria Laura
2015-12-01
Composites based on polypropylene (iPP) modified with a sorbitol derivative (NX8000) and siloxane-silsesquioxane resin (SiOPh) containing maleated polypropylene (MAPP) as compatibilizer were prepared by melt extrusion. Calorimetric investigations were carried out using differential scanning calorimetry (DSC), whereas the morphological and mechanical properties were investigated by scanning electron microscopy (SEM) and static tensile tests. DSC measurements revealed no influence of SiOPh and a slight effect of MAPP addition on the crystallization kinetics of polypropylene. Additionally, the introduction of MAPP into the iPP+NX8000+SiOPh composites increased plastic properties of the samples. All the above was attributed to the compatibilizing effect of MAPP which improved interfacial adhesion between iPP, NX8000 and SiOPh. This phenomenon was also confirmed by the SEM images illustrating more homogenous distribution of the filler in the compatibilized samples.
Ultrahigh molecular weight aromatic siloxane polymers
NASA Technical Reports Server (NTRS)
Ludwick, L. M.
1982-01-01
The condensation of a diol with a silane in toluene yields a silphenylene-siloxane polymer. The reaction of stiochiometric amounts of the diol and silane produced products with molecular weights in the range 2.0 - 6.0 x 10 to the 5th power. The molecular weight of the product was greatly increased by a multistep technique. The methodology for synthesis of high molecular weight polymers using a two step procedure was refined. Polymers with weight average molecular weights in excess of 1.0 x 10 to the 6th power produced by this method. Two more reactive silanes, bis(pyrrolidinyl)dimethylsilane and bis(gamma butyrolactam)dimethylsilane, are compared with the dimethyleminodimethylsilane in ability to advance the molecular weight of the prepolymer. The polymers produced are characterized by intrinsic viscosity in tetrahydrofuran. Weight and number average molecular weights and polydispersity are determined by gel permeation chromatography.
Tokuda, Shingo; Obata, Akiko; Kasuga, Toshihiro
2009-05-01
A poly(lactic acid) (PLA)/siloxane/calcium carbonate composite membrane containing mercapto groups (PSC-SH) with antibacterial ability and excellent bone-forming ability was prepared using 3-mercaptopropyltrimethoxysilane for application in guided bone regeneration. Mercapto groups were reported to adsorb silver ions, which are well known to show antibacterial activity. Ionic silicon species were reported to stimulate the proliferation of osteoblasts. A PSC-SH membrane with a thickness of about 10 microm shows high flexibility. The PLA in PSC-SH was converted from the crystalline phase to the amorphous phase due to dispersion of condensed siloxane clusters. The amount of mercapto group on PSC-SH surface was estimated to be about 55 nmol mm(-2) by quantitative analysis using the thiol-disulfide exchange reaction. PSC-SH adsorbed silver ions on its surface after being soaked in 6 microM silver acetate aqueous solution for 1 min. The adsorbed silver ions were seen by X-ray photoelectron spectroscopy to form SAg and SO3Ag bonds. A trace amount of ionic silicon species was released from the membrane after soaking in culture medium. PSC-SH with adsorbed silver ions showed good antibacterial activity and cellular compatibility in tests conducted with Staphylococcus aureus and mouse osteoblast-like cells, respectively. Antibacterial activity is expected to occur during the implantation operation by the silver ions but not to remain in the body for a long period, as the ions were present on the surface of the membrane but not inside the structure. The membrane should be useful as a biodegradable material with antibacterial activity and bone-forming ability.
Attenuation of iodine 125 radiation with vitreous substitutes in the treatment of uveal melanoma.
Oliver, Scott C N; Leu, Min Y; DeMarco, John J; Chow, Philip E; Lee, Steve P; McCannel, Tara A
2010-07-01
To demonstrate attenuation of radiation from iodine 125 ((125)I) to intraocular structures using liquid vitreous substitutes. Four candidate vitreous substitutes were tested for attenuation using empirical measurement and theoretical calculation. In vitro and ex vivo cadaveric dosimetry measurements were obtained with lithium fluoride thermoluminescent dosimeters to demonstrate the attenuation effect of vitreous substitution during (125)I simulated plaque brachytherapy. Theoretical dosimetry calculations were based on Monte Carlo simulation. In a cylindrical phantom at a 17-mm depth, liquid vitreous substitutes as compared with saline showed significant reduction of radiation penetration (48% for 1000-centistoke [cSt] silicone oil [polydimethyl-n-siloxane], 47% for 5000-cSt silicone oil [polydimethyl-n-siloxane], 40% for heavy oil [perfluorohexyloctane/polydimethyl-n-siloxane], and 35% for perfluorocarbon liquid [perfluoro-n-octane]). Human cadaveric ex vivo measurements demonstrated a 1000-cSt silicone oil to saline dose ratio of 35%, 52%, 55%, and 48% at arc lengths of 7.6, 10.6, 22.3, and 28.6 mm from the plaque edge, respectively, along the surface of the globe. Monte Carlo simulation of a human globe projected attenuation as high as 57% using 1000-cSt silicone oil. Intraocular vitreous substitutes including silicone oil, heavy oil, and perfluorocarbon liquid attenuate the radiation dose from (125)I. Cadaveric ex vivo measurements and Monte Carlo simulation both demonstrate radiation attenuation using 1000-cSt silicone oil at distances corresponding to vital ocular structures. Clinical Relevance Attenuation of radiation with silicone oil endotamponade in the treatment of uveal melanoma may significantly reduce radiation-induced injury to vital ocular structures.
NASA Technical Reports Server (NTRS)
Smith, Trent; Prince, Michael; DwWeese, Charles; Curtis, Leslie
2008-01-01
The Shuttle Ice Liberation Coating (SILC) has been developed to reduce the adhesion of ice to surfaces on the space shuttle. SILC, when coated on a surface (foam, metal, epoxy primer, polymer surfaces), will reduce the adhesion of ice by as much as 90 percent as compared to the corresponding uncoated surface. This innovation is a durable coating that can withstand several cycles of ice growth and removal without loss of anti-adhesion properties. SILC is made of a binder composed of varying weight percents of siloxane(s), ethyl alcohol, ethyl sulfate, isopropyl alcohol, and of fine-particle polytetrafluoroethylene (PTFE). The combination of these components produces a coating with significantly improved weathering characteristics over the siloxane system alone. In some cases, the coating will delay ice formation and can reduce the amount of ice formed. SILC is not an ice prevention coating, but the very high water contact angle (greater than 140 ) causes water to readily run off the surface. This coating was designed for use at temperatures near -170 F (-112 C). Ice adhesion tests performed at temperatures from -170 to 20 F (-112 to -7 C) show that SILC is a very effective ice release coating. SILC can be left as applied (opaque) or buffed off until the surface appears clear. Energy dispersive spectroscopy (EDS) and x-ray photoelectron spectroscopy (XPS) data show that the coating is still present after buffing to transparency. This means SILC can be used to prevent ice adhesion even when coating windows or other objects, or items that require transmission of optical light. Car windshields are kept cleaner and SILC effectively mitigates rain and snow under driving conditions.
Brocal, J; De Decker, S; José-López, R; Manzanilla, E G; Penderis, J; Stalin, C; Bertram, S; Schoenebeck, J J; Rusbridge, C; Fitzpatrick, N; Gutierrez-Quintana, R
2018-05-14
The number of cervical vertebrae in mammals is almost constant at seven, regardless of their neck length, implying that there is selection against variation in this number. Homebox (Hox) genes are involved in this evolutionary mammalian conservation, and homeotic transformation of cervical into thoracic vertebrae (cervical ribs) is a common phenotypic abnormality when Hox gene expression is altered. This relatively benign phenotypic change can be associated with fatal traits in humans. Mutations in genes upstream of Hox, inbreeding and stressors during organogenesis can also cause cervical ribs. The aim of this study was to describe the prevalence of cervical ribs in a large group of domestic dogs of different breeds, and explore a possible relation with other congenital vertebral malformations (CVMs) in the breed with the highest prevalence of cervical ribs. By phenotyping we hoped to give clues as to the underlying genetic causes. Twenty computed tomography studies from at least two breeds belonging to each of the nine groups recognized by the Federation Cynologique Internationale, including all the brachycephalic 'screw-tailed' breeds that are known to be overrepresented for CVMs, were reviewed. The Pug dog was more affected by cervical ribs than any other breed (46%; P < 0.001), and was selected for further analysis. No association was found between the presence of cervical ribs and vertebral body formation defect, bifid spinous process, caudal articular process hypoplasia/aplasia and an abnormal sacrum, which may infer they have a different aetiopathogenesis. However, Pug dogs with cervical ribs were more likely to have a transitional thoraco-lumbar vertebra (P = 0.041) and a pre-sacral vertebral count of 26 (P < 0.001). Higher C7/T1 dorsal spinous processes ratios were associated with the presence of cervical ribs (P < 0.001), supporting this is a true homeotic transformation. Relaxation of the stabilizing selection has likely occurred, and the Pug dog appears to be a good naturally occurring model to further investigate the aetiology of cervical ribs, other congenital vertebral anomalies and numerical alterations. © 2018 Anatomical Society.
Haghi, Hamidreza Rajati; Shiehzadeh, Masoud; Nakhaei, Mohammadreza; Ahrary, Fatemeh; Sabzevari, Saeid
2017-01-01
Introduction: A dental impression is a negative imprint of an oral structure that can be used to produce a positive cast of a patient's teeth as a permanent record. The accuracy of the impression affects the accuracy of the cast, and a precise impression is needed in order to create prosthesis with optimal fitting. Minimization of misfit is an important aim in prosthesis science and dental implants. The aim of this study was to evaluate the effects of the materials and techniques used to take an impression on the vertical misfit of implant-supported, screw-retained, three-unit bridges. Materials and Methods: The principal model used was an acrylic block with two ITI implants. A 1.5-mm abutment was attached to fixtures with torque of 25 N.cm. A base-metal framework was built on the abutment in the acrylic block. The abutments of the acrylic model were unscrewed and fixture-level impressions were made. The impression techniques included open/closed-tray techniques and the impression materials were polyether and polyvinyl siloxane. Forty acrylic custom trays were built for each impression. The marginal gap in the framework at three points (buccal, lingual, and distal) was measured using an optical microscope with ×250. Results: It is demonstrated that in all 360 evaluated samples, the mean vertical misfit in polyether samples of molar and premolar teeth was significantly lower than in polyvinyl siloxane (P < 0.001 and P = 0.017, respectively) in all three locations of the molar and lingual premolar examined (buccal, lingual, and distal), the mean vertical misfit of the polyether samples was significantly lower than those of polyvinyl siloxane (P < 0.01). On the other hand, although the mean vertical misfit using the open-tray technique in the molar teeth was significantly lower than with the closed-tray method (P = 0.002), no statistical difference was seen between the open-tray and closed-tray technique in general (P = 0.87). Conclusion: Within the limitations of this study, the following conclusions can be drawn: The impression method had no effect on marginal discrepancy of 3-unit screw retained fixed partial dentures. A higher marginal accuracy was obtained using polyether impression material compared to polyvinyl siloxane. PMID:28216844
Preparation of oxide glasses from metal alkoxides by sol-gel method
NASA Technical Reports Server (NTRS)
Kamiya, K.; Yoko, T.; Sakka, S.
1987-01-01
An investigation is carried out on the types of siloxane polymers produced in the course of the hydrolysis of silicon tetraethoxide, as well as the preparation of oxide glasses from metal alkoxides by the sol-gel method.
Evaluation of treatment options for ASR-affected concrete : final report, December 11, 2009.
DOT National Transportation Integrated Search
2009-12-11
This research project was undertaken to evaluate the potential of using surface treatments including lithium nitrate, : sodium tartarate, siloxanes, silane, and boiled linseed oil to mitigate or slow the rate of concrete deterioration : associated wi...
Menaa, Bouzid; Herrero, Mar; Rives, Vicente; Lavrenko, Mayya; Eggers, Daryl K.
2008-01-01
Organically-modified siloxanes were used as host materials to examine the influence of surface chemistry on protein conformation in a crowded environment. The sol-gel materials were prepared from tetramethoxysilane and a series of monosubstituted alkoxysilanes, RSi(OR′)3, featuring alkyl groups of increasing chain length in the R-position. Using circular dichroism spectroscopy in the far-UV region, apomyoglobin was found to transit from an unfolded state to a native-like helical state as the content of the hydrophobic precursor increased from 0–15%. At a fixed molar content of 5% RSi(OR’)3, the helical structure of apomyoglobin increased with the chain length of the R-group, i.e. methyl < ethyl < n-propyl < n-butyl < n-hexyl. This trend also was observed for the tertiary structure of ribonuclease A, suggesting that protein folding and biological activity are sensitive to the hydrophilic/hydrophobic balance of neighboring surfaces. The observed changes in protein structure did not correlate with total surface area or the average pore size of the modified glasses, but scanning electron microscopy images revealed an interesting relationship between surface morphology and alkyl chain length. The unexpected benefit of incorporating a low content of hydrophobic groups into a hydrophilic surface may lead to materials with improved biocompatibility for use in biosensors and implanted devices. PMID:18359512
Accuracy of various impression materials and methods for two implant systems: An effect size study.
Schmidt, Alexander; Häussling, Teresa; Rehmann, Peter; Schaaf, Heidrun; Wöstmann, Bernd
2018-04-01
An accurate impression is required for implant treatment. The aim of this in-vitro study was to determine the effect size of the impression material/method, implant system and implant angulation on impression transfer precision. An upper jaw model with three BEGO and three Straumann implants (angulations 0°, 15°, 20°) in the left and right maxilla was used as a reference model. One polyether (Impregum Penta) and two polyvinyl siloxanes (Flexitime Monophase/Aquasil Ultra Monophase) were examined with two impression techniques (open and closed tray). A total of 60 impressions were made. A coordinate measurement machine was used to measure the target variables for 3D-shift, implant axis inclination and implant axis rotation. All the data were subjected to a four-way ANOVA. The effect size (partial eta-squared [η 2 P ]) was reported. The impression material had a significant influence on the 3D shift and the implant axis inclination deviation (p-values=.000), and both factors had very large effect sizes (3D-shift [η 2 P ]=.599; implant axis inclination [η 2 P ]=.298). Impressions made with polyvinyl siloxane exhibited the highest transfer precision. When the angulation of the implants was larger, more deviations occurred for the implant axis rotational deviation. The implant systems and impression methods showed partially significant variations (p-values=.001-.639) but only very small effect sizes (η 2 P =.001-.031). The impression material had the greatest effect size on accuracy in terms of the 3D shift and the implant axis inclination. For multiunit restorations with disparallel implants, polyvinyl siloxane materials should be considered. In addition, the effect size of a multivariate investigation should be reported. Copyright © 2017 Japan Prosthodontic Society. Published by Elsevier Ltd. All rights reserved.
Organic silicon compounds anf hydrogen sulfide removal from biogas by mineral and adsorbent
NASA Astrophysics Data System (ADS)
Choi, J.
2015-12-01
Biogas utilized for energy production needs to be free from organic silicon compounds and hydrogen sulfide , as their burning has damaging effects on utilities and humans; organic silicon compounds and hydrogen sulfide can be found in biogas produced from biomass wastes, due to their massive industrial use in synthetic product,such as cosmetics, detergents and paints.Siloxanes and hydrogen sulfide removal from biogas can be carried out by various methods (Ajhar et al., 2010); aim of the present work is to find a single practical andeconomic way to drastically and simultaneously reduce both hydrogen sulfide and the siloxanes concentration to less than 1 ppm. Some commercial activated carbons previously selected (Monteleoneet al., 2011) as being effective in hydrogen sulfide up taking have been tested in an adsorption measurement apparatus, by flowing both hydrogen sulphide and volatile siloxane (Decamethycyclopentasiloxane or D5) in a nitrogen stream,typically 25-300 ppm D5 over N2, through an clay minerals, Fe oxides and Silica; the adsorption process was analyzed by varying some experimental parameters (concentration, grain size, bed height). The best silica shows an adsorption capacity of 0.2 g D5 per gram of silica. The next thermo gravimetric analysis (TGA) confirms the capacity data obtained experimentally by the breakthrough curve tests.The capacity results depend on D5 and hydrogen sulphide concentrations. A regenerative silica process is then carried out byheating the silica bed up to 200 ° C and flushing out the adsorbed D5 and hydrogen sulphide samples in a nitrogen stream in athree step heating procedure up to 200 ° C. The adsorption capacity is observed to degrade after cyclingthe samples through several adsorption-desorption cycles.
Del Frari, D; Bour, J; Bardon, J; Buchheit, O; Arnoult, C; Ruch, D
2010-04-01
Finding alternative treatments to reproduce anticorrosion properties of chromated coatings is challenging since both physical barrier and self-healing effects are needed. Siloxane based treatments are known to be a promising way to achieve physical barrier coatings, mainly plasma polymerized hexamethyldisiloxane (ppHMDSO). In addition, it is known that cerium-based coatings can also provide corrosion protection of metals by means of self-healing effect. In this frame, innovative nanoAlCeO3/ppHMDSO layers have thus been deposited and studied. These combinations allow to afford a good physical barrier effect and active properties. Liquid siloxane and cerium-based particles mixture is atomized and introduced as precursors into a carrier gas. Gas mixture is then injected into an atmospheric pressure dielectric barrier discharge (DBD) where plasma polymerization of the siloxane precursor occurs. The influence of cerium concentration on the coating properties is investigated: coating structure and topography have been studied by scanning electron microscopy (SEM) and interferometry, and corrosion resistance of these different coatings is compared by electrochemistry techniques: polarization curves and electrochemical impedance spectroscopy (EIS). Potential self-healing property afforded by cerium in the layer was studied by associating EIS measurements and nanoscratch controlled damaging. Among the different combinations investigated, mixing of plasma polymerized HMDSO and AICeO3 nanoparticles seems to give promising results with a good physical barrier and interesting electroactive properties. Indeed, corrosion currents measured on such coatings are almost as low as those measured with the chromated film. Combination of nanoscratch damaging of layers with EIS experiments to investigate self-healing also allow to measure the active protection property of such layers.
Dyke, Jason Christopher; Knight, Kelly Jane; Zhou, Huaxing; Chiu, Chi-Kai; Ko, Ching-Chang; You, Wei
2012-01-01
Causes of bone deficiency are numerous, but biomimetic alloplastic grafts provide an alternative to repair tissue naturally. Previously, a hydroxyapatite-gelatin modified siloxane (HAp-Gemosil) composite was prepared by cross-linking (N, N′-bis[(3-trimethoxysilyl)propyl]ethylene diamine (enTMOS) around the HAp-Gel nanocomposite particles, to mimic the natural composition and properties of bone. However, the tensile strength remained too low for many orthopedic applications. It was hypothesized that incorporating a polymer chain into the composite could help improve long range interaction. Furthermore, designing this polymer to interact with the enTMOS siloxane cross-linked matrix would provide improved adhesion between the polymer and the ceramic composite, and improve mechanical properties. To this end, copolymers of L-Lactide (LLA), and a novel alkyne derivatized trimethylene carbonate, propargyl carbonate (PC), were synthesized. Incorporation of PC during copolymerization affects properties of copolymers such as molecular weight, Tg, and % PC incorporation. More importantly, PC monomers bear a synthetic handle, allowing copolymers to undergo post-polymerization functionalization with graft monomers to specifically tailor the properties of the final composite. For our investigation, P(LLA-co-PC) copolymers were functionalized by an azido-silane (AS) via copper catalyzed azide-alkyne cycloaddition (CuAAC) through terminal alkyne on PC monomers. The new functionalized polymer, P(LLA-co-PC)(AS) was blended with HAp-Gemosil, with the azido-silane linking the copolymer to the silsesquioxane matrix within the final composite. These HAp-Gemosil/P(LLA-co-PC)(AS) composites were subjected to mechanical and biological testing, and the results were compared with those from the HAp-Gemosil composites. This study revealed that incorporating a cross-linkable polymer served to increase the flexural strength of the composite by 50%, while maintaining the biocompatibility of HAp-Gemosil ceramics. PMID:23139457
Sun, Bingbing; Pokhrel, Suman; Dunphy, Darren R.; Zhang, Haiyuan; Ji, Zhaoxia; Wang, Xiang; Wang, Meiying; Liao, Yu-Pei; Chang, Chong Hyun; Dong, Juyao; Li, Ruibin; Mädler, Lutz; Brinker, C. Jeffrey; Nel, André E.; Xia, Tian
2015-01-01
The production of pyrogenic (fumed) silica is increasing worldwide at a 7% annual growth rate, including expanded use in food, pharmaceuticals and other industrial products. Synthetic amorphous silica, including fumed silica, has been generally recognized as safe (GRAS) for use in food products by the Food and Drug Administration (FDA). However, emerging evidence from experimental studies now suggests that fumed silica could be hazardous due to its siloxane ring structure, high silanol density, and “string-of-pearl-like” aggregate structure, which could combine to cause membrane disruption, generation of reactive oxygen species, pro-inflammatory effects, and liver fibrosis. Based on this structure-activity analysis (SAA), we investigated whether calcination and rehydration of fumed silica changes its hazard potential in the lung due to an effect on silanol density display. This analysis demonstrated that the accompanying change in surface reactivity could indeed impact cytokine production in macrophages and acute inflammation in the lung, in a manner that is dependent on siloxane ring reconstruction. Confirmation of this SAA in vivo, prompted us to consider safer design of fumed silica properties by titanium (Ti) and aluminum (Al) doping (0–7%), using flame spray pyrolysis (FSP). Detailed characterization revealed that increased Ti and Al doping could reduce surface silanol density and expression of three-membered siloxane rings, leading to dose-dependent reduction in hydroxyl radical generation, membrane perturbation, potassium efflux, NLRP3 inflammasome activation and cytotoxicity in THP-1 cells. The reduction of NLRP3 inflammasome activation was also confirmed in bone marrow-derived macrophages (BMDMs). Ti- and to a lesser extent Al-doping, also ameliorated acute pulmonary inflammation, demonstrating the possibility of a safer design approach for fumed silica, should that be required for specific use circumstances. PMID:26200133
Polydimethyl siloxane (PDMS) and zeolite incorporated mixed matrix materials are gaining importance in a variety of applications including membrane separation. PDMS based membranes are used in pervaporation (PV), a membrane technology, for the selective removal of organics such ...
NASA Astrophysics Data System (ADS)
Hassan, Mohammad M.; Leighs, Samuel J.
2017-10-01
The surface of wool fabrics is frequently modified to make them shrink-resistant, water repellent and also to improve their handle properties. In this work, we investigated the effect of common surface modification treatments on fabric stain-resistance, hydrophilicity and UV absorption performance. The surface of wool fabrics was modified by chlorination and also by reacting the chlorinated wool fabrics with a polyamide, a fibre-reactive amino-functional siloxane and a fluorocarbon polymer. The surface of the various treated fabrics was characterised by ATR-FTIR, contact angle measurement and scanning electron microscopy. The effect of surface modification on the tensile strength, surface hydrophilicity, stain-resistance, and UV absorption capacity of the fabric was investigated. It was found that all the treatments except the treatment with the amino-functional siloxane polymer slightly improved the tensile strength of the fabric. The chlorination treatment and the treatment with the polyamide resin made the fabric hydrophilic, and fluorocarbon and silicone resin treatment made the fabric hydrophobic.
Wessels, Quenton; Pretorius, Etheresia
2015-08-01
Burn wound care today has a primary objective of temporary or permanent wound closure. Commercially available engineered alternative tissues have become a valuable adjunct to the treatment of burn injuries. Their constituents can be biological, alloplastic or a combination of both. Here the authors describe the aspects of the development of a siloxane epidermis for a collagen-glycosaminoglycan and for nylon-based artificial skin replacement products. A method to fabricate an ultra-thin epidermal equivalent is described. Pores, to allow the escape of wound exudate, were punched and a tri-filament nylon mesh or collagen scaffold was imbedded and silicone polymerisation followed at 120°C for 5 minutes. The ultra-structure of these bilaminates was assessed through scanning electron microscopy. An ultra-thin biomedical grade siloxane film was reliably created through precision coating on a pre-treated polyethylene terephthalate carrier. © 2013 The Authors. International Wound Journal © 2013 Medicalhelplines.com Inc and John Wiley & Sons Ltd.
Round-patterned ZnO nanostructure coated with siloxane-based polymer for nerve agent detection
NASA Astrophysics Data System (ADS)
Choi, Hyun Ji; Lee, Ji Won; Jeong, Dong-Cheol; Ha, Seonggyun; Song, Changsik; Boo, Jin-Hyo
2018-01-01
The alignment of zinc oxide (ZnO) nanostructures is expected to improve device sensitivities due to large surface areas which can be utilized to capture significant quantities of gas particles. In this study, we investigated patterned ZnO nanorods modified with polystyrene monolayers synthesized directly onto a quartz crystal microbalance (QCM) cell to increase the coating surface area of the sensing material. Also, we designed and synthesized a siloxane-based polymer (S1 polymer) as a sensing material. The patterned ZnO nanorods coated with S1 polymers were fabricated and used for the detection of dimethyl methylphosphonate (DMMP). The resonance frequency of QCM was shifted due to the adsorption and desorption of a compound at the surface of the modified electrodes. We have synthesized an S1 polymer that exhibited high sensitivity to DMMP. The patterned ZnO nanorods coated with the polymer also exhibited improved sensitivity due to an enhanced surface area capable of adsorbing more DMMP vapor.
Development of Co-Extrusion Technologies for Green Manufacture of Energetics
2006-04-01
extrusion, Cc-extruded, ETPE, TPE, Energetic thermoplastic elastomer , PDMS, Polydimethyl siloxane, Fast core propellant, Co-layered, Wall slip, Shear...first opportunity possible, the steady FEM models of SIT will need to be converted into time dependent models to allow time dependent calculations to be
77 FR 74473 - Certain New Chemicals; Receipt and Status Information
Federal Register 2010, 2011, 2012, 2013, 2014
2012-12-14
... polymer. building materials. P-13-0022 10/12/2012 1/9/2013 CBI (S) Surface (G) protection agent Perfluoroacrylate for use in polymer. building materials. P-13-0023 10/12/2012 1/9/2013 CBI (G) Coating (G) Siloxanes and additive. silicones, substituted alkyl group-terminated, alkoxylated, polymers with...
Code of Federal Regulations, 2010 CFR
2010-07-01
...-aminoethyl) amino]propyl Me, di-Me, reaction products with polyethylene-polypropylene glycol Bu glycidal..., reaction products with polyethylene-polypropylene glycol Bu glycidal ether. (a) Chemical substance and... silicones, 3-[(2-aminoethyl) amino]propyl Me, di-Me, reaction products with polyethylene-polypropylene...
Code of Federal Regulations, 2011 CFR
2011-07-01
...-aminoethyl) amino]propyl Me, di-Me, reaction products with polyethylene-polypropylene glycol Bu glycidal..., reaction products with polyethylene-polypropylene glycol Bu glycidal ether. (a) Chemical substance and... silicones, 3-[(2-aminoethyl) amino]propyl Me, di-Me, reaction products with polyethylene-polypropylene...
The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...
This presentation will report on work underway to inventory facilities currently utilizing biogas from anaerobic digestion and speak with practitioners to learn: techniques for preparing residuals for digestion, methods to use for cleaning biogas (e.g., of siloxane), and how gas...
EFFECT OF MOLECULAR ARCHITECTURE ON DBS-INDUCED BLOCK COPOLYMER GELS: A RHEOLOGICAL STUDY
Dibenzylidene sorbitol (DBS) is capable of gelling a variety of organic solvents and polymeric materials by forming a rigid, 3-D hydrogen-bonded network. In this work, two poly(siloxane)/poly(propylene oxide) segmented copolymers of equal composition and molecular weight, but di...
Organometalic carbosilane polymers containing vanadium and their preparation
NASA Technical Reports Server (NTRS)
Yajima, S.; Okamura, K.; Shishido, T.; Fukuda, K.
1983-01-01
The present invention concerns a new organometallic polymer material containing in part a vanadium-siloxane linkage (V-0-Si), which has excellent resistance to heat and oxidation and a high residue ratio after high temperature treatment in a non-oxidizing atmosphere, for example, nitrogen, argon, helium, ammonia, or hydrogen.
61 FR 41385 - Notice of Government-Owned Inventions; Availability for Licensing
Federal Register 2010, 2011, 2012, 2013, 2014
1996-08-08
... PRESSURE VESSEL; filed 24 February 1995; patented 21 November 1995.// Patent 5,468,356: LARGE SCALE...,477,482: ULTRA HIGH DENSITY, NON- VOLATILE FERROMAGNETIC RANDOM ACCESS MEMORY; filed 1 October 1993....// Patent 5,483,017: HIGH TEMPERATURE THERMOSETS AND CERAMICS DERIVED FROM LINEAR CARBORANE-(SILOXANE OR...
NASA Astrophysics Data System (ADS)
Kirchner, Robert; Chidambaram, Nachiappan; Schift, Helmut
2018-04-01
State-of-the-art, polymeric, refractive micro-optics simultaneously require an ultrasmooth three-dimensional (3-D) surface and a precise geometry for excellent optical performance with minimal stray light. In earlier work, we have established a surface finishing process for thermoplastic polymer master structures that is only effective on the surface and does not affect the designed optical geometry, thus enabling polishing without touching. Therewith, the high curvature corners of a 50-μm-tall optical diffuser device were maintained while the surface roughness was reduced to about 10-nm root mean square. For this, 3-D master structures were first fabricated by direct write laser-lithography with two-photon polymerization. The master structures were replicated into poly(methyl methacrylate) through a poly(dimethyl siloxane) intermediate replication stamp. Finally, all structures were surface-polished by selective high-energy photon exposure and thermal postprocessing. In this work, we focus on the comparison of the surface smoothening using either postprocessing or dedicated direct writing strategies. For this comparison, strategies for modifying the exposed voxel size and the writing discretization being the primary source of roughness were tested by sweeping the laser exposure dose for two different resist materials and objectives. In conclusion, the postprocessing smoothening resulted in a lower roughness compared to a direct writing strategy-even when 50-nm vertical discretization steps were used-and still enabled 10 times shorter writing times.
Induction of the Estrogenic Marker Calbindn-D9k by Octamethylcyclotetrasiloxane
Lee, Dongoh; Ahn, Changhwan; An, Beum-Soo; Jeung, Eui-Bae
2015-01-01
Interrupting the hormonal balance of an organism by interfering with hormones and their target receptors gives rise to various problems such as developmental disorders. Collectively, these reagents are known as endocrine disruptors (EDs). Cyclic volatile methyl siloxanes (cVMSs) are a group of silicone polymers that including octamethylcyclotetrasiloxane (D4). In the present study, we examined the estrogenicity of D4 through in vitro and in vivo assays that employed calcium-binding protein 9K (calbindin-D9k; CaBP-9K) as a biomarker. For in vitro investigation, GH3 rat pituitary cells were exposed to vehicle, 17β-estradiol (E2), or D4 with/without ICI 182 780 (ICI). CaBP-9K and progesterone receptor (PR) both were up-regulated by E2 and D4 which were completely blocked by ICI. Transcription of estrogen receptor α (ER α) was decreased by E2 and D4 but increased by ICI. D4 was also administered to immature female rats for an uterotrophic (UT) assay and detection of CaBP-9K. Ethinyl estradiol (EE) or D4 was administered subcutaneously with or without ICI. Although uterine weight was not significant altered by D4, an effect thought to be due to cytochrome P450 (CYP), it induced CaBP-9K and PR gene expression. Based on these results we reveal that D4 has estrogenic potential proven under in vitro and in vivo experimental conditions. PMID:26593928
Free-Standing and Self-Crosslinkable Hybrid Films by Core-Shell Particle Design and Processing.
Vowinkel, Steffen; Paul, Stephen; Gutmann, Torsten; Gallei, Markus
2017-11-15
The utilization and preparation of functional hybrid films for optical sensing applications and membranes is of utmost importance. In this work, we report the convenient and scalable preparation of self-crosslinking particle-based films derived by directed self-assembly of alkoxysilane-based cross-linkers as part of a core-shell particle architecture. The synthesis of well-designed monodisperse core-shell particles by emulsion polymerization is the basic prerequisite for subsequent particle processing via the melt-shear organization technique. In more detail, the core particles consist of polystyrene (PS) or poly(methyl methacrylate) (PMMA), while the comparably soft particle shell consists of poly(ethyl acrylate) (PEA) and different alkoxysilane-based poly(methacrylate)s. For hybrid film formation and convenient self-cross-linking, different alkyl groups at the siloxane moieties were investigated in detail by solid-state Magic-Angle Spinning Nuclear Magnetic Resonance (MAS, NMR) spectroscopy revealing different crosslinking capabilities, which strongly influence the properties of the core or shell particle films with respect to transparency and iridescent reflection colors. Furthermore, solid-state NMR spectroscopy and investigation of the thermal properties by differential scanning calorimetry (DSC) measurements allow for insights into the cross-linking capabilities prior to and after synthesis, as well as after the thermally and pressure-induced processing steps. Subsequently, free-standing and self-crosslinked particle-based films featuring excellent particle order are obtained by application of the melt-shear organization technique, as shown by microscopy (TEM, SEM).
Comparison of retention between maxillary milled and conventional denture bases: A clinical study.
AlHelal, Abdulaziz; AlRumaih, Hamad S; Kattadiyil, Mathew T; Baba, Nadim Z; Goodacre, Charles J
2017-02-01
Clinical studies comparing the retention values of milled denture bases with those of conventionally processed denture bases are lacking. The purpose of this clinical study was to compare the retention values of conventional heat-polymerized denture bases with those of digitally milled maxillary denture bases. Twenty individuals with completely edentulous maxillary arches participated in this study. Definitive polyvinyl siloxane impressions were scanned (iSeries; Dental Wings), and the standard tessellation language files were sent to Global Dental Science for the fabrication of a computer-aided design and computer-aided manufacturing (CAD-CAM) milled denture base (group MB) (AvaDent). The impression was then poured to obtain a definitive cast that was used to fabricate a heat-polymerized acrylic resin denture base resin (group HB). A custom-designed testing device was used to measure denture retention (N). Each denture base was subjected to a vertical pulling force by using an advanced digital force gauge 3 times at 10-minute intervals. The average retention of the 2 fabrication methods was compared using repeated ANOVA (α=.05). Significantly increased retention was observed for the milled denture bases compared with that of the conventional heat-polymerized denture bases (P<.001). The retention offered by milled complete denture bases from prepolymerized poly(methyl methacrylate) resin was significantly higher than that offered by conventional heat- polymerized denture bases. Copyright © 2016 Editorial Council for the Journal of Prosthetic Dentistry. Published by Elsevier Inc. All rights reserved.
Evaluation of certain food additives and contaminants.
2011-01-01
This report represents the conclusions of a Joint FAO/WHO Expert Committee convened to evaluate the safety of various food additives, with a view to recommending acceptable daily intakes (ADIs) and to preparing specifications for identity and purity. The Committee also evaluated the risk posed by two food contaminants, with the aim of deriving tolerable intakes where appropriate and advising on risk management options for the purpose of public health protection. The first part of the report contains a general discussion of the principles governing the toxicological evaluation of and assessment of dietary exposure to food additives and contaminants. A summary follows of the Committee's evaluations of technical, toxicological and dietary exposure data for certain food additives (aluminium-containing food additives, Benzoe Tonkinensis, glycerol ester of gum rosin, glycerol ester of tall oil rosin, glycerol ester of wood rosin, octenyl succinic acid modified gum arabic, polydimethyl siloxane, Ponceau 4R, pullulan, pullulanase from Bacillus deromificans expressed in Bacillus licheniformis, Quinoline Yellow and Sunset Yellow FCF) and two food contaminants (cyanogenic glycosides and fumonisins). Specifications for the following food additives were revised: aluminium lakes of colouring matters; beta-apo-8'-carotenal; beta-apo-8'-carotenoic acid ethyl ester; beta-carotene, synthetic; hydroxypropyl methyl cellulose; magnesium silicate, synthetic; modified starches; nitrous oxide; sodium carboxymethyl cellulose; and sucrose monoesters of lauric, palmitic or stearic acid. Annexed to the report are tables summarizing the Committee's recommendations for dietary exposures to and toxicological evaluations of the food additives and contaminants considered.
Federal Register 2010, 2011, 2012, 2013, 2014
2012-05-24
... EPA. EPA has evaluated the proposal and believes that proceeding with the negotiation of a consent... in participating in the negotiations to notify EPA and announces a public meeting to initiate negotiations. DATES: The meeting to initiate ECA negotiations for D4 and D5 environmental monitoring will be...
Crack-resistant siloxane molding compounds. [Patent application
McFarland, J.W.; Swearngin, C.B.
1980-11-03
The crack resistance of phenyl silicone molding resins containing siliceous fillers is improved by incorporating therein about 0.5 to 5.5% by weight of ..beta..-eucryptite, a lithium aluminum silicate having a negative thermal expansion coefficient. These molding resins are particularly suitable for encapsulating electronic devices such as diodes, coils, resistors, and the like.
High-silica ZSM 5 zeolites were incorporated into poly(dimethyl siloxane) (PDMS) polymers to form mixed matrix membranes for ethanol removal from water via pervaporation. Membrane formulation and preparation parameters were varied to determine the effect on pervaporation perform...
Low temperature cured poly-siloxane passivation for highly reliable a-InGaZnO thin-film transistors
NASA Astrophysics Data System (ADS)
Yoshida, Naofumi; Bermundo, Juan Paolo; Ishikawa, Yasuaki; Nonaka, Toshiaki; Taniguchi, Katsuto; Uraoka, Yukiharu
2018-05-01
Low temperature processable passivation materials are necessary to fabricate highly reliable amorphous InGaZnO (a-IGZO) thin-film transistors (TFT) on organic substrates for flexible device applications. We investigated 3 types of poly-siloxane (Poly-SX) passivation layers fabricated by a solution process and cured at low temperatures (180 °C) for a-IGZO TFTs. This passivation layer greatly improves the stability of the a-IGZO device even after being subjected to positive (PBS) and negative bias stress (NBS). The field effect mobility (μ) of MePhQ504010 passivated on the TFT reached 8.34 cm2/Vs and had a small threshold voltage shift of 0.9 V after PBS, -0.8 V after NBS without the hump phenomenon. Furthermore, we analyzed the hydrogen and hydroxide states in the a-IGZO layer by secondary ion mass spectrometry and X-ray photoelectron spectroscopy to determine the cause of excellent electrical properties despite the curing performed at a low temperature. These results show the potential of the solution processed Poly-SX passivation layer for flexible devices.
NASA Astrophysics Data System (ADS)
Kurbatov, A. O.; Balabaev, N. K.; Mazo, M. A.; Kramarenko, E. Yu.
2018-01-01
Molecular dynamics simulations of two types of isolated siloxane dendrimers of various generations (from the 2nd to the 8th) have been performed for temperatures ranging from 150 K to 600 K. The first type of dendrimer molecules has short spacers consisting of a single oxygen atom. In the dendrimers of the second type, spacers are longer and comprised of two oxygen atoms separated by a single silicon atom. A comparative analysis of molecular macroscopic parameters such as the gyration radius and the shape factor as well as atom distributions within dendrimer interior has been performed for varying generation number, temperature, and spacer length. It has been found that the short-spacer dendrimers of the 7th and 8th generations have a stressed central part with elongated bonds and deformed valence angles. Investigation of the time evolution of radial displacements of the terminal Si atoms has shown that a fraction of the Si groups have a reduced mobility. Therefore, rather long time trajectories (of the order of tens of nanoseconds) are required to study dendrimer intramolecular dynamics.
Sullivan, Alice C; Jayasinghe, Suwan N
2007-07-19
We demonstrate here the discovery of a unique and direct three-dimensional biomicrofabrication concept possessing the ability to revolutionize the jet-based fabrication arena. Previous work carried out on similar jet-based approaches have been successful in fabricating only vertical wallpillar-structures by the controlled deposition of stacked droplets. However, these advanced jet-techniques have not been able to directly fabricate self-supporting archeslinks (without molds or reaction methods) between adjacent structures (walls or pillars). Our work reported here gives birth to a unique type of jet determined by high intensity electric fields, which is derived from a specially formulated siloxane sol. The sol studied here has been chosen for its attractive properties (such as an excellent cross-linking nature as well as the ability to polymerize via polycondensation on deposition to its biocompatability), which promotes direct forming of biostructures with nanometer (<50 nm) sized droplets in three dimensions. We foresee that this direct three-dimensional biomicrofabrication jet technique coupled with a variety of formulated sols having focused and enhanced functionality will be explored throughout the physical and life sciences.
Optical and mechanical behaviors of glassy silicone networks derived from linear siloxane precursors
NASA Astrophysics Data System (ADS)
Jang, Heejun; Seo, Wooram; Kim, Hyungsun; Lee, Yoonjoo; Kim, Younghee
2016-01-01
Silicon-based inorganic polymers are promising materials as matrix materials for glass fiber composites because of their good process ability, transparency, and thermal property. In this study, for utilization as a matrix precursor for a glass-fiber-reinforced composite, glassy silicone networks were prepared via hydrosilylation of linear/pendant Si-H polysiloxanes and the C=C bonds of viny-lterminated linear/cyclic polysiloxanes. 13C nuclear magnetic resonance spectroscopy was used to determine the structure of the cross-linked states, and a thermal analysis was performed. To assess the mechanical properties of the glassy silicone networks, we performed nanoindentation and 4-point bending tests. Cross-linked networks derived from siloxane polymers are thermally and optically more stable at high temperatures. Different cross-linking agents led to final networks with different properties due to differences in the molecular weights and structures. After stepped postcuring, the Young's modulus and the hardness of the glassy silicone networks increased; however, the brittleness also increased. The characteristics of the cross-linking agent played an important role in the functional glassy silicone networks.
Temperature rise in pulpal chamber during fabrication of provisional resinous crowns.
Castelnuovo, J; Tjan, A H
1997-11-01
The heat generated during the exothermic polymerization reaction of autopolymerizing resinous materials and the heat generated by ultraviolet lamps during irradiation of photopolymerizing resinous materials could cause pulpal damage when a direct technique is used to fabricate provisional restorations. This could occur if temperature elevations overcome the physiological heat dissipating mechanisms of the dental-periodontal system. This in vitro study compared the rise in temperatures in the pulpal chamber during fabrication of provisional complete veneer crowns by direct method with different autopolymerizing and photopolymerizing resins. The effect of curing resinous crowns in different matrices, such as a polyvinyl siloxane impression and a vaccuum-formed polypropylene sheet, was also evaluated. The results demonstrated that the amount of heat generated during resin polymerization and transmitted to the pulpal chamber could be damaging to pulpal tissues including odontoblasts. When curing of provisional resinous crowns was performed in the polyvinyl siloxane impression, significantly lower temperatures were recorded compared with curing in the vacuum-formed polypropylene sheet. To prevent pulpal damage, effective cooling procedures are strongly recommended when directly fabricating resinous provisional crowns.
Melt Electrowriting of Thermoplastic Elastomers.
Hochleitner, Gernot; Fürsattel, Eva; Giesa, Reiner; Groll, Jürgen; Schmidt, Hans-Werner; Dalton, Paul D
2018-04-14
Melt electrowriting (MEW), an additive manufacturing process, is established using polycaprolactone as the benchmark material. In this study, a thermoplastic elastomer, namely, poly(urea-siloxane), is synthesized and characterized to identify how different classes of polymers are compatible with MEW. This polyaddition polymer has reversible hydrogen bonding from the melt upon heating/cooling and highly resolved structures are achieved by MEW. The influence of applied voltage, temperature, and feeding pressure on printing outcomes behavior is optimized. Balancing these parameters, highly uniform and smooth-surfaced fibers with diameters ranging from 10 to 20 µm result. The quality of the 3D MEW scaffolds is excellent, with very accurate fiber stacking capacity-up to 50 layers with minimal defects and good fiber fusion between the layers. There is also minimal fiber sagging between the crossover points, which is a characteristic of thicker MEW scaffolds previously reported with other polymers. In summary, poly(urea-siloxane) demonstrates outstanding compatibility with the MEW process and represents a class of polymer-thermoplastic elastomers-that are, until now, untested with this approach. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Structure/permeability relationships of silicon-containing polyimides
NASA Technical Reports Server (NTRS)
Stern, S. A.; Vaidyanathan, R.; Pratt, J. R.
1989-01-01
The permeability to H2, O2, N2, CO2 and CH4 of three silicone-polyimide random copolymers and two polyimides containing silicon atoms in their backbone chains, was determined at 35.0 C and at pressures up to about 120 psig (approximately 8.2 atm). The copolymers contained different amounts of BPADA-m-PDA and amine-terminated poly (dimethyl siloxane) and also had different numbers of siloxane linkages in their silicone component. The polyimides containing silicon atoms (silicon-modified polyimides) were SiDA-4,4'-ODA and SiDA-p-PDA. The gas permeability and selectivity of the copolymers are more similar to those of their silicone component than of the polyimide component. By contrast, the permeability and selectivity of the silicon-modified polyimides are more similar to those of their parent polyimides, PMDA-4,4'-ODA and SiDA-p-PDA. The substitution of SiDA for the PMDA moiety in a polyimide appears to result in a significant increase in gas permeability, without a correspondingly large decrease in selectivity. The potential usefulness of the above polymers and copolymers as gas separation membranes is discussed.
Rufin, M. A.; Gruetzner, J. A.; Hurley, M. J.; Hawkins, M. L.; Raymond, E. S.; Raymond, J. E.
2015-01-01
Silicones with superior protein resistance were produced by bulk-modification with poly(ethylene oxide) (PEO)-silane amphiphiles that demonstrated a higher capacity to restructure to the surface-water interface versus conventional non-amphiphilic PEO-silanes. The PEO-silane amphiphiles were prepared with a single siloxane tether length but variable PEO segment lengths: α-(EtO)3Si(CH2)2-oligodimethylsiloxane13-block-poly(ethylene oxide)n-OCH3 (n = 3, 8, and 16). Conventional PEO-silane analogues (n = 3, 8 and 16) as well as a siloxane tether-silane (i.e. no PEO segment) were prepared as controls. When surface-grafted onto silicon wafer, PEO-silane amphiphiles produced surfaces that were more hydrophobic and thus more adherent towards fibrinogen versus the corresponding PEO-silane. However, when blended into a silicone, PEO-silane amphiphiles exhibited rapid restructuring to the surface-water interface and excellent protein resistance whereas the PEO-silanes did not. Silicones modified with PEO-silane amphiphiles of PEO segment lengths n = 8 and 16 achieved the highest protein resistance. PMID:26339488
Gao, Changlu; Sun, Xiuhua; Gillis, Kevin D.
2016-01-01
The design, fabrication and test of a microfluidic cell trapping device to measure single cell exocytosis were reported. Research on the patterning of double layer template based on repetitive standard photolithography of AZ photoresist was investigated. The replicated poly(dimethyl siloxane) devices with 2.5 μm deep channels were proved to be efficient for stopping cells. Quantal exocytosis measurement can be achieved by targeting single or small clumps of chromaffin cells on top of the 10 μm ×10 μm indium tin oxide microelectrodes arrays with the developed microdevice. And about 72% of the trapping sites can be occupied by cells with hydrodynamic trapping method and the recorded amperometric signals are comparable to the results with traditional carbon fiber microelectrodes. The method of manufacturing the microdevices is simple, low-cost and easy to perform. The manufactured device offers a platform for the high throughput detection of quantal catecholamine exocytosis from chromaffin cells with sufficient sensitivity and broad application. PMID:23329291
Building on Sub-Arctic Soil: Geopolymerization of Muskeg to a Densified Load-Bearing Composite.
Waetzig, Gregory R; Cho, Junsang; Lacroix, Max; Banerjee, Sarbajit
2017-11-07
The marshy water-saturated soil typical of the sub-Arctic represents a considerable impediment to the construction of roads, thereby greatly hindering human habitation and geological excavation. Muskeg, the native water-laden topsoil characteristic of the North American sub-Arctic, represents a particularly vexing challenge for road construction. Muskeg must either be entirely excavated, or for direct construction on muskeg, a mix of partial excavation and gradual compaction with the strategic placement of filling materials must be performed. Here, we demonstrate a novel and entirely reversible geopolymerization method for reinforcing muskeg with wood fibers derived from native vegetation with the addition of inorganic silicate precursors and without the addition of extraneous metal precursors. A continuous siloxane network is formed that links together the muskeg, wood fibers, and added silicates yielding a load-bearing and low-subsidence composite. The geopolymerization approach developed here, based on catalyzed formation of a siloxane network with further incorporation of cellulose, allows for an increase of density as well as compressive strength while reducing the compressibility of the composite.
Gatidou, Georgia; Arvaniti, Olga S; Stasinakis, Athanasios S; Thomaidis, Nikolaos S; Andersen, Henrik R
2016-12-01
Hydrolysis of hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6) and dodecamethylcyclohexasilane (D6_silane) and their sorption to digested sludge was studied in batch experiments. Hydrolysis was affected by the type of the compound and the applied temperature, while the relevant half-life values ranged between 0.07±0.01d (D3, 55°C) and 48.4±17.1d (D6_silane, 4°C). D5 showed the greatest affinity for sorption to digested sludge (logK d : 3.84±3.42), the lowest LogK d value was found for D3 (1.46±0.95). Prediction of investigated compounds' fate in a single-stage anaerobic digestion system indicated that volatilization seems to be the major fate in both mesophilic and thermophilic conditions. The addition of a pre-digester with 3d retention time would significantly decrease the expected concentrations of all siloxanes in biogas, enhancing their removal through hydrolysis and sorption to sludge. Copyright © 2016 Elsevier Ltd. All rights reserved.
New transition metal complexes and their ring-opened polymers
NASA Astrophysics Data System (ADS)
Apodaca, Paula
An exciting new class of metallacycle (eta5-C5 H4Fe) (CO)2CH2SiR2 that undergoes ring-opening polymerization was recently reported by Sharma et al. [1]. We are interested in further expanding this research area by synthesizing related cyclopentadienyl derivatives containing Fe, Mo, and W in combination with other elements of the group 14. We report here the synthesis and crystal structure characterization of new germa-metallacyclobutanes of Mo and W. In addition, we have successfully synthesized and characterized new ring-opening polymers of the related germanium systems [(eta5-C5 H4Fe)(CO) 2(CH2GeR2)] n. The new polymers were characterized using various spectroscopic techniques and gel permeation chromatography. The recent report on the synthesis of a new class of siloxane polymers based upon base-catalyzed ring opening of phenylene-bridged cyclic siloxanes [2] encouraged us to investigate the related ferrocenyl (Fc, (C5H 5)Fe(C5H4)) siloxane systems. The incorporation of ferrocene could provide new materials with all the interesting properties usually associated with these groups such as thermal and photochemical stability, electrochemical activity and potentially conducting materials. Thus far a new required organometallic monomer containing Fc-R, where R = disilaoxacyclopentene 5 has been synthesized and completely characterized. Based-induced ring-opening polymerizations of 5 were attempted under different reaction conditions and produced, inter alia: (C5H5)Fe(C 5H4)C(SiMe2OH)=CH(SiMe2R), R = nBu (2), tBu (3), Ph (4). The single crystal X-ray structures and full spectroscopic analysis of such products has been accomplished. Furthermore, the reactivity of the ferrocenyl silanols concerning condensation and their behavior under acidic conditions has been investigated. 1Sharma, H.; Cervantes-Lee, F.; Pannell, K. H. J. Am. Chem. Soc. 2004, 126, 1326. 2 Loy, A. D.; Rahimian, K.; Samara, M. Angew. Chem. 1999, 38, 45.
Preliminary characterization of an expanding flow of siloxane vapor MDM
NASA Astrophysics Data System (ADS)
Spinelli, A.; Cozzi, F.; Cammi, G.; Zocca, M.; Gaetani, P.; Dossena, V.; Guardone, A.
2017-03-01
The early experimental results on the characterization of expanding flows of siloxane vapor MDM (C8H24O2Si3, octamethyltrisiloxane) are presented. The measurements were performed on the Test Rig for Organic VApors (TROVA) at the CREA Laboratory of Politecnico di Milano. The TROVA test-rig was built in order to investigate the non-ideal compressible-fluid behavior of typical expanding flows occurring within organic Rankine cycles (ORC) turbine passages. The test rig implements a batch Rankine cycle where a planar converging-diverging nozzle replaces the turbine and represents a test section. Investigations related to both fields of non-ideal compressible-fluid dynamics fundamentals and turbomachinery are allowed. The nozzle can be operated with different working fluids and operating conditions aiming at measuring independently the pressure, the temperature and the velocity field and thus providing data to verify the thermo-fluid dynamic models adopted to predict the behavior of these flows. The limiting values of pressure and temperature are 50 bar and 400 °C respectively. The early measurements are performed along the nozzle axis, where an isentropic process is expected to occur. In particular, the results reported here refer to the nozzle operated in adapted conditions using the siloxane vapor MDM as working fluid in thermodynamic regions where mild to medium non-ideal compressible-fluid effects are present. Both total temperature and total pressure of the nozzle are measured upstream of the test section, while static pressure are measured along the nozzle axis. Schlieren visualizations are also carried out in order to complement the pressure measurement with information about the 2D density gradient field. The Laser Doppler Velocimetry technique is planned to be used in the future for velocity measurements. The measured flow field has also been interpreted by resorting to the quasi-one-dimensional theory and two dimensional CFD viscous calculation. In both cases state-of-the-art thermodynamic models were applied.
Suresh, Supraja
2015-01-01
Intracranial pressure and volume vary considerably between hydrocephalic patients, and with age, health and haemodynamic status; if left untreated, intracranial pressure rises and the ventricular system expands to accommodate the excess cerebrospinal fluid, with significant morbidity and mortality. Cerebrospinal fluid shunts in use today have a high incidence of failure with shunt obstruction being the most serious. Conventional proximal shunt catheters are made from poly(dimethyl)siloxane, the walls of which are perforated with holes for the cerebrospinal fluid to pass through. The limited range of catheters, in terms of material selection and flow distribution, is responsible in large part for their poor performance. In this study, we present an alternative design of proximal catheter made of electrospun polyether urethane, and evaluate its performance in the presence of glial cells, which are responsible for shunt blockage. The viability and growth of cells on catheter materials such as poly(dimethyl)siloxane and polyurethane in the form of cast films, microfibrous mats and porous sponges were studied in the presence of proteins present in cerebrospinal fluid after 48 h and 96 h in culture. The numbers of viable cells on each substrate were comparable to untreated poly(dimethyl)siloxane, both in the presence and absence of serum proteins found in cerebrospinal fluid. A cell culture model of shunt obstruction was developed in which cells on electrospun polyether urethane catheters were subjected to flow during culture in vitro, and the degree of obstruction quantified in terms of hydraulic permeability after static and perfusion culture. The results indicate that a catheter made of electrospun polyether urethane would be able to maintain cerebrospinal fluid flow even with the presence of cells for the time period chosen for this study. These findings have implications for the design and deployment of microporous shunt catheter systems for the treatment of hydrocephalus. PMID:25245779
40 CFR 716.20 - Studies not subject to the reporting requirements.
Code of Federal Regulations, 2014 CFR
2014-07-01
... as a fertilizer. (2) For the specified chemicals in § 716.120(d) under the category “Siloxanes... Chemicals Program. Studies which have been initiated pursuant to a TSCA section 4(a) test rule, for which... §§ 716.30 and 716.35. (5) Studies of chemical substances which are not on the TSCA Chemical Substances...
40 CFR 716.20 - Studies not subject to the reporting requirements.
Code of Federal Regulations, 2012 CFR
2012-07-01
... as a fertilizer. (2) For the specified chemicals in § 716.120(d) under the category “Siloxanes... Chemicals Program. Studies which have been initiated pursuant to a TSCA section 4(a) test rule, for which... §§ 716.30 and 716.35. (5) Studies of chemical substances which are not on the TSCA Chemical Substances...
40 CFR 716.20 - Studies not subject to the reporting requirements.
Code of Federal Regulations, 2013 CFR
2013-07-01
... as a fertilizer. (2) For the specified chemicals in § 716.120(d) under the category “Siloxanes... Chemicals Program. Studies which have been initiated pursuant to a TSCA section 4(a) test rule, for which... §§ 716.30 and 716.35. (5) Studies of chemical substances which are not on the TSCA Chemical Substances...
40 CFR 716.20 - Studies not subject to the reporting requirements.
Code of Federal Regulations, 2011 CFR
2011-07-01
... as a fertilizer. (2) For the specified chemicals in § 716.120(d) under the category “Siloxanes... Chemicals Program. Studies which have been initiated pursuant to a TSCA section 4(a) test rule, for which... §§ 716.30 and 716.35. (5) Studies of chemical substances which are not on the TSCA Chemical Substances...
40 CFR 716.20 - Studies not subject to the reporting requirements.
Code of Federal Regulations, 2010 CFR
2010-07-01
... as a fertilizer. (2) For the specified chemicals in § 716.120(d) under the category “Siloxanes... Chemicals Program. Studies which have been initiated pursuant to a TSCA section 4(a) test rule, for which... §§ 716.30 and 716.35. (5) Studies of chemical substances which are not on the TSCA Chemical Substances...
Management of excessive movable tissue: a modified impression technique.
Shum, Michael H C; Pow, Edmond H N
2014-08-01
Excessive movable tissue is a challenge in complete denture prosthetics. A modified impression technique is presented with polyvinyl siloxane impression material and a custom tray with relief areas and perforations in the area of the excessive movable tissue. Copyright © 2014 Editorial Council for the Journal of Prosthetic Dentistry. Published by Elsevier Inc. All rights reserved.
Polymer-Attached Functional Inorganic-Organic Hybrid Nano-Composite Aerogels
2003-01-01
drugs. The chemistry to synthesize polyamino- siloxane based aerogel composite was discussed. In addition, two approaches to synthesize PHEMA aerogel... Composite Aerogels DISTRIBUTION: Approved for public release, distribution unlimited This paper is part of the following report: TITLE: Materials...Proc. Vol. 740 © 2003 Materials Research Society 112.24 Polymer-Attached Functional Inorganic-Organic Hybrid Nano- composite Aerogels Xipeng Liu, Mingzhe
Hydrogenation of biomass-derived substrates
Gordon, John C.; Waidmann, Christopher R.
2016-06-07
The .alpha.,.beta.-unsaturated ketone moiety of a substrate representative of non-food based biomass was hydrogenated to the corresponding saturated alcohol moiety using a composition including (1) a copper salt; (2) a phosphine; (3) a polar aprotic solvent such as acetonitrile, and (4) a compound suitable for providing hydrogen for the hydrogenation, such as a suitable silane material or a suitable siloxane material.
Catalytic Ketone Hydrodeoxygenation Mediated by Highly Electrophilic Phosphonium Cations.
Mehta, Meera; Holthausen, Michael H; Mallov, Ian; Pérez, Manuel; Qu, Zheng-Wang; Grimme, Stefan; Stephan, Douglas W
2015-07-06
Ketones are efficiently deoxygenated in the presence of silane using highly electrophilic phosphonium cation (EPC) salts as catalysts, thus affording the corresponding alkane and siloxane. The influence of distinct substitution patterns on the catalytic effectiveness of several EPCs was evaluated. The deoxygenation mechanism was probed by DFT methods. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Method for making block siloxane copolymers
Butler, N.L.; Jessop, E.S.; Kolb, J.R.
1981-02-25
A method for synthesizing block polysiloxane copolymers is disclosed. Diorganoscyclosiloxanes and an end-blocking compound are interacted in the presence of a ring opening polymerization catalyst, producing a blocked prepolymer. The prepolymer is then interacted with a silanediol, resulting in condensation polymerization of the prepolymers. A second end-blocking compound is subsequently introduced to end-cap the polymers and copolymers formed from the condensation polymerization.
Method for making block siloxane copolymers
Butler, Nora; Jessop, Edward S.; Kolb, John R.
1982-01-01
A method for synthesizing block polysiloxane copolymers. Diorganoscyclosiloxanes and an end-blocking compound are interacted in the presence of a ring opening polymerization catalyst, producing a blocked prepolymer. The prepolymer is then interacted with a silanediol, resulting in condensation polymerization of the prepolymers. A second end-blocking compound is subsequently introduced to end-cap the polymers and copolymers formed from the condensation polymerization.
2013-03-01
remain nonvolatile during the entire fiber-infusion process and curing operation. The resin must offer several days of storage life before the prepreg ...shipboard handling and in-flight cyclic loading. The raw materials for the new resin and the process for making and curing the prepreg must be affordable
Synthetic Lubricating Oil Greases Containing Metal Chelates of Schiff Bases
1992-09-15
bearing tester. The data generated from the test is pres- . ol Oil/10rs•al~s okfa, otl/ i.03 - ented in Table il1. cloy Thicsed Grews TABLE MI +3% aeys...groups having I to 6 hydrocarbons. the polysilicones . the siloxanes e.g. sili- carbon atoms and X is a number rankbing from I to 12. cone esters, the
Evaluation of Rigid-Rod Polymeric Fibers by Post-Treatment in scC02
2008-12-30
small molecular weight vinyl substituted polysiloxane prepolymer and hydride containing crosslinker to the fiber, swelling the fiber with the siloxane... prepolymer and subsequently initiating crosslinking by introduction of a Karstedt’s catalyst known to be highly soluble and robust in a scCO2...polydimethylsiloxane Prepolymer (PVMS) Polymethylvinylsiloxane-polydimethylsiloxane resin was prepared in a condensation reaction from
Zhao, Hui; Hao, Tong-Hui; Hu, Guo-Hua; Shi, Dean; Huang, Da; Jiang, Tao; Zhang, Qun-Chao
2017-01-01
A series of novel polyurethanes containing cross-linked siloxane in the side chain (SPU) were successfully synthesized through a sol-gel process. The SPU was composed of 0%–20% N-(n-butyl)-3-aminopropyltriethoxysilane (HDI-T) modified hexamethylene diisocynate homopolymer. The effects of HDI-T content on both the structure and properties of SPU were investigated by Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), mechanical properties tests, gel content test, water contact angle measurement and water absorption test. FT-IR, XPS and XRD results confirmed the successful incorporation of HDI-T onto polyurethanes and the formation of Si–O–Si. The surface roughness and the Si content of SPU enhanced with the increase of HDI-T content. Both crystallization and melting temperature shifted to a lower point after the incorporation of HDI-T. The hydrophobicity, tensile strength, Young’s modulus and pencil hardness overall increased with the increasing of HDI-T content, whereas the thermal stability and the elongation at break of SPU slightly decreased. PMID:28772607
The development of an SC1 removable si-anti-reflective-coating
NASA Astrophysics Data System (ADS)
Yamada, Shintaro; Ke, Iou-Sheng; Cutler, Charlotte; Cui, Li; LaBeaume, Paul; Greene, Daniel; Popere, Bhooshan; Sullivan, Chris; Leonard, JoAnne; Coley, Suzanne; Wong, Sabrina; Ongayi, Owendi; Cameron, Jim; Clark, Michael B.; Fitzgibbons, Thomas C.
2018-03-01
A trilayer stack of spin-on-carbon (SOC), silicon anti-reflective coating (SiARC) and photoresist (PR) is often used to enable high resolution implant layers for integrated circuit manufacturing. Damage to substrates from SiARC removal using dry etching or aqueous hydrogen fluoride has increased the demand for innovative SiARC materials for implant lithography process. Wet strippable SiARCs (WS-SiARCs) capable of stripping under mild conditions such as SC1 (ammonium hydroxide/hydrogen peroxide/water) while maintaining key performance metrics of standard SiARCs is highly desirable. Minimizing the formation of Si-O-Si linkages by introducing organic crosslink sites was effective to impart SC1 solubility particularly after O2 dry etching. Incorporation of acidic groups onto the crosslinking site further improved SC1 solubility. A new siloxane polymer architecture that has SC1 active functionality in the polymer backbone was developed to further enhance SC1 solubility. A new SiARC formulation based on the new siloxane polymer achieved equivalent lithographic performances to a classic SiARC and SC1 strip rate >240Å/min under a relatively low concentration SC1 condition such as ammonium hydroxide/hydrogen peroxide/water=1/1/40.
Superstretchable, Self-Healing Polymeric Elastomers with Tunable Properties
DOE Office of Scientific and Technical Information (OSTI.GOV)
Cao, Peng-Fei; Li, Bingrui; Hong, Tao
Utilization of self-healing chemistry to develop synthetic polymer materials that can heal themselves with restored mechanical performance and functionality is of great interest. Self-healable polymer elastomers with tunable mechanical properties are especially attractive for a variety of applications. In this paper, a series of urea functionalized poly(dimethyl siloxane)-based elastomers (U-PDMS-Es) are reported with extremely high stretchability, self-healing mechanical properties, and recoverable gas-separation performance. Tailoring the molecular weights of poly(dimethyl siloxane) or weight ratio of elastic cross-linker offers tunable mechanical properties of the obtained U-PDMS-Es, such as ultimate elongation (from 984% to 5600%), Young's modulus, ultimate tensile strength, toughness, and elasticmore » recovery. The U-PDMS-Es can serve as excellent acoustic and vibration damping materials over a broad range of temperature (over 100 °C). The strain-dependent elastic recovery behavior of U-PDMS-Es is also studied. After mechanical damage, the U-PDMS-Es can be healed in 120 min at ambient temperature or in 20 min at 40 °C with completely restored mechanical performance. Lastly, the U-PDMS-Es are also demonstrated to exhibit recoverable gas-separation functionality with retained permeability/selectivity after being damaged.« less
Sullivan, Alice C.; Jayasinghe, Suwan N.
2007-01-01
We demonstrate here the discovery of a unique and direct three-dimensional biomicrofabrication concept possessing the ability to revolutionize the jet-based fabrication arena. Previous work carried out on similar jet-based approaches have been successful in fabricating only vertical wall∕pillar-structures by the controlled deposition of stacked droplets. However, these advanced jet-techniques have not been able to directly fabricate self-supporting arches∕links (without molds or reaction methods) between adjacent structures (walls or pillars). Our work reported here gives birth to a unique type of jet determined by high intensity electric fields, which is derived from a specially formulated siloxane sol. The sol studied here has been chosen for its attractive properties (such as an excellent cross-linking nature as well as the ability to polymerize via polycondensation on deposition to its biocompatability), which promotes direct forming of biostructures with nanometer (<50 nm) sized droplets in three dimensions. We foresee that this direct three-dimensional biomicrofabrication jet technique coupled with a variety of formulated sols having focused and enhanced functionality will be explored throughout the physical and life sciences. PMID:19693359
DOE Office of Scientific and Technical Information (OSTI.GOV)
Zhong, Wei; Jiang, Ting; Jafari, Tahereh
In this work, mesoporous aluminas (MAs) with uniform and monomodal pores were fabricated via a modified inverse micelle synthesis method, using a non-polar solvent (to minimize the effect of water content) and short reaction time (for a fast evaporation process). The effects of reaction times (4–8 h), surfactant chain lengths (non-ionic surfactants), and calcination temperatures and hold times (450–600 °C; 1–4 h) on the textural properties of MA were studied. Additionally, the targeted pore sizes of MA were obtained in the range of 3.1–5.4 nm by adjusting the surfactant and reaction time. The surface area and pore volume were controlledmore » by the calcination temperature and hold time while maintaining the thermal stability of the materials. The tuned MA of the large mesopore volume achieved 168 mg/g octamethylcyclotetrasiloxane (D4 siloxane) adsorption capacity, a 32% improvement compared to commercially activated alumina. Finally, after three adsorption recycles, the synthesized MA still maintained approximate 85% of its original adsorption capacity, demonstrating a sustainable adsorption performance and high potential for related industrial applications.« less
Zhong, Wei; Jiang, Ting; Jafari, Tahereh; ...
2016-10-18
In this work, mesoporous aluminas (MAs) with uniform and monomodal pores were fabricated via a modified inverse micelle synthesis method, using a non-polar solvent (to minimize the effect of water content) and short reaction time (for a fast evaporation process). The effects of reaction times (4–8 h), surfactant chain lengths (non-ionic surfactants), and calcination temperatures and hold times (450–600 °C; 1–4 h) on the textural properties of MA were studied. Additionally, the targeted pore sizes of MA were obtained in the range of 3.1–5.4 nm by adjusting the surfactant and reaction time. The surface area and pore volume were controlledmore » by the calcination temperature and hold time while maintaining the thermal stability of the materials. The tuned MA of the large mesopore volume achieved 168 mg/g octamethylcyclotetrasiloxane (D4 siloxane) adsorption capacity, a 32% improvement compared to commercially activated alumina. Finally, after three adsorption recycles, the synthesized MA still maintained approximate 85% of its original adsorption capacity, demonstrating a sustainable adsorption performance and high potential for related industrial applications.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Small, Ward; Pearson, Mark A.; Jensen, Wayne A.
2015-09-13
Compression set of solid (non-porous) Dow Corning SE 1700, Sylgard 184, and “new” M9787 siloxane elastomers was measured according to ASTM D395 Method B. Specimens of SE 1700 were made using (1) the manufacturer’s suggested cure of 150°C for 30 min and (2) an extended cure of 60°C for 6 h and 150°C for 1 h followed by a post-cure under nitrogen purge at 125°C for 12 h. Four specimens of each material were aged at 25-27% compressive strain at 70°C under nitrogen purge for 70 h. Final thickness of each specimen was measured after a 30-min cooling/relaxation period, andmore » compression set relative to deflection was calculated. The average compression set relative to deflection was 6.0% for SE 1700 made using the extended cure and post-cure, 11.3% for SE 1700 made using the manufacturer’s suggested cure, 12.1% for Sylgard 184, and 1.9% for M9787. The extended cure and post-cure reduced the amount of compression set in SE 1700.« less
NASA Astrophysics Data System (ADS)
Birajdar, Mallinath S.; Cho, Hyunjoo; Seo, Youngmin; Choi, Jonghoon; Park, Hansoo
2018-04-01
Poly (dimethyl siloxane) (PDMS) is widely used in various biomedical applications. However, the PDMS surface is known to cause bacterial adhesion and protein absorption issues due to its high hydrophobicity. Therefore, the development of antibacterial and anti-protein products is necessary to prevent these problems. In this study, to improve its antibacterial property and prevent protein adsorption, PDMS surfaces were conjugated with itaconic acid (IA) and poly (itaconic acid) (PIA) via a chemical method. Additionally, IA and PIA were physically blended with PDMS to compare the antibacterial properties of these materials with those of the chemically conjugated PDMS surfaces. The successful synthesis of the PIA polymer structure was confirmed by proton nuclear magnetic resonance (1H NMR) spectroscopy. The successful conjugation of IA and PIA on PDMS was confirmed by attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), water contact angle measurements, and microbicinchoninic acid (BCA) protein assay analyses. The PDMS surfaces functionalized with IA and PIA by the conjugation method better prevented protein adsorption than the bare PDMS. Therefore, these surface-conjugated PDMS can be used in various biomedical applications.
Baheiraei, Nafiseh; Gharibi, Reza; Yeganeh, Hamid; Miragoli, Michele; Salvarani, Nicolò; Di Pasquale, Elisa; Condorelli, Gianluigi
2016-03-01
Tissue-engineered cardiac patch aims at regenerating an infarcted heart by improving cardiac function and providing mechanical support to the diseased myocardium. In order to take advantages of electroactivity, a new synthetic method was developed for the introduction of an electroactive oligoaniline into the backbone of prepared patches. For this purpose, a series of electroactive polyurethane/siloxane films containing aniline tetramer (AT) was prepared through sol-gel reaction of trimethoxysilane functional intermediate polyurethane prepolymers made from castor oil and poly(ethylene glycol). Physicochemical, mechanical, and electrical conductivity of samples were evaluated and the recorded results were correlated to their structural characteristics. The optimized films were proved to be biodegradable and have tensile properties suitable for cardiac patch application. The embedded AT moieties in the backbone of the prepared samples preserved their electroactivity with the electrical conductivity in the range of 10 -4 S/cm. The prepared films were compatible with proliferation of C2C12 and had potential for enhancing myotube formation even without external electrical stimulation. © 2015 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 104A: 775-787, 2016. © 2015 Wiley Periodicals, Inc.
Superstretchable, Self-Healing Polymeric Elastomers with Tunable Properties
Cao, Peng-Fei; Li, Bingrui; Hong, Tao; ...
2018-04-16
Utilization of self-healing chemistry to develop synthetic polymer materials that can heal themselves with restored mechanical performance and functionality is of great interest. Self-healable polymer elastomers with tunable mechanical properties are especially attractive for a variety of applications. In this paper, a series of urea functionalized poly(dimethyl siloxane)-based elastomers (U-PDMS-Es) are reported with extremely high stretchability, self-healing mechanical properties, and recoverable gas-separation performance. Tailoring the molecular weights of poly(dimethyl siloxane) or weight ratio of elastic cross-linker offers tunable mechanical properties of the obtained U-PDMS-Es, such as ultimate elongation (from 984% to 5600%), Young's modulus, ultimate tensile strength, toughness, and elasticmore » recovery. The U-PDMS-Es can serve as excellent acoustic and vibration damping materials over a broad range of temperature (over 100 °C). The strain-dependent elastic recovery behavior of U-PDMS-Es is also studied. After mechanical damage, the U-PDMS-Es can be healed in 120 min at ambient temperature or in 20 min at 40 °C with completely restored mechanical performance. Lastly, the U-PDMS-Es are also demonstrated to exhibit recoverable gas-separation functionality with retained permeability/selectivity after being damaged.« less
Synthesis of a novel multi N-halamines siloxane precursor and its antimicrobial activity on cotton
NASA Astrophysics Data System (ADS)
Wu, Lin; Xu, Yan; Cai, Lu; Zang, Xiong; Li, Zhanxiong
2014-09-01
A novel N-halamine siloxane antibacterial precursor N-(3-triethoxysilylpropyl)-N‧- (N″‧-heptylcarbamido-N″-ethyl)-butanediamide (TSHCEB) was synthesized and characterized in this study. The compound was then tethered to the surface of cotton fabrics through covalent ether linkages, followed by exposure to dilute sodium hypochlorite solutions to confer the cotton fabrics antibacterial property. The chemical structure of the monomer was confirmed by FTIR, 1H NMR and MS, and the surface of the treated cotton fabrics was characterized by FTIR, TGA, SEM, and XPS analysis. The antimicrobial cotton materials were then challenged with Gram-negative Escherichia coli O157:H7 (ATCC 43895) and Gram-positive Staphylococcus aureus (ATCC 6538). Results showed that it provided excellent antimicrobial properties against E. coli O157:H7 and S. aureus via direct contacting for 2-15 min. The controlled release of diverse chlorines was proved by inhibition zone. The chlorine bonded to the coating was stable under standard washing test and routine storage, stability toward UVA irradiation was also investigated, and the lost chlorine could be regenerated by rechlorination. The new N-halamine antibacterial precursor can provide superior antibacterial property within a short contact time.
2010-03-18
quantum dots composed of a photopolymerizable outer corona constituting methacrylate and an inner siloxane layer, with a view making them photo...nanostructures. The inherent properties of photopolymerizable QDs such as their stability, PL, and ease of solution processability, make them suitable...Thiophenes are important compounds that are used as building blocks in many chemical synthesis. The thiophene oligomers and thiophene-based
Thiophenyl ether disiloxanes and trisiloxanes useful as lubricant fluids
NASA Technical Reports Server (NTRS)
Bilow, N.; Akawie, R. I. (Inventor)
1974-01-01
The characteristics of organosilicon compounds for lubrication under extreme conditions are discussed. The substances considered are thiophenyl ether disiloxanes and trisiloxanes. These substances have low pour points and a high degree of radiation resistance. Substitution of sulfur for the phenoxy group oxygen of either siloxane compounds has been found to result in a marked improvement in lubricity. The chemical formulas of the organic compounds are presented.
Siloxane Modifiers for Epoxy Resins.
1983-12-01
similarly prepared ATBN- and CTBN -modified epoxies. Wear rate was quite dramatically reduced with some of the modifiers. Wear results are discussed in...similarly prepared ATBN- and CTBN -modified epoxies. Wear rate was quite dramatically reduced with some of the modifiers. Wear results are discussed...acrylonitrile copolymers having both carboxyl ( CTBN ) and amine (ATBN) end groups have been widely used as epoxy modifiers (4-11). During the curing process, the
Microwave Hydrogen Production from Methane
2012-04-01
combustion NOx control of reciprocating engine exhaust and fuel cell application of biogas . Our target is to obtain the methane conversion efficiency...demonstration of MW technology removing and destroying hydrogen sulfide (H2S) and siloxanes from biogas produced by Sacramento Regional Wastewater...running on biogas and is currently conducting the field demonstration of the unit at Tollenaar Dairy in Elk Grove, CA. SMUD, California Air Resources
1983-09-01
disponibles et on en a compare les resultats avec ceux qui ont 6ti obtenus dans le cas des finis expe’rimentaux. Les essais de durabilit englobaient...short sumary of these tests has been included in ref. 10. PHOSPHAIE RESISTANCE TESI The resistance of treated fabrics to wetting by organo-phosphorus
Anti-reflective and anti-soiling coatings with self-cleaning properties
DOE Office of Scientific and Technical Information (OSTI.GOV)
Nair, Vinod; Brophy, Brenor L.
Disclosed herein is a coated glass element including a glass component and a coating adhered to the glass component through siloxane linkages, the coating having at least one of an anti-reflective property, a high abrasion resistance property and a hydrophobic property, wherein the coating comprises a dried gel formed from at least one hydrolyzed alkoxysilane-based sol and at least one hydrolyzed organosilane-based sol.
Ionic liquid compatibility in polyethylene oxide/siloxane ion gel membranes
Kusuma, Victor A.; Macala, Megan K.; Liu, Jian; ...
2018-10-02
Ion gel films were prepared by incorporating eight commercially available ionic liquids in two different cross-linked polymer matrices to evaluate their phase miscibility, gas permeability and ionic conductivity for potential applications as gas separation membranes and solid electrolyte materials. The ionic liquids cations were 1-ethyl-3-methylimidazolium, 1-ethyl-3-methylpyridinium, 1-butyl-1-methylpyrrolidinium, tributylmethylphosphonium, and butyltrimethylammonium with a common anion (bis(trifluoromethylsulfonyl)imide). In addition, ionic liquids with 1-ethyl-3-methylimidazolium cation with acetate, dicyanamide and tetrafluoroborate counterions were evaluated. The two polymers were cross-linked poly(ethylene oxide) and cross-linked poly(ethylene oxide)/siloxane copolymer. Differential scanning calorimetry, X-ray diffractometry and visual observations were performed to evaluate the ion gels’ miscibility, thermal stabilitymore » and homogeneity. Ionic liquids with the least basic anion (bis(trifluoromethylsulfonyl)imide) and aromatic cations containing acidic proton (e.g. imidazolium and pyridinium) gave the most stable and miscible ion gels. Phase stability was shown to be a function of both ionic liquid content and temperature, with phase separation observed at elevated temperatures. In conclusion, gas permeability testing with carbon dioxide and nitrogen and ionic conductivity measurements confirmed that these ionic liquids increased the gas permeability and ionic conductivity of the polymers.« less
Ionic liquid compatibility in polyethylene oxide/siloxane ion gel membranes
DOE Office of Scientific and Technical Information (OSTI.GOV)
Kusuma, Victor A.; Macala, Megan K.; Liu, Jian
Ion gel films were prepared by incorporating eight commercially available ionic liquids in two different cross-linked polymer matrices to evaluate their phase miscibility, gas permeability and ionic conductivity for potential applications as gas separation membranes and solid electrolyte materials. The ionic liquids cations were 1-ethyl-3-methylimidazolium, 1-ethyl-3-methylpyridinium, 1-butyl-1-methylpyrrolidinium, tributylmethylphosphonium, and butyltrimethylammonium with a common anion (bis(trifluoromethylsulfonyl)imide). In addition, ionic liquids with 1-ethyl-3-methylimidazolium cation with acetate, dicyanamide and tetrafluoroborate counterions were evaluated. The two polymers were cross-linked poly(ethylene oxide) and cross-linked poly(ethylene oxide)/siloxane copolymer. Differential scanning calorimetry, X-ray diffractometry and visual observations were performed to evaluate the ion gels’ miscibility, thermal stabilitymore » and homogeneity. Ionic liquids with the least basic anion (bis(trifluoromethylsulfonyl)imide) and aromatic cations containing acidic proton (e.g. imidazolium and pyridinium) gave the most stable and miscible ion gels. Phase stability was shown to be a function of both ionic liquid content and temperature, with phase separation observed at elevated temperatures. In conclusion, gas permeability testing with carbon dioxide and nitrogen and ionic conductivity measurements confirmed that these ionic liquids increased the gas permeability and ionic conductivity of the polymers.« less
Jesus, Celso R N; Molina, Eduardo F; Pulcinelli, Sandra H; Santilli, Celso V
2018-06-06
In this work, we report the effects of incorporation of variable amounts (1-20 wt %) of sodium montmorillonite (MMT) into a siloxane-poly(ethylene oxide) hybrid hydrogel prepared by the sol-gel route. The aim was to control the nanostructural features of the nanocomposite, improve the release profile of the sodium diclofenac (SDCF) drug, and optimize the swelling behavior of the hydrophilic matrix. The nanoscopic characteristics of the siloxane-cross-linked poly(ethylene oxide) network, the semicrystallinity of the hybrid, and the intercalated or exfoliated structure of the clay were investigated by X-ray diffraction, small-angle X-ray scattering, and differential scanning calorimetry. The correlation between the nanoscopic features of nanocomposites containing different amounts of MMT and the swelling behavior revealed the key role of exfoliated silicate in controlling the water uptake by means of a flow barrier effect. The release of the drug from the nanocomposite displayed a stepped pattern kinetically controlled by the diffusion of SDCF molecules through the mass transport barrier created by the exfoliated silicate. The sustained SDCF release provided by the hybrid hydrogel nanocomposite could be useful for the prolonged treatment of painful conditions, such as arthritis, sprains and strains, gout, migraine, and pain after surgical procedures.
Siloxane nanoprobes for labeling and dual modality imaging of neural stem cells
Addington, Caroline P.; Cusick, Alex; Shankar, Rohini Vidya; Agarwal, Shubhangi; Stabenfeldt, Sarah E.; Kodibagkar, Vikram D.
2015-01-01
Cell therapy represents a promising therapeutic for a myriad of medical conditions, including cancer, traumatic brain injury, and cardiovascular disease among others. A thorough understanding of the efficacy and cellular dynamics of these therapies necessitates the ability to non-invasively track cells in vivo. Magnetic resonance imaging (MRI) provides a platform to track cells as a non-invasive modality with superior resolution and soft tissue contrast. We recently reported a new nanoprobe platform for cell labeling and imaging using fluorophore doped siloxane core nanoemulsions as dual modality (1H MRI/Fluorescence), dual-functional (oximetry/detection) nanoprobes. Here, we successfully demonstrate the labeling, dual-modality imaging, and oximetry of neural progenitor/stem cells (NPSCs) in vitro using this platform. Labeling at a concentration of 10 μl/104 cells with a 40%v/v polydimethylsiloxane core nanoemulsion, doped with rhodamine, had minimal effect on viability, no effect on migration, proliferation and differentiation of NPSCs and allowed for unambiguous visualization of labeled NPSCs by 1H MR and fluorescence and local pO2 reporting by labeled NPSCs. This new approach for cell labeling with a positive contrast 1H MR probe has the potential to improve mechanistic knowledge of current therapies, and guide the design of future cell therapies due to its clinical translatability. PMID:26597417
Influence of liquid phase on nanoparticle-based giant electrorheological fluid.
Gong, Xiuqing; Wu, Jinbo; Huang, Xianxiang; Wen, Weijia; Sheng, Ping
2008-04-23
We show that the chemical structures of silicone oils can have an important role in the giant electrorheological (GER) effect. The interaction between silicone oils and solid nanoparticles is found to significantly influence the ER effect. By increasing the kinematic viscosity of silicone oils, which is a function of siloxane chain length, sol-like, gel-like and clay-like appearances of the constituted ER fluids were observed. Different functional-group-terminated silicone oils were also employed as the dispersing media. Significant differences of yield stress were found. We systematically study the effect of siloxane chain lengths on the permeability of oils traveling through the porous spaces between the particles (using the Washburn method), oils adsorbed on the particles' surface (using FT-IR spectra), as well as their particle size distribution (using dynamic light scattering). Our results indicate the hydrogen bonds are instrumental in linking the silicone oil to GER solid particles, and long chain lengths can enhance the agglomeration of the GER nanoparticles to form large clusters. An optimal oil structure, with hydroxyl-terminated silicone oil and a suitable viscosity, was chosen which can create the highest yield stress of ∼300 kPa under a 5 kV mm(-1) DC electric field.
2016-01-01
Monodisperse oligodimethylsiloxanes end-functionalized with the hydrogen-bonding ureidopyrimidinone (UPy) motif undergo phase separation between their aromatic end groups and dimethylsiloxane midblocks to form ordered nanostructures with domain spacings of <5 nm. The self-assembly behavior of these well-defined oligomers resembles that of high degree of polymerization (N)–high block interaction parameter (χ) linear diblock copolymers despite their small size. Specifically, the phase morphology varies from lamellar to hexagonal to body-centered cubic with increasing asymmetry in molecular volume fraction. Mixing molecules with different molecular weights to give dispersity >1.13 results in disorder, showing importance of molecular monodispersity for ultrasmall ordered phase separation. In contrast, oligodimethylsiloxanes end-functionalized with an O-benzylated UPy derivative self-assemble into lamellar nanostructures regardless of volume fraction because of the strong preference of the end groups to aggregate in a planar geometry. Thus, these molecules display more classically liquid-crystalline self-assembly behavior where the lamellar bilayer thickness is determined by the siloxane midblock. Here the lamellar nanostructure is tolerant to molecular polydispersity. We show the importance of end groups in high χ–low N block molecules, where block-copolymer-like self-assembly in our UPy-functionalized oligodimethylsiloxanes relies upon the dominance of phase separation effects over directional end group aggregation. PMID:27054381
Characterization of 3-Aminopropyl Oligosilsesquioxane.
Dimzon, Ian Ken D; Frömel, Tobias; Knepper, Thomas P
2016-05-03
The synthesis routes in the production of polysilsesquioxanes have largely relied upon in situ formations. This perspective often leads to polymers in which their basic structures including molecular weight and functionality are unknown [ Lichtenhan , J. D. ; et al. Silsesquioxane-siloxane copolymers from polyhedral silsesquioxanes Macromolecules , 1993 , 26 , 2141 - 2142 , http://dx.doi.org/10.1021/ma0060a053 ]. For a better understanding of the polysilsesquioxane properties and applications, there is a need to develop more techniques to enable their chemical characterization. An innovative method was developed to determine the molecular weight distribution (MWD) of an oligosilsesquioxane synthesized in-house from (3-aminopropyl)triethoxysilane. This method, which can be applied to other silsesquioxanes, siloxanes, and similar oligomers and polymers, involved separation using high performance liquid chromatography (HPLC) and detection using mass spectrometry (MS) with electrospray ionization (ESI). The novelty of the method lies on the unique determination of the absolute concentrations of the individual homologues present in the sample formulation. The use of absolute concentrations is necessary in estimating the MWD of the formulation when relative percentage, which is based solely on mass spectral ion intensities, becomes irrelevant due to the disproportionate response factors of the homologues. Determination of absolute concentration requires the use of single-homologue calibration standards. Because of commercial unavailability, these standards were prepared by efficient fractionation of the original formulation.
Takahashi, Hidekazu; Finger, Werner J; Kurokawa, Rie; Furukawa, Masae; Komatsu, Masashi
2010-03-01
To determine the sulcus penetration ability of hydrophilic and hydrophobic polyvinyl siloxane (PVS) impression materials by impression technique, temperature, and sulcus width. Hydrophilic Flexitime (FLE; Heraeus Kulzer) and its hydrophobic counterpart (EXP) without surfactant were investigated, using light (L), monophase (M), and heavy (H) consistencies. A truncated steel cone surrounded by a 2-mm-deep and 50-, 100-, or 200-microm-wide sulcus, simulating the gingival tissue with agar, served as the test model. Impressions were made with single-mix (L or M) and double-mix (LM or LH) techniques at 23 degrees C and 37 degrees C, respectively. The reproduced sulcus heights were measured with a 3D laser scanner. Data were analyzed by ANOVA and Tukey HSD (P < .05). Irrespective of sulcus widths and temperature FLE-L penetrated deepest (> 1.9 mm); FLE-M, -LM, and-LH reproductions were shorter with narrow sulci. Reproductions of 50- and 100-microm sulci with EXP-L were shallower than with FLE-L. The shortest reproduction was, however, greater than 1.6 mm. In spite of some significant differences found in sulcus-reproducing ability with hydrophilic and hydrophobic impression materials applied at different impression-making temperatures and with different techniques, the practical relevance is limited.
Selectivity and resistance to poisons of commercial hydrogen sensors
Palmisano, V.; Weidner, E.; Boon-Brett, L.; ...
2015-03-20
The resistance of several models of catalytic, workfunction-based metal-oxide-semiconductor and electrochemical hydrogen sensors to chemical contaminants such as SO 2, H 2S, NO 2 and hexamethyldisiloxane (HMDS) has been investigated. These sensor platforms are among the most commonly used for the detection of hydrogen. The evaluation protocols were based on the methods recommended in the ISO 26142:2010 standard. Permanent alteration of the sensor response to the target analyte (H 2) following exposure to potential poisons at the concentrations specified in ISO 26142 was rarely observed. Although a shift in the baseline response was often observed during exposure to the potentialmore » poisons, only in a few cases did this shift persist after removal of the contaminants. Overall, the resistance of the sensors to poisoning was good. However, a change in sensitivity to hydrogen was observed in the electrochemical platform after exposure to NO 2 and for a catalytic sensor during exposure to SO 2. The siloxane resistance test prescribed in ISO 26142, based on exposure to 10 ppm HMDS, may possibly not properly reflect sensor robustness to siloxanes. In conclusion, further evaluation of the resistance of sensors to other Si-based contaminants and other exposure profiles (e.g., concentration, exposure times) is needed.« less
Cell adhesion and guidance by micropost-array chemical sensors
NASA Astrophysics Data System (ADS)
Pantano, Paul; Quah, Soo-Kim; Danowski, Kristine L.
2002-06-01
An array of ~50,000 individual polymeric micropost sensors was patterned across a glass coverslip by a photoimprint lithographic technique. Individual micropost sensors were ~3-micrometers tall and ~8-micrometers wide. The O2-sensitive micropost array sensors (MPASs) comprised a ruthenium complex encapsulated in a gas permeable photopolymerizable siloxane. The pH-sensitive MPASs comprised a fluorescein conjugate encapsulated in a photocrosslinkable poly(vinyl alcohol)-based polymer. PO2 and pH were quantitated by acquiring MPAS luminescence images with an epifluorescence microscope/charge coupled device imaging system. O2-sensitive MPASs displayed linear Stern-Volmer quenching behavior with a maximum Io/I of ~8.6. pH-sensitive MPASs displayed sigmoidal calibration curves with a pKa of ~5.8. The adhesion of undifferentiated rat pheochromocytoma (PC12) cells across these two polymeric surface types was investigated. The greatest PC12 cell proliferation and adhesion occurred across the poly(vinyl alcohol)-based micropost arrays relative to planar poly(vinyl alcohol)-based surfaces and both patterned and planar siloxane surfaces. An additional advantage of the patterned MPAS layers relative to planar sensing layers was the ability to direct the growth of biological cells. Preliminary data is presented whereby nerve growth factor-differentiated PC12 cells grew neurite-like processes that extended along paths defined by the micropost architecture.
Supercritical fluid processing: a new dry technique for photoresist developing
NASA Astrophysics Data System (ADS)
Gallagher-Wetmore, Paula M.; Wallraff, Gregory M.; Allen, Robert D.
1995-06-01
Supercritical fluid (SCF) technology is investigated as a dry technique for photoresist developing. Because of their unique combination of gaseous and liquid-like properties, these fluids offer comparative or improved efficiencies over liquid developers and, particularly carbon dioxide, would have tremendous beneficial impact on the environment and on worker safety. Additionally, SCF technology offers the potential for processing advanced resist systems which are currently under investigation as well as those that may have been abandoned due to problems associated with conventional developers. An investigation of various negative and positive photoresist systems is ongoing. Initially, supercritical carbon dioxide (SC CO2) as a developer for polysilane resists was explored because the exposure products, polysiloxanes, are generally soluble in this fluid. These initial studies demonstrated the viability of the SCF technique with both single layer and bilayer systems. Subsequently, the investigation focused on using SC CO2 to produce negative images with polymers that would typically be considered positive resists. Polymers such as styrenes and methacrylates were chemically modified by fluorination and/or copolymerization to render them soluble in SC CO2. Siloxane copolymers and siloxane-modified methacrylates were examined as well. The preliminary findings reported here indicate the feasibility of using SC CO2 for photoresist developing.
Design and testing of high temperature micro-ORC test stand using Siloxane as working fluid
NASA Astrophysics Data System (ADS)
Turunen-Saaresti, Teemu; Uusitalo, Antti; Honkatukia, Juha
2017-03-01
Organic Rankine Cycle is a mature technology for many applications e.g. biomass power plants, waste heat recovery and geothermal power for larger power capacity. Recently more attention is paid on an ORC utilizing high temperature heat with relatively low power. One of the attractive applications of such ORCs would be utilization of waste heat of exhaust gas of combustion engines in stationary and mobile applications. In this paper, a design procedure of the ORC process is described and discussed. The analysis of the major components of the process, namely the evaporator, recuperator, and turbogenerator is done. Also preliminary experimental results of an ORC process utilizing high temperature exhaust gas heat and using siloxane MDM as a working fluid are presented and discussed. The turbine type utilized in the turbogenerator is a radial inflow turbine and the turbogenerator consists of the turbine, the electric motor and the feed pump. Based on the results, it was identified that the studied system is capable to generate electricity from the waste heat of exhaust gases and it is shown that high molecular weight and high critical temperature fluids as the working fluids can be utilized in high-temperature small-scale ORC applications. 5.1 kW of electric power was generated by the turbogenerator.
Liang, Wuu-Jyh; Chen, Ying-Pin; Wu, Chien-Pang; Kuo, Ping-Lin
2005-12-29
The chemical-covalent polyether-siloxane hybrids (EDS) doped with various amounts of LiClO4 salt were characterized by FT-IR, DSC, TGA, and solid-state NMR spectra as well as impedance measurements. These observations indicate that different types of complexes by the interactions of Li+ and ClO4- ions are formed within the hybrid host, and the formation of transient cross-links between Li+ ions and ether oxygens results in the increase in T(g) of polyether segments and the decrease in thermal stability of hybrid electrolyte. Initially a cation complexation dominated by the oxirane-cleaved cross-link site and PEO block is present, and after the salt-doped level of O/Li+ = 20, the complexation through the PPO block becomes more prominent. Moreover, a significant degree of ionic association is examined in the polymer-salt complexes at higher salt uptakes. A VTF-like temperature dependence of ionic conductivity is observed in all of the investigated salt concentrations, implying that the diffusion of charge carrier is assisted by the segmental motions of the polymer chains. The behavior of ion transport in these hybrid electrolytes is further correlated with the interactions between ions and polymer host.
Cosmetics use and age at menopause: Is there a connection?
Chow, Erika; Mahalingaiah, Shruthi
2016-01-01
Short Narrative Abstract Cosmetics contain a vast number of chemicals, most of which are not under the regulatory purview of the Food and Drug Administration. Only a few of these chemicals have been evaluated for potential deleterious health impact – parabens, phthalates, polycyclic aromatic hydrocarbons, and siloxanes. A review of the ingredients in the best-selling and top rated products of the top beauty brands in the world, as well as a review of highlighted chemicals by non-profit environmental organizations reveal 11 chemicals and chemical families of concern: butylated hydroxyanisole/butylated hydroxytoluene, coal tar dyes, diethanolamine, formaldehyde releasing preservatives, parabens, phthalates, 1,4 dioxane, polycyclic aromatic hydrocarbons, siloxanes, talc/asbestos, and triclosan. Age at menopause can be affected by a variety of mechanisms, including endocrine disruption, failure of DNA repair, oxidative stress, shortened telomere length, and ovarian toxicity. There is a lack of available studies to make a conclusion regarding cosmetics use and age at menopause. What little data there is suggests future studies are warranted. Women with chronic and consistent use of cosmetics across their lifespan may be a population of concern. More research is required to better elucidate the relationship and time windows of vulnerability and the effects of mixtures and combinations of products on ovarian health. PMID:27545020
Kitagawa, Fumihiko; Nakagawara, Syo; Nukatsuka, Isoshi; Hori, Yusuke; Sueyoshi, Kenji; Otsuka, Koji
2015-01-01
A simple and rapid vacuum-drying modification method was applied to several neutral and charged polymers to obtain coating layers for controlling electroosmotic flow (EOF) and suppressing sample adsorption on poly(dimethyl siloxane) (PDMS)-glass hybrid microchips. In the vacuum-dried poly(vinylpyrrolidone) coating, the electroosmotic mobility (μeo) was suppressed from +2.1 to +0.88 × 10(-4) cm(2)/V·s, and the relative standard deviation (RSD) of μeo was improved from 10.2 to 2.5% relative to the bare microchannel. Among several neutral polymers, poly(vinylalcohol) (PVA) and poly(dimethylacrylamide) coatings gave more suppressed and repeatable EOF with RSDs of less than 2.3%. The vacuum-drying method was also applicable to polyanions and polycations to provide accelerated and inversed EOF, respectively, with acceptable RSDs of less than 4.9%. In the microchip electrophoresis (MCE) analysis of bovine serum albumin (BSA) in the vacuum-dried and thermally-treated PVA coating channel, an almost symmetric peak of BSA was obtained, while in the native microchannel a significantly skewed peak was observed. The results demonstrated that the vacuum-dried polymer coatings were effective to control the EOF, and reduced the surface adsorption of proteins in MCE.
Polydimethyl siloxane based nanocomposites with antibiofilm properties for biomedical applications.
Sankar, G Gomathi; Murthy, P Sriyutha; Das, Arindam; Sathya, S; Nankar, Rakesh; Venugopalan, V P; Doble, Mukesh
2017-07-01
Polydimethyl siloxane (PDMS) is an excellent implant material for biomedical applications, but often fails as it is prone to microbial colonization which forms biofilms. In the present study CuO, CTAB capped CuO, and ZnO nanoparticles were tested as nanofillers to enhance the antibiofilm property of PDMS against Staphylococcus aureus and Escherichia coli. In general S. aurues (Gram positive and more hydrophobic) favor PDMS surface than glass while E. coli (Gram negative and more hydrophilic) behaves in a reverse way. Incorporation of nanofillers renders the PDMS surface antibacterial and reduces the attachment of both bacteria. These surfaces are also not cytotoxic nor show any cell damage. Contact angle of the material and the cell surface hydrophobicity influenced the extent of bacterial attachment. Cell viability in biofilms was dependent on the antimicrobial property of the nanoparticles incorporated in the PDMS matrix. Simple regression relationships were able to predict the bacterial attachment and number of dead cells on these nanocomposites. Among the nanocomposites tested, PDMS incorporated with CTAB (cetyl trimethylammonium bromide)-capped CuO appears to be the best antibacterial material with good cyto-compatibility. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 105B: 1075-1082, 2017. © 2016 Wiley Periodicals, Inc.
Mettler, Esther; Trenkler, Anja; Feilen, Peter J; Wiegand, Frederik; Fottner, Christian; Ehrhart, Friederike; Zimmermann, Heiko; Hwang, Yong Hwa; Lee, Dong Yun; Fischer, Stefan; Schreiber, Laura M; Weber, Matthias M
2013-01-01
Islet cell transplantation is a promising option for the restoration of normal glucose homeostasis in patients with type 1 diabetes. Because graft volume is a crucial issue in islet transplantations for patients with diabetes, we evaluated a new method for increasing functional tissue yield in xenogeneic grafts of encapsulated islets. Islets were labeled with three different superparamagnetic iron oxide nano particles (SPIONs; dextran-coated SPION, siloxane-coated SPION, and heparin-coated SPION). Magnetic separation was performed to separate encapsulated islets from the empty capsules, and cell viability and function were tested. Islets labeled with 1000 μg Fe/ml dextran-coated SPIONs experienced a 69.9% reduction in graft volume, with a 33.2% loss of islet-containing capsules. Islets labeled with 100 μg Fe/ml heparin-coated SPIONs showed a 46.4% reduction in graft volume, with a 4.5% loss of capsules containing islets. No purification could be achieved using siloxane-coated SPIONs due to its toxicity to the primary islets. SPION labeling of islets is useful for transplant purification during islet separation as well as in vivo imaging after transplantation. Furthermore, purification of encapsulated islets can also reduce the volume of the encapsulated islets without impairing their function by removing empty capsules. © 2013 John Wiley & Sons A/S.
Historical Material Analysis of DC745U Pressure Pads
DOE Office of Scientific and Technical Information (OSTI.GOV)
Ortiz-Acosta, Denisse
As part of the Enhance Surveillance mission, it is the goal to provide suitable lifetime assessment of stockpile materials. This report is an accumulation of historical publication on the DC745U material and their findings. It is the intention that the B61 LEP program uses this collection of data to further develop their understanding and potential areas of study. DC745U is a commercially available silicone elastomer consisting of dimethyl, methyl-phenyl, and methyl-vinyl siloxane repeat units. Originally, this material was manufactured by Dow Corning as Silastic{reg_sign} DC745U at their manufacturing facility in Kendallville, IN. Recently, Dow Corning shifted this material to themore » Xiameter{reg_sign} brand product line. Currently, DC745U is available through Xiameter{reg_sign} or Dow Corning's distributor R. D. Abbott Company. DC745U is cured using 0.5 wt% vinyl-specific peroxide curing agent known as Luperox 101 or Varox DBPH-50. This silicone elastomer is used in numerous parts, including two major components (outer pressure pads and aft cap support) in the W80 and as pressure pads on the B61. DC745U is a proprietary formulation, thus Dow Corning provides limited information on its composition and properties. Based on past experience with Dow Corning, DC745U is at risk of formulation changes without notification to the costumer. A formulation change for DC745U may have a significant impact because the network structure is a key variable in determining material properties. The purpose of this report is to provide an overview of historical DC745U studies and identify gaps that need to be addressed in future work. Some of the previous studies include the following: 1. Spectroscopic characterization of raw gum stock. 2. Spectroscopic, thermal, and mechanical studies on cured DC745U. 3. Nuclear Magnetic Resonance (NMR) and solvent swelling studies on DC745U with different crosslink densities. 4. NMR, solvent swelling, thermal, and mechanical studies on thermally aged DC745U. 5. NMR, solvent swelling, thermal, and mechanical studies on radiolytically aged DC745U. Each area is reviewed and further work is suggested to improve our understanding of DC745U for systems engineering, surveillance, aging assessments, and lifetime assessment.« less
Negative-tone development of photoresists in environmentally friendly silicone fluids
NASA Astrophysics Data System (ADS)
Ouyang, Christine Y.; Lee, Jin-Kyun; Ober, Christopher K.
2012-03-01
The large amount of organic solvents and chemicals that are used in today's microelectronic fabrication process can lead to environmental, health and safety hazards. It is therefore necessary to design new materials and new processes to reduce the environmental impact of the lithographic process. In addition, as the feature sizes decrease, other issues such as pattern collapse, which is related to the undesirable high surface tension of the developers and rinse liquids, can occur and limit the resolution. In order to solve these issues, silicone fluids are chosen as alternative developing solvents in this paper. Silicone fluids, also known as linear methyl siloxanes, are a class of mild, non-polar solvents that are non-toxic, not ozone-depleting, and contribute little to global warming. They are considered as promising developers because of their environmental-friendliness and their unique physical properties such as low viscosity and low surface tension. Recently, there have been emerging interests in negative-tone development (NTD) due to its better ability in printing contact holes and trenches. It is also found that the performance of negative-tone development is closely related to the developing solvents. Silicone fluids are thus promising developers for NTD because of their non-polar nature and high contrast negative-tone images are expected with chemical amplification photoresists due to the high chemical contrast of chemical amplification. We have previously shown some successful NTD with conventional photoresists such as ESCAP in silicone fluids. In this paper, another commercially available TOK resist was utilized to study the NTD process in silicone fluids. Because small and non-polar molecules are intrinsically soluble in silicone fluids, we have designed a molecular glass resist for silicone fluids. Due to the low surface tension of silicone fluids, we are able achieve high aspect-ratio, high-resolution patterns without pattern collapse.
2010-11-15
alkyl-terminated, (c) photpatternable QD with siloxane inner layer and the photopolymerizable methacrylate corona. (d)-(f) Effect of irradiation on PL...cross- linked QDs (scale 10 nm). The inherent properties of photopolymerizable QDs such as their stability, PL, and ease of solution...distinctive signature of both compounds , they are easily recognizable in the CIE coordinate system given in the inset. A second inset shows an image of the
Enhancing Peripheral Nerve Regeneration with a Novel Drug Delivering Nerve Conduit
2014-10-01
tubes of the PLGA nerve conduit. A polyether sulfone (PES) filter membrane, a polydimethyl siloxane (PDMS) plug and silicone sealant (RTV silicone, Dow...harvested from chicken embryos. 1 DRG/well was plated in 24-well plates coated with laminin (1 µg/ml). Finally, different doses of NGF, GDNF and NGF...application in nerve regeneration, Biomedical Microdevices, in preparation, acknowledgement of federal support (yes) Books or other non-periodical, one
Sequential Desorption of Nitroaromatic Compounds (NAC) from Soils
2005-03-01
the soil solution . Weissmahr et al. [20] suggest an electron donor acceptor (EDA) complex between oxygens of the siloxane surface of the clays and the...release of NACs into the soil solution . At high pH values desorption is superimposed by NACs hydrolysis. Therefore, in- creasing pH values impedes the...presented demonstrate that both the cation present in the soil solution and its concentration may affect the desorption behavior of NACs in contaminated soils
Radiation Resistances of Dielectric Liquids
NASA Technical Reports Server (NTRS)
Bouquet, Frank L.; Somoano, Robert B.
1987-01-01
Report presents data on effects of ionizing radiation on dielectric liquids for high-energy-density, pulsed-power capacitors. Based on Jet Propulsion Laboratory test results, search of NASA and Department of Energy computer files, survey of open literature, and contacts with manufacturers and suppliers. Covers 22 organic liquids, although detailed data found for only one compound, polydimethyl siloxane. Generic data on effects of radiation on compounds with similar chemical structures provided where data on specific compounds lacking.
NASA Astrophysics Data System (ADS)
Urbaniak, Daniel J.
2004-11-01
In the research reported here, the surface modification of medical grade poly(dimethyl siloxane), polyetherurethane, and stainless steel through gamma-radiation grafting of hydrophilic polymers was investigated. Emphasis was placed on developing improved and simplified surface modification methods that produce more stable and more bioacceptible hydrophilic graft surfaces. As a result of this research, new surface modification techniques were developed that yield significantly improved surface stability unachievable using previous surface modification techniques. The surface modification of poly(dimethyl siloxane) with hydrophilic polymers was carried out using gamma radiation initiated graft polymerization. The addition of alkali metal hydroxides afforded a unique way to enhance the grafting of N-vinyl-2 pyrrolidone, dimethylacryamide, 2-methacryloyloxyethyl phosphoryl choline, N,N-dimethyl-N-(methacryloyloxyethyl)-N-(3-sulfopropyl)-ammonium-betaine, N,N-dimethyl-N-(methacrylamidopropyl)-N-(3-sulfopropyl)-ammonium-betaine, and copolymers thereof to silicones. Ethanolamine was found to further enhance the grafting of some hydrophilic polymers to silicone. The resulting hydrophilic surface grafts were resistant to hydrophobic surface rearrangement. This process overcomes previous problems inherent in silicone surface modification. The technique was also found to moderately enhance the grafting of hydrophilic monomers to polyetherurethane and to 316-L stainless steel. The surface modification of 316-L stainless steel was further enhanced by treating the substrates with a chromium III methacrylate bonding agent prior to irradiation. The coatings were evaluated for their potential use as depots for delivering therapeutic agents. The release of ofloxacin from surface-modified poly(dimethyl siloxane) and dexamethasone from surface-modified 316-L stainless steel was evaluated by in-vitro experiments. Therapeutic levels of drugs were released from surface-modified specimens via a burst effect. Improved surface characterization methods were another aspect of this research. New nanomechanical testing techniques were developed and used to evaluate the viscoelastic surface mechanical properties of low modulus surface-modified specimens. Dynamic nanoindentation characterization techniques were designed to measure the storage modulus and loss modulus of compliant viscoelastic substrate surfaces. The results of these experiments were compared with modulus data obtained by conventional dynamic mechanical spectroscopy. Nanoscratch testing methods were also developed that qualitatively compared the abrasion resistance of surface-modified substrates. (Abstract shortened by UMI.)
NASA Astrophysics Data System (ADS)
Kusada, Kentaro
The objective of this study is to evaluate corrosion resistance and durability of siloxane ceramic/polymer films for aluminum alloys in marine environments. Al5052-H3 and Al6061-T6 were selected as substrates, and HCLCoat11 and HCLCoat13 developed in the Hawaii Corrosion Laboratory were selected for the siloxane ceramic/polymer coatings. The HCLCoat11 is a quasi-ceramic coating that has little to no hydrocarbons in its structure. The HCLCoat13 is formulated to incorporate more hydrocarbons to improve adhesion to substrate surfaces with less active functionalities. In this study, two major corrosion evaluation methods were used, which were the polarization test and the immersion test. The polarization tests provided theoretical corrosion rates (mg/dm 2/day) of bare, HCLCoat11-coated, and HCLCoat13-coated aluminum alloys in aerated 3.15wt% sodium chloride solution. From these results, the HCLCoat13-coated Al5052-H3 was found to have the lowest corrosion rate which was 0.073mdd. The next lowest corrosion rate was 0.166mdd of the HCLCoat11-coated Al5052-H3. Corrosion initiation was found to occur at preexisting breaches (pores) in the films by optical microscopy and SEM analysis. The HCLCoat11 film had many preexisting breaches of 1-2microm in diameter, while the HCLCoat13 film had much fewer preexisting breaches of less than 1microm in diameter. However, the immersion tests showed that the seawater immersion made HCLCoat13 film break away while the HCLCoat11 film did not apparently degrade, indicating that the HCLCoat11 film is more durable against seawater than the HCLCoat13. Raman spectroscopy revealed that there was some degradation of HCLCoat11 and HCLCoat13. For the HCLCoat11 film, the structure relaxation of Si-O-Si linkages was observed. On the other hand, seawater generated C-H-S bonds in the HCLCoat13 film resulting in the degradation of the film. In addition, it was found that the HCLCoat11 coating had anti-fouling properties due to its high water contact angle. As candidate materials for a marine construction (e.g. the heat exchangers for ocean thermal energy conversion (OTEC) plants), the HCLCoat11-coated Al5052-H3 proved to be a durable, corrosion resistant combination with anti-fouling characteristics.
1985-05-01
OK 3-600 IV -5 D. ELECTRON-BEAM (EB) CURABLE "OATINGS These coatings are formed by curing or crosslinking a complex mixture of multifunctional acrylic ...1. 8p. Cooper, B.E., D.W. Butler, inventors; Dow Coming Corp., assignee. Curable siloxane resin coating composition. EP patent 048,114. (1982) March...limit use in the water-prone firefighters environment. We believe other high-temperature melting resins , such as polysulfone or polyether-imide, would
Yamada, Shinya; Maeda, Hirotaka; Obata, Akiko; Lohbauer, Ulrich; Yamamoto, Akiko; Kasuga, Toshihiro
2013-12-12
Poly(l-lactic acid)-based films which include 60 wt % of vaterite (V) or siloxane-containing vaterite (SiV) were coated on a pure magnesium substrate, denoted by PLLA/V or PLLA/SiV, respectively, to suppress early corrosion and improve its cytocompatibility. Both coating films adhered to the Mg substrate with 2.3-2.8 MPa of tensile bonding strength. Soaking test for 7 days in α-modified minimum essential medium revealed that the morphological instability of the PLLA/V film caused a higher amount of Mg 2+ ion to be released from the coating sample. On the other hand, in the case of the coating with the PLLA/SiV film, no morphological change even after the soaking test was observed, owing to the suppression of the degradation rate. In cell culture tests, the proliferation of mouse osteoblast-like cell (MC3T3-E1) was significantly enhanced by both coatings, in comparison with the uncoated magnesium substrate. The cell morphology revealed that a few less-spread cells were observed on the PLLA/V film, while more elongated cells were done on the PLLA/SiV film. The cells on the PLLA/SiV film exhibited an extremely higher alkaline phosphatase activity after 21 days of incubation than that on the PLLA/V one. The PLLA/SiV film suppressed the early corrosion and enhanced cytocompatibility on metallic magnesium.
Quantum Dot/Siloxane Composite Film Exceptionally Stable against Oxidation under Heat and Moisture.
Kim, Hwea Yoon; Yoon, Da-Eun; Jang, Junho; Lee, Daewon; Choi, Gwang-Mun; Chang, Joon Ha; Lee, Jeong Yong; Lee, Doh C; Bae, Byeong-Soo
2016-12-21
We report on the fabrication of a siloxane-encapsulated quantum dot (QD) film (QD-silox film), which exhibits stable emission intensity for over 1 month even at elevated temperature and humidity. QD-silox films are solidified via free radical addition reaction between oligosiloxane resin and ligand molecules on QDs. We prepare the QD-oligosiloxane resin by sol-gel condensation reaction of silane precursors with QDs blended in the precursor solution, forgoing ligand-exchange of QDs. The resulting QD-oligosiloxane resin remains optically clear after 40 days of storage, in contrast to other QD-containing resins which turn turbid and ultimately form sediments. QDs also disperse uniformly in the QD-silox film, whose photoluminescence (PL) quantum yield (QY) remains nearly unaltered under harsh conditions; for example, 85 °C/5% relative humidity (RH), 85 °C/85% RH, strongly acidic, and strongly basic environments for 40 days. The QD-silox film appears to remain equally emissive even after being immersed into boiling water (100 °C). Interestingly, the PL QY of the QD-silox film noticeably increases when the film is exposed to a moist environment, which opens a new, facile avenue to curing dimmed QD-containing films. Given its excellent stability, we envision that the QD-silox film is best suited in display applications, particularly as a PL-type down-conversion layer.
Birdilla Selva Donio, Mariathason; Chelladurai Karthikeyan, Subbiahanadar; Michaelbabu, Mariavincent; Uma, Ganapathi; Raja Jeya Sekar, Ramaiyan; Citarasu, Thavasimuthu
2018-05-18
Bioemulsifier (BE)-producing Haererehalobacter sp. JS1 was isolated and identified from the solar salt works in India. The BE was extracted, purified, and characterized by Gas Chromatography-Mass Spectrometry (GC-MS) analysis. Emulsification activity was performed against different oils and dye degradation potential against different dyes. The production of BE was optimized using different carbon sources (C), nitrogen sources (N), pH, and NaCl. BE screening methods revealed that, Haererehalobacter sp. JS1 was highly positive BE production. Identification by 16S rRNA sequencing and analyses was found that, the Haererehalobacter sp. JS1 was closely related to Salinicoccus halophilus and Haererehalobacter sp. The structural characterization analysis confirmed that the partially purified bioemulsifier belongs to siloxane-type. Emulsification activity (E24) revealed that the bioemulsifier significantly (p < = 0.001) emulsified the commercial oils including coconut oil, gingelly oil, olive oil, and palmolein oils. Haererehalobacter sp. JS1 also significantly (p < = 0.001) degraded the dyes such as orange MR, direct violet, cotton red, reactive yellow, nitro green, and azo dye. RSM regression co-efficient and contour plot analysis clearly indicated that the combination of pH and NaCl helped to increase BE production. Siloxane-type of BE obtained from Haererehalobacter sp. JS1 was able to emulsify different oils and commercial dyes. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Influence of tray rigidity and impression technique on accuracy of polyvinyl siloxane impressions.
Hoyos, Alex; Soderholm, Karl-Johan
2011-01-01
The aim of this study was to determine how tray rigidity and impression technique affect the accuracy of polyvinyl siloxane impressions. Disposable plastic trays and metallic Rim-Lock trays were used in combination with a heavy/light body technique or with two different putty-wash techniques. For each technique-tray combination, 10 impressions were made of a master cast with two steel abutments representing the mandibular right first premolar and second molar, between which a steel rod was placed at the ridge level. Each steel abutment had five marks, while the steel rod in between the two abutments had only one mark, which served as a reference point. With a universal measuring microscope, the x-, y-, and z-coordinates were recorded for each mark on the master cast and impressions. The distances between the different marks and the reference point on the impressions were calculated and compared with those of the master cast. All techniques used with the plastic trays had distances that were significantly different from the master cast (P < .05), while for the metal trays, it was only the heavy/light body technique that resulted in distances that were significantly different from the master cast (P < .05). Plastic trays produced less accurate impressions than metal trays. When metal trays were used, putty-based impressions were dimensionally better than heavy/light body impressions.
1988-05-13
Encapsulants H6rnig, Jahanna Kron and Wolfgang Hepp 2:40 B41 Recent Advances in Organosiloxane Copolymers 3:00 BREAK James E. McGrath New Developments in the...Mobility of H2 ontaining Oligomeric Siloxanes by Si-NMR S 10:10 B48 Syntheses and Reactions N. Heo, R. Krause and R. Kos- of Uniform Size Poly...Technical University Graz Stremayrgasse 16 A-8010 Graz, Austria Kirsten Hinrichs Department of Chemistry University of Wisconsin-Madison Wolfgang
DOE Office of Scientific and Technical Information (OSTI.GOV)
Doherty, Mark Daniel; O'Brien, Michael Joseph; Lee, Jason
A compound represented by the following formula is provided: ##STR00001## Also provided is a solution including a compound disclosed herein, a volume of dense carbon dioxide (CO.sub.2), and a co-solvent, where the solution has an increased viscosity greater than the viscosity of dense CO.sub.2. Methods of increasing the viscosity of dense CO.sub.2 and natural gas liquids (NGLs) by, for example, dissolving a compound disclosed herein to form a solution, are also provided.
Cardiano, P; Sergi, S; Triscari, M; Piraino, P
2001-01-01
The effectiveness, as preserving agents, of a series of chemical compounds (silanes, siloxanes, epoxides, perfluoropolyethers, acrylates, acrylsilicones) has been tested on lithic materials mainly used in artistic stoneworks of north-eastern Sicily. The selection and classification of the stone types, based on geomineralogical criteria follows a brief excursus about their use as artistic materials. The results of the porosimetric investigations, before and after conservation treatments, are reported. In addition, polarizing mineralogical microscope photos of the studied lithoid materials are presented.
Marks, Daniel L; Oldenburg, Amy L; Reynolds, J Joshua; Boppart, Stephen A
2003-01-10
The resolution of optical coherence tomography (OCT) often suffers from blurring caused by material dispersion. We present a numerical algorithm for computationally correcting the effect of material dispersion on OCT reflectance data for homogeneous and stratified media. This is experimentally demonstrated by correcting the image of a polydimethyl siloxane microfludic structure and of glass slides. The algorithm can be implemented using the fast Fourier transform. With broad spectral bandwidths and highly dispersive media or thick objects, dispersion correction becomes increasingly important.
NASA Astrophysics Data System (ADS)
Marks, Daniel L.; Oldenburg, Amy L.; Reynolds, J. Joshua; Boppart, Stephen A.
2003-01-01
The resolution of optical coherence tomography (OCT) often suffers from blurring caused by material dispersion. We present a numerical algorithm for computationally correcting the effect of material dispersion on OCT reflectance data for homogeneous and stratified media. This is experimentally demonstrated by correcting the image of a polydimethyl siloxane microfludic structure and of glass slides. The algorithm can be implemented using the fast Fourier transform. With broad spectral bandwidths and highly dispersive media or thick objects, dispersion correction becomes increasingly important.
NASA Materials Research for Extreme Conditions
NASA Technical Reports Server (NTRS)
Sharpe, R. J.; Wright, M. D.
2009-01-01
This Technical Memorandum briefly covers various innovations in materials science and development throughout the course of the American Space program. It details each innovation s discovery and development, explains its significance, and describes the applications of this material either in the time period discovered or today. Topics of research include silazane polymers, solvent-resistant elastomeric polymers (polyurethanes and polyisocyanurates), siloxanes, the Space Shuttle thermal protection system, phenolic-impregnated carbon ablator, and carbon nanotubes. Significance of these developments includes the Space Shuttle, Apollo programs, and the Constellation program.
A radiograph positioning technique to evaluate prosthetic misfit and bone loss around implants.
Lin, Kevin C; Wadhwani, Chandur P K; Sharma, Arun; Finzen, Frederick
2014-02-01
A radiograph positioning device was developed to fit with commercially available film holders and implant systems. The device is indexed to the dental implant body and the adjacent dentition by using an implant placement driver and polyvinyl siloxane occlusal registration material. By fitting the device to a conventional film holder, accurate orthogonal radiographs can monitor changes in bone architecture and prosthetic misfit. Copyright © 2014 Editorial Council for the Journal of Prosthetic Dentistry. Published by Mosby, Inc. All rights reserved.
Farah, Ra'fat I; Alshabi, Abdullah M
2016-09-01
This report describes a straightforward technique for verifying the accuracy of a definitive cast by using a maximal intercuspation record fabricated from polyvinyl siloxane occlusal registration material. This precise verification method detects inaccurate casts before the dental prosthesis is fabricated, thus saving chairside and laboratory time while reducing the number of costly prosthesis remakes. Copyright © 2016 Editorial Council for the Journal of Prosthetic Dentistry. Published by Elsevier Inc. All rights reserved.
Polyimide foam for the thermal insulation and fire protection
NASA Technical Reports Server (NTRS)
Rosser, R. W. (Inventor)
1973-01-01
The preparation of chemically resistant and flame retardant foams from polyfunctional aromatic carboxylic acid derivatives and organic polyisocyanates is outlined. It was found that polyimide foams of reproducible density above 1 lb./ft. and below 6 lbs./cu ft. can be obtained by employing in the reaction of least 2% by weight of siloxane-glycol copolymer as a surfactant which acts as a specific density control agent. Polyimide foams into which reinforcing fibers such as silicon dioxide and carbon fibers may be incorporated were also produced.
Photocatalytic Nanocomposites for the Protection of European Architectural Heritage.
Gherardi, Francesca; Roveri, Marco; Goidanich, Sara; Toniolo, Lucia
2018-01-03
In the field of stone protection, the introduction of inorganic nanoparticles, such as TiO₂, ZnO, and Ag in polymeric blends can enhance the protective action of pristine treatments, as well as confer additional properties (photocatalytic, antifouling, and antibacterial). In the framework of the "Nano-Cathedral" European project, nanostructured photocatalytic protective treatments were formulated by using different TiO₂ nanoparticles, solvents, and silane/siloxane systems in the blends. The results about the characterization and application of two promising nano-TiO₂ based products applied on Apuan marble and Ajarte limestone are here reported, aiming at investigating the complex system "treatment/stone-substrate". The nanocomposites show better performances when compared to a commercial reference siloxane based protective treatment, resulting in different performances once applied on different carbonatic substrates, with very low and high open porosity, confirming the necessity of correlating precisely the characteristics of the stone material to those of the protective formulations. In particular, the TiO₂ photocatalytic behavior is strictly linked to the amount of available nanoparticles and to the active surface area. The alkyl silane oligomers of the water-based formulation have a good penetration into the microstructure of Ajarte limestone, whereas the solvent-based and small size monomeric formulation shows better results for Apuan marble, granting a good coverage of the pores. The encouraging results obtained so far in lab will be confirmed by monitoring tests aiming at assessing the effectiveness of the treatments applied in pilot sites of historical Gothic Cathedrals.
Poly(dimethyl siloxane) surface modification with biosurfactants isolated from probiotic strains.
Pinto, S; Alves, P; Santos, A C; Matos, C M; Oliveiros, B; Gonçalves, S; Gudiña, E; Rodrigues, L R; Teixeira, J A; Gil, M H
2011-09-15
Depending on the final application envisaged for a given biomaterial, many surfaces must be modified before use. The material performance in a biological environment is mainly mediated by its surface properties that can be improved using suitable modification methods. The aim of this work was to coat poly(dimethyl siloxane) (PDMS) surfaces with biosurfactants (BSs) and to evaluate how these compounds affect the PDMS surface properties. BSs isolated from four probiotic strains (Lactococcus lactis, Lactobacillus paracasei, Streptococcus thermophilus A, and Streptococcus thermophilus B) were used. Bare PDMS and PDMS coated with BSs were characterized by contact angle measurements, infrared spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM). The influence of the surface modifications on the materials blood compatibility was studied through thrombosis and hemolysis assays. The cytotoxicity of these materials was tested against rat peritoneal macrophages. AFM results demonstrated the successful coating of the surfaces. Also, by contact angle measurements, an increase of the coated surfaces hydrophilicity was seen. Furthermore, XPS analysis indicated a decrease of the silicon content at the surface, and ATR-FTIR results showed the presence of BS characteristic groups as a consequence of the modification. All the studied materials revealed no toxicity and were found to be nonhemolytic. The proposed approach for the modification of PDMS surfaces was found to be effective and opens new possibilities for the application of these surfaces in the biomedical field. Copyright © 2011 Wiley Periodicals, Inc.
Yamada, Shinya; Maeda, Hirotaka; Obata, Akiko; Lohbauer, Ulrich; Yamamoto, Akiko; Kasuga, Toshihiro
2013-01-01
Poly(l-lactic acid)-based films which include 60 wt % of vaterite (V) or siloxane-containing vaterite (SiV) were coated on a pure magnesium substrate, denoted by PLLA/V or PLLA/SiV, respectively, to suppress early corrosion and improve its cytocompatibility. Both coating films adhered to the Mg substrate with 2.3–2.8 MPa of tensile bonding strength. Soaking test for 7 days in α-modified minimum essential medium revealed that the morphological instability of the PLLA/V film caused a higher amount of Mg2+ ion to be released from the coating sample. On the other hand, in the case of the coating with the PLLA/SiV film, no morphological change even after the soaking test was observed, owing to the suppression of the degradation rate. In cell culture tests, the proliferation of mouse osteoblast-like cell (MC3T3-E1) was significantly enhanced by both coatings, in comparison with the uncoated magnesium substrate. The cell morphology revealed that a few less-spread cells were observed on the PLLA/V film, while more elongated cells were done on the PLLA/SiV film. The cells on the PLLA/SiV film exhibited an extremely higher alkaline phosphatase activity after 21 days of incubation than that on the PLLA/V one. The PLLA/SiV film suppressed the early corrosion and enhanced cytocompatibility on metallic magnesium. PMID:28788425
Photocatalytic Nanocomposites for the Protection of European Architectural Heritage
Roveri, Marco; Goidanich, Sara; Toniolo, Lucia
2018-01-01
In the field of stone protection, the introduction of inorganic nanoparticles, such as TiO2, ZnO, and Ag in polymeric blends can enhance the protective action of pristine treatments, as well as confer additional properties (photocatalytic, antifouling, and antibacterial). In the framework of the “Nano-Cathedral” European project, nanostructured photocatalytic protective treatments were formulated by using different TiO2 nanoparticles, solvents, and silane/siloxane systems in the blends. The results about the characterization and application of two promising nano-TiO2 based products applied on Apuan marble and Ajarte limestone are here reported, aiming at investigating the complex system “treatment/stone-substrate”. The nanocomposites show better performances when compared to a commercial reference siloxane based protective treatment, resulting in different performances once applied on different carbonatic substrates, with very low and high open porosity, confirming the necessity of correlating precisely the characteristics of the stone material to those of the protective formulations. In particular, the TiO2 photocatalytic behavior is strictly linked to the amount of available nanoparticles and to the active surface area. The alkyl silane oligomers of the water-based formulation have a good penetration into the microstructure of Ajarte limestone, whereas the solvent-based and small size monomeric formulation shows better results for Apuan marble, granting a good coverage of the pores. The encouraging results obtained so far in lab will be confirmed by monitoring tests aiming at assessing the effectiveness of the treatments applied in pilot sites of historical Gothic Cathedrals. PMID:29301338
Reactive Molecular Dynamics Investigations of Alkoxysilane Sol-Gel and Surface Coating Processes
NASA Astrophysics Data System (ADS)
Deetz, Joshua David
The ability to generate nanostructured materials with tailored morphology or chemistry is of great technological interest. One proven method of generating metal-oxide materials, and chemically modifying metal-oxide surfaces is through the reactions of molecular building blocks known as alkoxysilanes. Alkoxysilanes are a class of chemicals which contain one or more organic alkoxy groups bonded to silicon atoms. Alkoxysilane (Si-O-R) chemical groups can undergo reactions to form bridges (Si-O-M) with metal oxides. Due to their ability to "attach" to metal-oxides through condensation reactions, alkoxysilanes have a number of interesting applications, such as: the generation of synthetic siloxane materials through the sol-gel process, and the formation of functionalized surface coatings on metal-oxide surfaces. Despite widespread study of sol-gel and surface coatings processes, it is difficult to predict the morphology of the final products due to the large number of process variables involved, such as precursor molecule structure, solvent effects, solution composition, temperature, and pH. To determine the influence of these variables on the products of sol-gel and coatings processes reactive molecular dynamics simulations are used. A reactive force field was used (ReaxFF) to allow the chemical bonds in simulation to dynamically form and break. The force field parameters were optimized using a parallel optimization scheme with a combination of experimental information, and density functional theory calculations. Polycondensation of alkoxysilanes in mixtures of alcohol and water were studied. Steric effects were observed to influence the rates of hydrolysis and condensation in solutions containing different precursor monomers. By restricting the access of nucleophiles to the central silicon atom, the nucleation rate of siloxanes can be controlled. The influence of solution precursor, water, and methanol composition on reaction rates was explored. It was determined that the rate of alkoxysilane hydrolysis is strongly dependent on the concentration of water. The dynamics of siloxane cluster formation are revealed, which provides insight for experimentalists. The silanization of hydroxylated silica surfaces by alkoxysilanes was modeled in pseudo-infinite liquid solution. Butyl-, octyl-, or dodecylsilanes were exposed to hydroxylated silica surfaces in order to observe the influence of silyl headgroup size on the morphology and formation kinetics of silane films on silica substrates. The radius of gyration and order parameter of the hydrocarbon silyl groups were found to increase with grafting density. This was the first simulation study of the dynamic grafting of alkoxysilanes to a substrate.
Siloxane containing addition polyimides. II - Acetylene terminated polyimides
NASA Technical Reports Server (NTRS)
Maudgal, S.; St. Clair, T. L.
1984-01-01
Acetylene terminated polyimide oligomers having a range of molecular weights have been synthesized by reacting bis (gamma-aminopropyl) tetramethyldisiloxane, aminophenylacetylene and 3, 3', 4, 4' benzophenonetetracarboxylic dianhydride in different molar ratios. The prepolymers were isolated and characterized for melt flow and cure properties. They show promise as adhesives for bonding titanium to titanium and as matrix resins for graphite cloth reinforced composites. The most promising system has been blended in varying proportions with Thermid 600, a commercially available acetylene terminated polyimide oligomer, and the mixtures have been tested for application as composite matrix resins.
Siloxane containing addition polyimides
NASA Technical Reports Server (NTRS)
Maudgal, S.; St. Clair, T. L.
1984-01-01
Addition polyimide oligomers have been synthesized from bis(gamma-aminopropyl) tetramethyldisiloxane and 3, 3', 4, 4'-benzophenonetetracarboxylic dianhydride using a variety of latent crosslinking groups as endcappers. The prepolymers were isolated and characterized for solubility (in amide, chlorinated and ether solvents), melt flow and cure properties. The most promising systems, maleimide and acetylene terminated prepolymers, were selected for detailed study. Graphite cloth reinforced composites were prepared and properties compared with those of graphite/Kerimid 601, a commercially available bismaleimide. Mixtures of the maleimide terminated system with Kerimid 601, in varying proportions, were also studied.
Lee, Min Wook; An, Seongpil; Jo, Hong Seok; Yoon, Sam S; Yarin, Alexander L
2015-09-09
The present work aims at development of self-healing materials capable of partially restoring their mechanical properties under the conditions of prolonged periodic loading and unloading, which is characteristic, for example, of aerospace applications. Composite materials used in these and many other applications frequently reveal multiple defects stemming from their original inhomogeneity, which facilitates microcracking and delamination at ply interfaces. Self-healing nanofiber mats may effectively prevent such damage without compromising material integrity. Two types of core-shell nanofibers were simultaneously electrospun onto the same substrate in order to form a mutually entangled mat. The first type of core-shell fibers consisted of resin monomer (dimethylsiloxane) within the core and polyacrylonitrile within the shell. The second type of core-shell nanofibers consisted of cure (dimethyl-methyl hydrogen-siloxane) within the core and polyacrylonitrile within the shell. These mutually entangled nanofiber mats were used for tensile testing, and they were also encased in polydimethylsiloxane to form composites that were also subsequently subjected to tensile testing. During tensile tests, the nanofibers can be damaged in stretching up to the plastic regime of deformation. Then, the resin monomer and cure was released from the cores and the polydimethylsiloxane resin was polymerized, which might be expected to result in the self-healing properties of these materials. To reveal and evaluate the self-healing properties of the polyacrylonitrile-resin-cure nanofiber mats and their composites, the results were compared to the tensile test results of the monolithic polyacrylonitrile nanofiber mats or composites formed by encasing polyacrylonitrile nanofibers in a polydimethylsiloxane matrix. The latter do not possess self-healing properties, and indeed, do not recover their mechanical characteristics, in contrast to the polyacrylonitrile-resin-cure nanofiber mats and the composites reinforced by such mats. This is the first work, to the best of our knowledge, where self-healing nanofibers and composites based on them were developed, tested, and revealed restoration of mechanical properties (stiffness) in a 24 h rest period at room temperature.
Comparison of Fit of Dentures Fabricated by Traditional Techniques Versus CAD/CAM Technology.
McLaughlin, J Bryan; Ramos, Van; Dickinson, Douglas P
2017-11-14
To compare the shrinkage of denture bases fabricated by three methods: CAD/CAM, compression molding, and injection molding. The effect of arch form and palate depth was also tested. Nine titanium casts, representing combinations of tapered, ovoid, and square arch forms and shallow, medium, and deep palate depths, were fabricated using electron beam melting (EBM) technology. For each base fabrication method, three poly(vinyl siloxane) impressions were made from each cast, 27 dentures for each method. Compression-molded dentures were fabricated using Lucitone 199 poly methyl methacrylate (PMMA), and injection molded dentures with Ivobase's Hybrid Pink PMMA. For CAD/CAM, denture bases were designed and milled by Avadent using their Light PMMA. To quantify the space between the denture and the master cast, silicone duplicating material was placed in the intaglio of the dentures, the titanium master cast was seated under pressure, and the silicone was then trimmed and recovered. Three silicone measurements per denture were recorded, for a total of 243 measurements. Each silicone measurement was weighed and adjusted to the surface area of the respective arch, giving an average and standard deviation for each denture. Comparison of manufacturing methods showed a statistically significant difference (p = 0.0001). Using a ratio of the means, compression molding had on average 41% to 47% more space than injection molding and CAD/CAM. Comparison of arch/palate forms showed a statistically significant difference (p = 0.023), with shallow palate forms having more space with compression molding. The ovoid shallow form showed CAD/CAM and compression molding had more space than injection molding. Overall, injection molding and CAD/CAM fabrication methods produced equally well-fitting dentures, with both having a better fit than compression molding. Shallow palates appear to be more affected by shrinkage than medium or deep palates. Shallow ovoid arch forms appear to benefit from the use of injection molding compared to CAD/CAM and compression molding. © 2017 by the American College of Prosthodontists.
Rampazzi, Vincent; Roger, Julien; Amardeil, Régine; Penouilh, Marie-José; Richard, Philippe; Fleurat-Lessard, Paul; Hierso, Jean-Cyrille
2016-11-07
A smart steric control of the metallocene backbone in bis- and poly(phosphino)ferrocene ligands favors intramolecular aurophilic interactions between [AuCl] fragments in polynuclear gold(I) complexes. We synthesized and characterized by multinuclear NMR and X-ray diffraction analysis mono-, di-, and polynuclear gold complexes of constrained ferrocenyl diphosphines, which bear either bulky tert-butyl groups or more flexible siloxane substituents at the cyclopentadienyl rings. The complexes meso-1,1'-bis(diphenylphosphino)-3,3'-di-tert-butylferrocene (4-m), rac-1,1'-bis[bis(5-methyl-2-furyl)phosphino]-3,3'-di-tert-butylferrocene (5-r), and rac-1,1'-bis(diphenylphosphino)-3,3'-bis[(tri-iso-propylsilyl)oxy]ferrocene (6-r) were used to form dinuclear gold complexes. Coordination of tert-butylated ferrocenyl phosphines generated aurophilic interactions in the corresponding dinuclear gold complexes, contrary to gold(I) complexes reported with 1,1'-bis(diphenylphosphino)ferrocene. The structurally related tetraphosphine 1,1',2,2'-tetrakis(diphenylphosphino)-4,4'-di-tert-butylferrocene (11) also gave access to mononuclear, dinuclear, and the original trinuclear gold chloride aurophilic complexes in which 14e - to 16e - gold centers coexist. In such complexes, nonbonded ("through-space") 31 P- 31 P' nuclear spin couplings were evidenced by high-resolution NMR. In these interactions nuclear spin information is transferred between the lone-pair electron of an uncoordinated phosphorus P and a phosphorus P' that is involved in a σ covalent bond Au-P'. The dinuclear aurophilic complex displayed a concerted shuttling of its [ClAu···AuCl] fragment between the four phosphorus donors of the tetraphosphine ligand. Thus, an aurophilic Au···Au bond, which is assumed to be a weak energy interaction, can be conserved within a dynamic shuttling process at high temperature involving an intramolecular coordination-decoordination process of digold(I) at phosphorus atoms.
New Approaches to Waterproofing of Space Shuttle Insulating Materials
NASA Technical Reports Server (NTRS)
Blum, Yigal D.; Johnson, Sylvia M.; Chen, Paul
1997-01-01
Future reusable space vehicles will be in service much more frequently than current space shuttles. Therefore, rapid reconditioning of spacecraft will be required. Currently, the waterproofing of space shuttles after each re-entry takes 72 hours and requires substantial labor. In addition, the currently used waterproofing reagent, DiMethylEthoxySilane (DMES), is considered toxic, and ethanol fumes are released during its hydrolytic activation. Consequently, a long time period, which is not acceptable for future operations, is needed to ensure that 0 the excess volatile compounds are removed before further maintenance of the space vehicle can be performed. The objective of this project was to assist NASA Ames in finding improved waterproofing systems by identifying suitable waterproofing agents that can be applied by vapor phase deposition and will be less toxic, bond more rapidly to the insulation material surface, and potentially have higher thermal stability than the DMES system. Several approaches to achieve faster waterproofing with less toxicity were assessed using the following alternatives: Reactive volatile compounds that are rapidly deposited by chemical bonding at the surface and leave no toxic volatiles. Reactive reagents that are the least toxic. Nonvolatile reagents that are very reactive and bond strongly to the insulating material surface. Three specific types of potential reagents were chosen for evaluation in this project: 1. Volatile reagents with Si-Cl functional groups for vapor deposition 2. Volatile reagents with Si-H functional groups for vapor deposition 3. Nonvolatile oligomeric or polymeric reactive siloxanes that are assumed to have higher thermal stability and/or strong bonding to the insulating material. The chemistry involved in the project was targeted at the generation of intermediates having reactive Si-OH bonds for the formation of either volatile species or polymeric species that bond rapidly to the surface and also cure rapidly. We focused on two chemical reactions@-hydrolysis of Si-Cl bonds and catalytic dehydrocoupling of Si-H bonds.
NASA Astrophysics Data System (ADS)
Singh, Arun K.; Singh, Jayant K.
2017-09-01
In this study, we have developed super-repellent surface on cotton fabric via a facile and eco-friendly strategy using zirconia particles with water-soluble siloxane emulsion. The coated fabric using zirconia-siloxane (ZS) coating showed super-repellency of liquids with surface tension >47.7 mN/m, like water, mixtures of isopropyl alcohol with deionized water (2% and 5%, v/v), and ethylene glycol with contact angle of 158°, 155°, 153° and 152°, respectively. Furthermore, the coated fabric displays low sliding angle, <10°, with these liquids. The super-repellency of the coated fabric is attributed due to its lower surface energy (<1.0 mJ m-2). The produced coating exhibited excellent durability and retained its super-repelling properties under harsh environment conditions like acidic, alkaline, salty, ultraviolet irradiation, mechanical abrasion and repeated tear test with an adhesive tape. In addition, in a mixture of water and oil (having surface tension <30 mN/m), the developed coated fabric exhibited dual nature viz., superhydrophobicity and superoleophilicity, maintaining the super-repellency with water even they are wetted with oily liquids. The materials with ability to repel water in the presence of oily pollutants are very useful in application related to sea water. Thus as-prepared coated fabric, with dual functionality, is a promising material for many applications including anti-wetting, self-cleaning, support for aquatic floating devices and as a filtration material for rapid and continuous oil-water separation.
Morphological Properties of Siloxane-Hydrogel Contact Lens Surfaces.
Stach, Sebastian; Ţălu, Ştefan; Trabattoni, Silvia; Tavazzi, Silvia; Głuchaczka, Alicja; Siek, Patrycja; Zając, Joanna; Giovanzana, Stefano
2017-04-01
The aim of this study was to quantitatively characterize the micromorphology of contact lens (CL) surfaces using atomic force microscopy (AFM) and multifractal analysis. AFM and multifractal analysis were used to characterize the topography of new and worn siloxane-hydrogel CLs made of Filcon V (I FDA group). CL surface roughness was studied by AFM in intermittent-contact mode, in air, on square areas of 25 and 100 μm 2 , by using a Nanoscope V MultiMode (Bruker). Detailed surface characterization of the surface topography was obtained using statistical parameters of 3-D (three-dimensional) surface roughness, in accordance with ISO 25178-2: 2012. Before wear, the surface was found to be characterized by out-of-plane and sharp structures, whilst after a wear of 8 h, two typical morphologies were observed. One morphology (sharp type) has a similar aspect as the unworn CLs and the other morphology (smooth type) is characterized by troughs and bumpy structures. The analysis of the AFM images revealed a multifractal geometry. The generalized dimension D q and the singularity spectrum f(α) provided quantitative values that characterize the local scale properties of CL surface geometry at nanometer scale. Surface statistical parameters deduced by multifractal analysis can be used to assess the CL micromorphology and can be used by manufacturers in developing CLs with improved surface characteristics. These parameters can also be used in understanding the tribological interactions of the back surface of the CL with the corneal surface and the front surface of the CL with the under-surface of the eyelid (friction, wear, and micro-elastohydrodynamic lubrication at a nanometer scale).
Paper based colorimetric biosensing platform utilizing cross-linked siloxane as probe.
Zhou, Miao; Yang, Minghui; Zhou, Feimeng
2014-05-15
Paper based colorimetric biosensing platform utilizing cross-linked siloxane 3-aminopropyltriethoxysilane (APTMS) as probe was developed for the detection of a broad range of targets including H2O2, glucose and protein biomarker. APTMS was extensively used for the modification of filter papers to develop paper based analytical devices. We discovered when APTMS was cross-linked with glutaraldehyde (GA), the resulting complex (APTMS-GA) displays brick-red color, and a visual color change was observed when the complex reacted with H2O2. By integrating the APTMS-GA complex with filter paper, the modified paper enables quantitative detection of H2O2 through the monitoring of the color intensity change of the paper via software Image J. Then, with the immobilization of glucose oxidase (GOx) onto the modified paper, glucose can be detected through the detection of enzymatically generated H2O2. For protein biomarker prostate specific antigen (PSA) assay, we immobilized capture, not captured anti-PSA antibody (Ab1) onto the paper surface and using GOx modified gold nanorod (GNR) as detection anti-PSA antibody (Ab2) label. The detection of PSA was also achieved via the liberated H2O2 when the GOx label reacted with glucose. The results demonstrated the possibility of this paper based sensor for the detection of different analytes with wide linear range. The low cost and simplicity of this paper based sensor could be developed for "point-of-care" analysis and find wide application in different areas. © 2013 Published by Elsevier B.V.
Sweeney, Sunya; Smith, Derek K; Messersmith, Marion
2015-08-01
One method of articulating digital models is to use a digitized interocclusal record. However, the accuracy of different interocclusal record materials to articulate digital models has yet to be evaluated. A plastic typodont was modified with reference points for interarch measurements and articulated in maximum intercuspal position on a semiadjustable hinge articulator. Twenty-five interocclusal records of each of the 5 experimental materials (Regisil Rigid, Dentsply, York, Pa; Futar Scan, Kettenbach, Huntington Beach, Calif; Byte Right, Motion View Software, Chattanooga, Tenn; Aluwax, Aluwax Dental Products, Allendale, Mich; and Beauty Pink wax, Miltex, York, Pa) were made on the mounted typodont and digitized using an Ortho Insight 3D laser surface scanner (Motion View Software). Motion View Software was used to articulate the digital models by matching points from the models to the digitized interocclusal records. The distances between corresponding interarch markers were measured and compared with the measurements taken on the physical typodont (gold standard). Polyvinyl siloxane materials were significantly more likely to lead to successful articulation than were the other interocclusal record materials. Statistical analysis showed a significant effect of the bite registration material on the probability of success of the articulation (P <0.005). Polyvinyl siloxane is a more accurate interocclusal recording material when articulating digital models according to the process described in this study. Using a bite registration to articulate digital models should be considered the first step in the articulation process, with a likely residual need to manipulate the models manually. Copyright © 2015 American Association of Orthodontists. Published by Elsevier Inc. All rights reserved.
Influence of loading forces on the vertical accuracy of interocclusal records.
Ghazal, Muhamad; Kern, Matthias
2010-02-01
To evaluate the influence of loading forces on the vertical discrepancies caused by interocclusal recording materials. A custom-made apparatus was used to simulate the maxilla and mandible. Eight interocclusal records were made in each of the following groups: G1-Aluwax (aluminum wax; Aluwax), G2-Beauty Pink wax (hydrocarbon wax compound; Miltex), G3-Futar D, G4-Futar D Fast, G5-Futar Scan (polyvinyl siloxanes; Kettenbach), and G6-Ramitec (polyether; 3M ESPE). The vertical discrepancies were measured by an inductive displacement transducer connected to a carrier frequency amplifier after storage of the records for 1 hour at room temperature. Different compressive loading forces up to 1 kg were applied onto the upper part of the apparatus to evaluate the influence on the vertical discrepancies of the records. Two-way ANOVA was used for statistical analysis. The compressive loading force had a statistically significant influence on the vertical discrepancies (P<.01) (ie, higher forces reduced the vertical discrepancies). When a compressive force of 1 kg was applied to the upper part of the apparatus, the mean vertical discrepancies for G1 (11+/-3 microm) and G2 (12+/-3 microm) were statistically significantly higher than in groups G3 (1+/-1 microm), G4 (2+/-1 microm), G5 (0+/-1 microm), and G6 (-2+/-2 microm). A compressive force of 1 kg could be used to stabilize the cast during mounting procedures in an articulator using an interocclusal record made of polyvinyl siloxane without vertically changing the interocclusal relationships.
Tough Amphiphilic Gels for Antifouling Applications
NASA Astrophysics Data System (ADS)
Villada, Laura M.
Biofouling is the attachment of unwanted organisms on a surface, and it is influenced by a host of variables including the chemistry of the material as well as both the surface and bulk properties, and controlling and understanding the effect of these properties is critical for the development of effective materials to combat biofouling. All surfaces that are submerged in water are subject to the rapid colonization of a wide range of marine organisms. Marine biofouling decreases fuel efficiency, costing the Navy millions of dollars in penalty, as well as having drastic environmental effects. Previous prevention of biofouling in marine systems has been accomplished by the administration of biocides and toxic coatings. In recent years, increased concerns about the impacts of these hazardous compounds into marine ecosystems has spurred efforts to develop cost effective, non-toxic, and durable anti-fouling coatings. Hydrogels, hydrophilic crosslinked networks, are being used to modify silicone marine coatings and have demonstrated potential at combatting biofouling. Understanding the impact of amphiphilic materials, i.e. their structure and properties, on biofouling is of great importance in order to address the need in the industry. In this study, poly(2-hydroxyethyl methacrylate) (HEMA) crosslinked networks were tailored to investigate the influence of their surface and bulk properties on biofouling. Previous research utilizing HEMA-siloxane gels suggested a relationship between molecular weight between crosslinks, M c, and the attachment of soft fouling sporelings of the green algae U. linza and adsorption of the protein bovine serum albumin (BSA), and the initial thrust of this dissertation was aimed at resolving this relationship. Gel composition was modified by varying the siloxane crosslinking agent and the siloxane hydrophobic monomer concentrations. The gels exhibited an increase in elastic modulus from 0.17 to 8.55 MPa that coincided with an increasing concentration of crosslinking agent. The resultant variation in network mesh size had the strongest correlation with the BSA adsorption (R2 = 0.90) and algal spore attachment (R2 = 0.73). The second system evaluated was based upon a new siloxane non-isocyanate urethane divinyl monomer (NIUDMA) that was synthesized using environmentally friendly methods in order to produce more mechanically durable gels. A crosslinked amphiphilic network was synthesized utilizing NIUDMA in conjunction with the relatively hydrophobic hexafluorobutyl methacrylate (HFBMA) with hydrophilic HEMA. The initial HFBMA and HEMA feed composition was varied, and the effect on gel properties was equated to anti-biofouling efficacy. The different gel compositions altered the surface chemistry slightly and the structure of their surface; however, the greatest difference was seen in the bulk structure and mechanical properties. The elastic moduli measured for these gels was much higher than the gels previously tested; it ranged from 2 MPa to as high as 140 MPa by varying the ratio of hydrophilic (20 - 90 mol%) to hydrophobic (0 - 70 mol%) monomer concentration. For the NIUDMA gels, the biofouling assays performed to probe the effect of gel properties included U. linza sporeling attachment, N. incerta diatom and C. lytica bacteria biofilm growth and removal, and A. Amphitrite adult barnacle reattachment. The most effective results were seen with the fouling release results of diatoms, with up to 96% reduction, and marine bacteria with up to 98% reduction after an applied water pressure of 138 kPa. These two microfouling marine organisms are part of the first stages of the biofouling process, and reducing their attachment and adhesion is critical for preventing or reducing the later stages. There were complex trends seen with the properties of the gels and the bioassay results. Overall, the NIUDMA10 networks had comparable results to commercial coatings against spores, diatoms and marine bacteria.
Optically Defined Multifunctional Patterning of Photosensitive Thin-Film Silica Mesophases
NASA Astrophysics Data System (ADS)
Doshi, Dhaval A.; Huesing, Nicola K.; Lu, Mengcheng; Fan, Hongyou; Lu, Yunfeng; Simmons-Potter, Kelly; Potter, B. G.; Hurd, Alan J.; Brinker, C. Jeffrey
2000-10-01
Photosensitive films incorporating molecular photoacid generators compartmentalized within a silica-surfactant mesophase were prepared by an evaporation-induced self-assembly process. Ultraviolet exposure promoted localized acid-catalyzed siloxane condensation, which can be used for selective etching of unexposed regions; for ``gray-scale'' patterning of refractive index, pore size, surface area, and wetting behavior; and for optically defining a mesophase transformation (from hexagonal to tetragonal) within the film. The ability to optically define and continuously control both structure and function on the macro- and mesoscales is of interest for sensor arrays, nanoreactors, photonic and fluidic devices, and low-dielectric-constant films.
Development of a dynamic pressure calibration technique
NASA Technical Reports Server (NTRS)
Vezzetti, C. F.; Hilten, J. S.; Lederer, P. S.
1975-01-01
The report deals with work continuing on the development of a method of producing sinusoidally varying pressures of at least 34 kPa zero-to-peak with amplitude variations within plus or minus 5% up to 2 kHz for the dynamic calibration of pressure transducers. Sinusoidally varying pressures of 34 kPa zero-to-peak were produced between 40 Hz and 750 Hz by vibrating a 10-cm column of a dimethyl siloxane liquid at 36gn zero-to-peak. Damping of the liquid column was accomplished by packing the fixture tube with a number of smaller diameter tubes.
NASA Astrophysics Data System (ADS)
Cao, Wenzhe; Görrn, Patrick; Wagner, Sigurd
2011-05-01
The electrical resistance of gold film conductors on polydimethyl siloxane substrates at stages of uniaxial stretching is measured and modeled. The surface area of a gold conductor is assumed constant during stretching so that the exposed substrate takes up all strain. Sheet resistances are calculated from frames of scanning electron micrographs by numerically solving for the electrical potentials of all pixels in a frame. These sheet resistances agree sufficiently well with values measured on the same conductors to give credence to the model of a stretchable network of gold links defined by microcracks.
Kurashina, Takayuki; Aoki, Shotaro; Hirasawa, Ryota; Hasegawa, Takeshi; Kasahara, Yuhki; Yoshida, Shoko; Yoza, Kenji; Nomiya, Kenji
2009-07-28
The title compound with the formula (Me2NH2)13H5[{alpha2-P2W17O61(Si2O)}3(micro-O)3].39H2O Me2NH(2)-1 was obtained in 12.8% (0.258 g scale) yield by a 1:2 molar ratio reaction of alpha2-mono-lacunary Dawson polyoxometalate (POM) [alpha2-P2W17O61]10- with SiCl4 in water and unequivocally characterized by complete elemental analysis, TG/DTA, FTIR, (solution and solid-state) 31P NMR, solid-state 29Si NMR and X-ray crystallography. [Note: the moieties of the polyoxoanions in Me2NH(2)-1 and Me2NH(2)-2 are abbreviated simply as 1 and 2, respectively.] X-Ray crystallography revealed that the molecular structure of polyoxoanion 1 was a cyclic trimer consisting of three alpha2-mono-lacunary Dawson POM subunits constituted through intra- and intermolecular siloxane bonds. The compound resulted in an approximate Cs symmetry, but not the idealized C3v symmetry, because one Dawson unit was unequivalently incorporated into the cyclic framework. This compound is the first example of a siloxane-bonding cyclic trimer of POMs and its formation suggests that the oxygen atoms in the lacunary site of POM are reactive just like the surface oxygen atoms of silica. The formation of the cyclic trimer was also clarified by two control experiments: (1) the reaction of [alpha2-P2W17O61]10- with Si(OEt)4 under acidic conditions (pH 1), and (2) oligomerization under 6 M aqueous HCl acidic conditions (pH approximately 0) of the reactive monomer units (RMUs: tentatively assigned as "[alpha2-P2W17O61{O(SiOH)2}]6-"), derived from the cleavage of Ph-Si bonds by the thermal degradation of [alpha2-P2W17O61{O(SiPh)2}]6-. On the other hand, the reactions of alpha2-mono-lacunary Dawson POMs with GeX4 (X=OEt, Cl) gave the monomeric species of mono-germanium-substituted Dawson POM (Me2NH2)7[alpha2-P2W17O61(GeOH)].5H2O Me2NH(2)-2, which was characterized by CHN analysis, TG/DTA, FTIR, X-ray crystallography, and (solid-state and solution) 31P NMR spectroscopy. X-ray crystallography revealed that compound Me2NH(2)-2 was a monomeric species, but the Ge site per formula unit was not determined due to disorder of alpha-Dawson structure.
Al-Jabrah, Osama; Al-Shumailan, Yousef; Al-Rashdan, Manhal
2007-01-01
Dental impressions often carry microorganisms that may cause cross infection from patients to dental staff. The aim of the current study was to determine the effectiveness of 4 different disinfectant solutions on 3 commonly used impression materials--alginate, polyether, and polyvinyl siloxane--to establish a protocol for disinfection of these impression materials after clinical exposure and prior to handling in the dental laboratory. A total of 45 impressions were taken from the maxillary dentate arches of 15 dental staff participants at the Department of Dentistry, Prince Rashid Hospital, Irbid, Jordan. For each participant, 3 successive impressions were recorded in the different impression materials. For each impression, 6 specimens were dissected from 6 different locations and exposed to 6 different regimens: 1 was left untreated, 1 was immersed in sterile water for 10 minutes to serve as a control, and the remaining 4 specimens were exposed to 4 different disinfection treatments (Dimenol, Perform-ID, MD 520, and Haz-tabs). Serial dilutions of the suspension were carried out and counted by the Miles-Misra technique (inoculation on Columbia blood agar for quantification). The dilutions were aerobically incubated at 37 degrees C for 48 hours. The disinfectants were able to completely eliminate microorganisms carried by the impressions. For those undisinfected specimens, the results showed that untreated alginate impressions appear to carry more microorganisms (P < .05) than the other 2 rubber impression materials used in the study. For those specimens immersed in sterile water for 10 minutes (control group), the number of microorganisms eliminated was increased from 62% to 90% compared to those left untreated. Impression materials may act as a vehicle for the transfer of microorganisms from the patient's mouth to dental personnel. Impressions should be disinfected to eliminate the risk of cross contamination.
Al Kheraif, Abdulaziz Abdullah
2013-05-01
Autoclave sterilization and microwave sterilization has been suggested as the effective methods for the disinfection of elastomeric impressions, but subjecting elastomeric impressions to extreme temperature may have adverse effects on critical properties of the elastomers. To evaluate the effect of chemical disinfection as well as autoclave and microwave sterilization on the surface roughness of elastomeric impression materials. The surface roughness of five commercially available polyvinyl siloxane impression materials (Coltene President, Affinis Perfect impression, Aquasil, 3M ESPE Express and GC Exafast) were evaluated after subjecting them to chemical disinfection, autoclaving and microwave sterilization using a Talysurf Intra 50 instrument. Twenty specimens from each material were fabricated and divided into four equal groups, three experimental and one control (n=25). The differences in the mean surface roughness between the treatment groups were recorded and statistically analyzed. No statistically significant increase in the surface roughness was observed when the specimens were subjected to chemical disinfection and autoclave sterilization, increase in roughness and discoloration was observed in all the materials when specimens were subjected to microwave sterilization. Chemical disinfection did not have a significant effect but, since it is less effective, autoclave sterilization can be considered effective and autoclaving did not show any specimen discoloration as in microwave sterilization. Microwave sterilization may be considered when impressions are used to make diagnostic casts. A significant increase in surface roughness may produce rougher casts, resulting in rougher tissue surfaces for denture and cast restorations. Autoclave sterilization of vinyl polysiloxane elastomeric impressions for 5 minutes at 134°C at 20 psi may be considered an effective method over chemical disinfection and microwave sterilization, because chemical disinfection does not eliminate all disease-causing microorganisms and microwave sterilization leads to a rougher impression surface.
Cattani-Scholz, Anna; Pedone, Daniel; Blobner, Florian; Abstreiter, Gerhard; Schwartz, Jeffrey; Tornow, Marc; Andruzzi, Luisa
2009-03-09
The synthesis and characterization of two types of silicon-based biofunctional interfaces are reported; each interface bonds a dense layer of poly(ethylene glycol) (PEG(n)) and peptide nucleic acid (PNA) probes. Phosphonate self-assembled monolayers were derivatized with PNA using a maleimido-terminated PEG(45). Similarly, siloxane monolayers were functionalized with PNA using a maleimido-terminated PEG(45) spacer and were subsequently modified with a shorter methoxy-terminated PEG(12) ("back-filling"). The long PEG(45) spacer was used to distance the PNA probe from the surface and to minimize undesirable nonspecific adsorption of DNA analyte. The short PEG(12) "back-filler" was used to provide additional passivation of the surface against nonspecific DNA adsorption. X-ray photoelectron spectroscopic (XPS) analysis near the C 1s and N 1s ionization edges was done to characterize chemical groups formed in the near-surface region, which confirmed binding of PEG and PNA to the phosphonate and silane films. XPS also indicated that additional PEG chains were tethered to the surface during the back-filling process. Fluorescence hybridization experiments were carried out with complementary and noncDNA strands; both phosphonate and siloxane biofunctional surfaces were effective for hybridization of cDNA strands and significantly reduced nonspecific adsorption of the analyte. Spatial patterns were prepared by polydimethylsiloxane (PDMS) micromolding on the PNA-functionalized surfaces; selective hybridization of fluorescently labeled DNA was shown at the PNA functionalized regions, and physisorption at the probe-less PEG-functionalized regions was dramatically reduced. These results show that PNA-PEG derivatized phosphonate monolayers hold promise for the smooth integration of device surface chemistry with semiconductor technology for the fabrication of DNA biosensors. In addition, our results confirm that PNA-PEG derivatized self-assembled carboxyalkylsiloxane films are promising substrates for DNA microarray applications.
Fabrication and characterization of bolus material using polydimethyl-siloxane
NASA Astrophysics Data System (ADS)
Wiratma Jaya, Gede; Sutanto, Heri
2018-01-01
Bolus has been used in radiotherapy to reduce tissue harm and to increase the superficial dose for skin cancer treatment. Commonly, a bolus is made of melamine in several hospitals. In this research, polydimethyl-siloxane (PDMS) material was used for bolus fabrication. The aims of the study are to investigate bolus density, percentage surface dose and its structural strength for each various composition. In bolus preparation, bolus material used composition variation between PDMS volume and catalyst volume. Composition variation were 20:1, 22:1, 24:1, 26:1, 28:1, 30:1 and 32:1. PDMS and catalyst were mixed by chemical solution deposition method. Bolus was molded by using glass cast with the size of 10 × 10 × 0.5 cm3. Bolus density was analyzed by mass per volume equation, for bolus radiation was examined by the linear accelerator using two electron energy (5 and 7 MeV) and bolus strain and tensile strength were examined by Brookfield CT 3 machine. The results of bolus density were similar with soft tissue density, while the lowest and highest density each variation are 22:1 and 28:1. In general, the use of bolus has increased the surface dose. Percentage of surface dose at 5 MeV energy is higher than 7 MeV energy. The highest percentage of surface dose at 5 MeV energy with 0.5 and 1.0 cm bolus thickness was achieved at composition of 32:1. For strain and tensile strength result, the lowest and highest strain each variation are 22:1 and 28:1, then the lowest and highest tensile strength each variation are 32:1 and 28:1. These results is important to select composition material for bolus fabrication in radiotherapy treatment.
Yamada, Shinya; Obata, Akiko; Maeda, Hirotaka; Ota, Yoshio; Kasuga, Toshihiro
2015-01-01
Development of novel biomaterials with Mg2+, Ca2+, and silicate ions releasability for bone regeneration is now in progress. Several inorganic ions have been reported to stimulate bone-forming cells. We featured Ca2+, silicate, and especially, Mg2+ ions as growth factors for osteoblasts. Various biomaterials, such as ceramic powders and organic–inorganic composites, that release the ions, have been developed and investigated for their cytocompatibilities in our previous work. Through the investigation, providing the three ions was found to be effective to activate osteogenic cells. Magnesium and siloxane-containing vaterite was prepared by a carbonation process as an inorganic particle that can has the ability to simultaneously release Ca2+, silicate, and Mg2+ ions to biodegradable polymers. Poly (l-lactic acid) (PLLA)- and bioactive PLLA-based composites containing vaterite coatings were discussed regarding their degradability and cytocompatibility using a metallic Mg substrate as Mg2+ ion source. PLLA/SiV composite film, which has a releasability of silicate ions besides Ca2+ ion, was coated on a pure Mg substrate to be compared with the PLLA/V coating. The degradability and releasability of inorganic ions were morphologically and quantitatively monitored in a cell culture medium. The bonding strength between the coatings and Mg substrates was one of the key factors to control Mg2+ ion release from the substrates. The cell culture tests were conducted using mouse osteoblast-like cells (MC3T3-E1 cells); cellular morphology, proliferation, and differentiation on the materials were evaluated. The PLLA/V and PLLA/SiV coatings on Mg substrates were found to enhance the proliferation, especially the PLLA/SiV coating possessed a higher ability to induce the osteogenic differentiation of the cells. PMID:26697421
A Comparison of implant impression precision: Different materials and techniques
Tabesh, Mahtab; Alikhasi, Marzieh
2018-01-01
Background Precision of implant impressions is a prerequisite for long-term success of implant supported prostheses. Impression materials and impression techniques are two important factors that impression precision relies on. Material and Methods A model of edentulous maxilla containing four implants inserted by All-on-4 guide was constructed. Seventy two impressions using polyether (PE), polyvinyl siloxane (PVS), and vinyl siloxanether (VSE) materials with direct and indirect techniques were made (n=12). Coordinates of implants in casts were measured using coordinate measuring machine (CMM). Data were analyzed with ANOVA; t-test and Tukey test were used for post hoc. Results With two-way ANOVA, mean values of linear displacements of implants were significantly different among materials and techniques. One-way ANOVA and Tukey showed significant difference between PE and VSE (P=0.019), PE and PVS (P=0.002) in direct technique, and between PVS and PE (P<0.001), PVS and VSE (P<0.001) in indirect technique. One-way ANOVA and t-test showed significant difference between the two techniques in PVS groups (P<0.001) and in PE groups (P=0.02). Two-way ANOVA showed mean values of rotational displacement of implants were significantly different among materials. One-way ANOVA and Tukey test showed significant difference between PVS and PE (P=0.001) and between PVS and VSE (P=0.012) in indirect groups. Conclusions On the basis of the results, when deciding on the material to make an impression of implants, PE is recommended for direct technique while PE and VSE are recommended for indirect technique. Recommended technique for VSE is either direct or indirect; and for PE and PVS is direct. Key words:Polyvinyl siloxane, polyether, vinyl siloxanether, direct technique, indirect technique, All-on-4, coordinate measuring machine. PMID:29670733
Ebadian, Behnaz; Rismanchian, Mansor; Dastgheib, Badrosadat; Bajoghli, Farshad
2015-01-01
Different factors such as impression techniques and materials can affect the passive fit between the superstructure and implant. The aim of this study was to determine the effect of different impression materials and techniques on the dimensional accuracy of implant definitive casts. Four internal hex implants (Biohorizons Ø4 mm) were placed on a metal maxillary model perpendicular to the horizontal plane in maxillary lateral incisors, right canine and left first premolar areas. Three impression techniques including open tray, closed tray using ball top screw abutments and closed tray using short impression copings and two impression materials (polyether and polyvinyl siloxane) were evaluated (n = 60). The changes in distances between implant analogues in mediolateral (x) and anteroposterior (y) directions and analogue angles in x/z and y/z directions in the horizontal plane on the definitive casts were measured by coordinate measuring machine. The data were analyzed by multivariate two-way analysis of variance and one sample t-test (α = 0.05). No statistical significant differences were observed between different impression techniques and materials. However, deviation and distortion of definitive casts had a significant difference with the master model when short impression copings and polyvinyl siloxane impression material were used (P < 0.05). In open tray technique, there was a significant difference in the rotation of analogs compared with the master model with both impression materials (P < 0.05). There was no difference between open and closed tray impression techniques; however, less distortion and deviation were observed in the open tray technique. In the closed tray impression technique, ball top screw was more accurate than short impression copings.
Ebadian, Behnaz; Rismanchian, Mansor; Dastgheib, Badrosadat; Bajoghli, Farshad
2015-01-01
Background: Different factors such as impression techniques and materials can affect the passive fit between the superstructure and implant. The aim of this study was to determine the effect of different impression materials and techniques on the dimensional accuracy of implant definitive casts. Materials and Methods: Four internal hex implants (Biohorizons Ø4 mm) were placed on a metal maxillary model perpendicular to the horizontal plane in maxillary lateral incisors, right canine and left first premolar areas. Three impression techniques including open tray, closed tray using ball top screw abutments and closed tray using short impression copings and two impression materials (polyether and polyvinyl siloxane) were evaluated (n = 60). The changes in distances between implant analogues in mediolateral (x) and anteroposterior (y) directions and analogue angles in x/z and y/z directions in the horizontal plane on the definitive casts were measured by coordinate measuring machine. The data were analyzed by multivariate two-way analysis of variance and one sample t-test (α = 0.05). Results: No statistical significant differences were observed between different impression techniques and materials. However, deviation and distortion of definitive casts had a significant difference with the master model when short impression copings and polyvinyl siloxane impression material were used (P < 0.05). In open tray technique, there was a significant difference in the rotation of analogs compared with the master model with both impression materials (P < 0.05). Conclusion: There was no difference between open and closed tray impression techniques; however, less distortion and deviation were observed in the open tray technique. In the closed tray impression technique, ball top screw was more accurate than short impression copings. PMID:25878678
Rufin, Marc A.; Barry, Mikayla E.; Adair, Paige A.; Hawkins, Melissa L.; Raymond, Jeffery E.; Grunlan, Melissa A.
2016-01-01
In contrast to modification with conventional PEO-silanes (i.e. no siloxane tether), silicones with dramatically enhanced protein resistance have been previously achieved via bulk-modification with poly (ethylene oxide) (PEO)-silane amphiphiles α-(EtO)3Si(CH2)2-oligodimethylsiloxane13-block-PEOn-OCH3 when n = 8 and 16 but not when n = 3. In this work, their efficacy was evaluated in terms of optimal PEO-segment length and minimum concentration required in silicone. For each PEO-silane amphiphile (n = 3, 8, and 16), five concentrations (5, 10, 25, 50, and 100 μmol per 1 g silicone) were evaluated. Efficacy was quantified in terms of the modified silicones’ abilities to undergo rapid, water-driven surface restructuring to form hydrophilic surfaces as well as resistance to fibrinogen adsorption. Only n = 8 and 16 were effective, with a lower minimum concentration in silicone required for n = 8 (10 μmol per 1 g silicone) versus n = 16 (25 μmol per 1 g silicone). Statement of Significance Silicone is commonly used for implantable medical devices, but its hydrophobic surface promotes protein adsorption which leads to thrombosis and infection. Typical methods to incorporate poly(ethylene oxide) (PEO) into silicones have not been effective due to the poor migration of PEO to the surface-biological interface. In this work, PEO-silane amphiphiles – comprised of a siloxane tether (m = 13) and variable PEO segment lengths (n = 3, 8, 16) – were blended into silicone to improve its protein resistance. The efficacy of the amphiphiles was determined to be dependent on PEO length. With the intermediate PEO length (n = 8), water-driven surface restructuring and resulting protein resistance was achieved with a concentration of only 1.7 wt%. PMID:27090588
Jeyapalan, Vidhya; Krishnan, Chitra Shankar; Ramasubramanian, Hariharan; Sampathkumar, Jayakrishnakumar; Azhagarasan, N S; Krishnan, Madhusudan
2016-07-06
To comparatively evaluate the antimicrobial efficacy of freshly prepared electrolyzed oxidizing water (EOW) with that of 2.4% glutaraldehyde (GA) and 1% sodium hypochlorite (SH) on clinically derived poly vinyl siloxane (PVS) impressions. Four clinically derived PVS impressions each were obtained from 10 subjects. One impression from each subject was randomly kept as control (group I), without disinfection. The remaining three impressions were randomly disinfected by immersion in either 2.4% GA (group II), 1% SH (group III), or freshly prepared EOW (group IV). The samples were subjected to microbial culture individually on brain heart infusion (BHI) agar medium. The organisms isolated were confirmed by visual examination and gram staining. Mean colony forming units (CFU) were counted, log 10 reduction obtained and compared. Data were statistically analyzed using one-way ANOVA, followed by multiple comparisons using Tukey-HSD post hoc tests (p < 0.05). Streptococci, Staphylococci, Pseudomonas, Candida, Proteus, Klebsiella, and E. coli were isolated from all impressions including the controls, except those disinfected by EOW. All three disinfectants showed significant reduction in CFU and log 10 reduction values as compared to the controls. EOW showed significantly higher reduction in log 10 values compared to GA and SH, whereas GA and SH showed similar reductions. EOW, GA, and SH showed kill rates of 100%, 99.60%, and 99.82%, respectively. EOW showed significant antimicrobial efficacy as evidenced by reduction in log 10 values when used as an immersion disinfectant for PVS impressions when compared with the results obtained using GA and SH. These results need further investigation. EOW shows high antimicrobial efficacy when used as an immersion disinfectant as compared to GA and SH for clinically derived PVS impressions. © 2016 by the American College of Prosthodontists.
Functionalised graphene sheets as effective high dielectric constant fillers
2011-01-01
A new functionalised graphene sheet (FGS) filled poly(dimethyl)siloxane insulator nanocomposite has been developed with high dielectric constant, making it well suited for applications in flexible electronics. The dielectric permittivity increased tenfold at 10 Hz and 2 wt.% FGS, while preserving low dielectric losses and good mechanical properties. The presence of functional groups on the graphene sheet surface improved the compatibility nanofiller/polymer at the interface, reducing the polarisation process. This study demonstrates that functionalised graphene sheets are ideal nanofillers for the development of new polymer composites with high dielectric constant values. PACS: 78.20.Ci, 72.80.Tm, 62.23.Kn PMID:21867505
Functionalised graphene sheets as effective high dielectric constant fillers
NASA Astrophysics Data System (ADS)
Romasanta, Laura J.; Hernández, Marianella; López-Manchado, Miguel A.; Verdejo, Raquel
2011-08-01
A new functionalised graphene sheet (FGS) filled poly(dimethyl)siloxane insulator nanocomposite has been developed with high dielectric constant, making it well suited for applications in flexible electronics. The dielectric permittivity increased tenfold at 10 Hz and 2 wt.% FGS, while preserving low dielectric losses and good mechanical properties. The presence of functional groups on the graphene sheet surface improved the compatibility nanofiller/polymer at the interface, reducing the polarisation process. This study demonstrates that functionalised graphene sheets are ideal nanofillers for the development of new polymer composites with high dielectric constant values. PACS: 78.20.Ci, 72.80.Tm, 62.23.Kn
Electrochemical properties of all solid state Li/S battery
DOE Office of Scientific and Technical Information (OSTI.GOV)
Yu, Ji-Hyun; Park, Jin-Woo; Wang, Qing
All-solid-state lithium/sulfur (Li/S) battery is prepared using siloxane cross-linked network solid electrolyte at room temperature. The solid electrolytes show high ionic conductivity and good electrochemical stability with lithium and sulfur. In the first discharge curve, all-solid-state Li/S battery shows three plateau potential regions of 2.4 V, 2.12 V and 2.00 V, respectively. The battery shows the first discharge capacity of 1044 mAh g{sup −1}-sulfur at room temperature. This first discharge capacity rapidly decreases in 4th cycle and remains at 512 mAh g{sup −1}-sulfur after 10 cycles.
NASA Astrophysics Data System (ADS)
Setiya Pradana, Jalu; Hidayat, Rahmat
2018-04-01
In this paper, we report our research work on developing a Surface Plasmon Resonance (SPR) element with sub-micron (hundreds of nanometers) periodicity grating structure. This grating structure was fabricated by using a simple nano-imprint lithography technique from an organically siloxane polymers, which was then covered by nanometer thin gold layer. The formed grating structure was a very well defined square-shaped periodic structure. The measured reflectance spectra indicate the SPR wave excitation on this grating structure. For comparison, the simulations of reflectance spectra have been also carried out by using Rigorous Coupled-Wave Analysis (RCWA) method. The experimental results are in very good agreement with the simulation results.
Striking Confinement Effect: AuCl[subscript 4][superscript -] Binding to Amines in a Nanocage Cavity
DOE Office of Scientific and Technical Information (OSTI.GOV)
Henao, Juan D.; Suh, Young-Woong; Lee, Jeong-Kyu
2009-02-23
Binding of AuCl{sub 4}{sup -} to amine groups tethered to the interior of a 2 nm siloxane nanocage was determined in solutions containing various concentrations of acid. The mode of binding was inferred from EXAFS and UV-vis spectra to be by ligand exchange of amine for chloride, which implies that the amines remain unprotonated. Cyclic voltammetry confirmed that the Au complexes bind to the nanocage interior and established a 1:1 relationship between bound Au complex and amine groups. The results suggested a 5-7 pH unit shift in the protonation constant of the interior amines relative to free amines in solution.
Selectivity assessment of DB-200 and DB-VRX open-tubular capillary columns.
Kiridena, W; Koziola, W W; Poole, C F
2001-10-12
The solvation parameter model is used to study the influence of composition and temperature on the selectivity of two poly(siloxane) stationary phases used for open-tubular capillary column gas chromatography. The poly(methyltrifluoropropyldimethylsiloxane) stationary phase, DB-200, has low cohesion, intermediate dipolarity/polarizability, low hydrogen-bond basicity, no hydrogen-bond acidity, and repulsive electron lone pair interactions. The DB-VRX stationary phase has low cohesion, low dipolarity/polarizability, low hydrogen-bond basicity and no hydrogen-bond acidity and no capacity for electron lone pair interactions. The selectivity of the two stationary phases is complementary to those in a database of 11 stationary phase chemistries determined under the same experimental conditions.
Development and characterization of lubricants for use near nuclear reactors in space vehicles
NASA Technical Reports Server (NTRS)
Robinson, G. L.; Akawie, R. I.; Gardos, M. N.; Krening, K. C.
1972-01-01
The synthesis and evaluation program was conducted to develop wide-temperature range lubricants suitable for use in space vehicles particularly in the vicinity of nuclear reactors. Synthetic approaches resulted in nonpolymeric, large molecular weight materials, all based on some combination of siloxane and aromatic groups. Evaluation of these materials indicated that certain tetramethyl and hexamethyl disiloxanes containing phenyl thiophenyl substituents are extremely promising with respect to radiation stability, wide temperature range, good lubricity, oxidation resistance and additive acceptance. The synthesis of fluids is discussed, and the equipment and methods used in evaluation are described, some of which were designed to evaluate micro-quantities of the synthesized lubricants.
Martinez-Solorio, Dionicio; Melillo, Bruno; Sanchez, Luis; Liang, Yong; Lam, Erwin; Houk, K. N.; Smith, Amos B.
2016-01-01
A reusable silicon-based transfer agent (1) has been designed, synthesized, and validated for effective room-temperature palladium-catalyzed cross-coupling reactions (CCRs) of aryl and heteroaryl chlorides with readily accessible aryl lithium reagents. The crystalline, bench-stable siloxane transfer agent (1) is easily prepared via a one-step protocol. Importantly, this “green” CCR protocol circumvents prefunctionalization, isolation of organometallic cross-coupling partners, and/or stoichiometric waste aside from LiCl. DFT calculations support a σ-bond metathesis mechanism during transmetalation and lead to insights on the importance of the CF3 groups. PMID:26835838
DOE Office of Scientific and Technical Information (OSTI.GOV)
Mahurin, Shannon Mark; Sokolov, Alexei P.; Saito, Tomonori
Here, the vinyl addition polymerization of norbornylbased monomers bearing polar functional groups is often problematic, leading to low molecular weight polymers in poor yield. Herein, we provide proof-of-principle evidence that addition-type homopolymers of siloxane substituted norbornyl-based monomers may be readily synthesized using the catalyst trans-[Ni(C 6F 5) 2(SbPh 3) 2]. Polymerizations using this catalyst reached moderate to high conversion in just 5 min of polymerization and produced siloxanesubstituted polymers with molecular weights exceeding 100 kg/mol. These polymers showed excellent thermal stability (T d ≥ 362 °C) and were cast into membranes that displayed high CO 2 permeability and enhanced COmore » 2/N 2 selectivity as compared to related materials.« less
Non-aqueous electrolytes for electrochemical cells
Dong, Jian; Zhang, Zhengcheng; Amine, Khalil
2016-07-12
A electrolyte for a lithium battery includes a silane/siloxane compound represented by SiR.sub.4-x-yR'.sub.xR''.sub.y, by Formula II, or Formula III: ##STR00001## where each R is individually an alkenyl, alkynyl, alk(poly)enyl, alk(poly)ynyl, aryl; each R' is represented by; ##STR00002## each R'' is represented by Formula I-B; ##STR00003## R.sup.1 is an organic spacer; R.sup.2 is a bond or an organic spacer; R.sup.3 is alkyl or aryl; k is 1-15; m is 1-15; n is 1 or 2; p is 1-3; x' is 1-2; and y' is 0-2.
NASA Astrophysics Data System (ADS)
Carmona-Quiroga, Paula María; Panas, Itai; Svensson, Jan-Erik; Johansson, Lars-Gunnar; Blanco-Varela, María Teresa; Martínez-Ramírez, Sagrario
2010-11-01
Specific strategies for protection are being developed to counter both the staining and corrosive effects of polluted air in cities, as well as to allow for efficient removal of unwanted graffiti paintings. These protection strategies employ molecules with tailored functionalities, e.g. being hydrophobic, while maintaining porosity for molecular water vapour permeation. The present study employs SO 2 and water to probe the behaviors of two anti-graffiti treatments, a water-base fluoroalkylsiloxane ("Protectosil Antigraffiti" marketed by Degussa) and an organically modified silicate (Ormosil) synthesized from a polymer chain (polydimethyl siloxane, PDMS) and two network forming alkoxides (Zr propoxide and methyl triethoxy silane, MTES) dissolved in n-propanol, on five building materials, comprising limestone, aged lime mortar, hydrated cement mortar, granite, and brick material. The materials were exposed to a synthetic atmosphere for 20 h in a climate chamber, 0.78 ± 0.03 ppm of SO 2 and 95% RH. Diffuse reflectance Fourier transform infrared (DR-FTIR) spectra were registered before and after exposure in the climate chamber in the cases of both treated and untreated samples. DR-FTIR, scanning electron microscope (SEM) images and energy dispersive X-ray (EDX) analyses, suggest the anti-graffiti Ormosil to suppress formation of calcium sulfite hemihydrate (the primary initial product of the reaction of calcium compounds with SO 2 and water) on carbonate materials (limestone and lime mortar). In case of the granite, brick and cement mortar, Ormosil has a negligible influence on the SO 2 capture. While no sulfite formation was detected by DR-FTIR, gypsum is inferred to form due to metal oxides and minority compounds catalysed oxidation of sulfite to sulfate. In case of brick, this understanding finds support from SEM images as well as EDX. A priori presence of gypsum in hydrated cement mortars prevents positive identification by SEM. However, support for sulfur accumulation in hydrated cement mortar is provided by means of EDX. In case of a second anti-graffiti considered, Protectosil, no influence of the anti-graffiti treatment on the SO 2 uptake of any of the building materials was observed.
Spectroscopic study of carbaryl sorption on smectite from aqueous suspension.
de Oliveira, Maurilio Fernandes; Johnston, Cliff T; Premachandra, G S; Teppen, Brian J; Li, Hui; Laird, David A; Zhu, Dongqiang; Boyd, Stephen A
2005-12-01
Sorption of carbaryl (1-naphthyl-N-methyl-carbamate) from aqueous suspension to smectite was studied using Fourier transform infrared (FTIR), high-performance liquid chromatography (HPLC) (for batch sorption), and quantum chemical methods. The amount of carbaryl sorbed was strongly dependent on the surface-charge density of the smectite with more sorption occurring on the two "low" surface-charge density smectites (SHCa-1 and SWy-2) compared to that of the high surface-charge SAz-1 smectite. In addition, the amount of carbaryl sorbed was strongly dependent on the nature of the exchangeable cation and followed the order of Ba approximately Cs approximately Ca > Mg approximately K > Na approximately Li for SWy-2. A similartrend was found for hectorite (SHCa-1) of Cs > Ba > Ca > K approximately Mg > Na approximately Li. Using the shift of the carbonyl stretching band as an indicator of the strength of interaction between carbaryl and the exchangeable cation, the observed order was Mg > Ca > Ba approximately K > Na > Cs. The position of the carbonyl stretching band shifted to lower wavenumbers with increasing ionic potential of the exchangeable cation. Density functional theory predicted a cation-induced lengthening of the C=O bond, resulting from the carbonyl group interacting directly with the exchangeable cation in support of the spectroscopic observations. Further evidence was provided by a concomitant shift in the opposite direction by several vibrational bands in the 1355-1375 cm(-1) region assigned to stretching bands of the carbamate N-Ccarbonyl and Oether-Ccarbonyl bonds. These data indicate that carbaryl sorption is due, in part, to site-specific interactions between the carbamate functional group and exchangeable cations, as evidenced by the FTIR data. However, these data suggest that hydrophobic interactions also contribute to the overall amount of carbaryl sorbed. For example, the FTIR data indicated thatthe weakest interaction occurred when Cs+ was the exchangeable cation. In contrast, the highest amount of carbaryl sorption was observed on Cs-exchanged smectite. Of all the cations studied, Cs has the lowest enthalpy of hydration. It is suggested that this low hydration energy provides the carbaryl with greater access to the hydrophobic regions of the siloxane surface.
Santercole, Viviana; Delmonte, Pierluigi; Kramer, John K G
2012-03-01
Commercial fish oils and foods containing fish may contain trans and/or isomerized fatty acids (FA) produced during processing or as part of prepared foods. The current American Oil Chemists' Society (AOCS) official method for marine oils (method Ce 1i-07) is based on separation by use of poly(ethylene glycol) (PEG) columns, for example Supelcowax-10 or equivalent, which do not resolve most unsaturated FA geometric isomers. Highly polar 100-m cyanopropyl siloxane (CPS) columns, for example SP-2560 and CP Sil 88 are recommended for separation of geometric FA isomers. Complementary separations were achieved by use of two different elution temperature programs with the same CPS column. This study is the first direct comparison of the separations achieved by use of 30-m Supelcowax-10 and 100-m SP-2560 columns for fatty acid methyl esters (FAME) prepared from the same fish oil and fish muscle sample. To simplify the identification of the FA in these fish samples, FA were fractionated on the basis of the number and type of double bonds by silver-ion solid-phase extraction (Ag⁺-SPE) before GC analysis. The results showed that a combination of the three GC separations was necessary to resolve and identify most of the unsaturated FA, FA isomers, and other components of fish products, for example phytanic and phytenic acids. Equivalent chain length (ECL) values of most FAME in fish were calculated from the separations achieved by use of both GC columns; the values obtained were shown to be consistent with previously reported values for the Supelcowax-10 column. ECL values were also calculated for the FA separated on the SP-2560 column. The calculated ECL values were equally valid under isothermal and temperature-programmed elution GC conditions, and were valuable for confirmation of the identity of several unsaturated FAME in the fish samples. When analyzing commercially prepared fish foods, deodorized marine oils, or foods fortified with marine oils it is strongly recommended that quantitative data acquired by use of PEG columns is complemented with data obtained from separations using highly polar CPS columns.
Physical properties and application in the confined geometrical systems
NASA Astrophysics Data System (ADS)
Pak, Hunkyun
Surface viscoelasticity of a vitamin E modified polyethylene glycol (vitamin E-TPGS) monolayers at the air/water interface is deduced by the surface light scattering method and Wilhelmy plate method. It was found that the viscoelasticity of vitamin E-TPGS monolayer is similar to that of PEO monolayer at the surface pressure lower than the collapse pressure of the polyethylene oxide (PEO). However, at higher surface pressure than the collapse pressure of PEO, it deviates from the viscoelastic behavior of PEO. Lateral diffusion constants of a probe lipid (NBD-PC) in a binary monolayer of L-a-dilauroylphosphatidylcholine (DLPC) and poly-(di-isobutylene-alt-maleic acid) (PDIBMA) were determined by the fluorescence recovery after photobleaching (FRAP) method at the air/pH 7 buffer interface as a function of composition. The diffusion constant is found to retard down to less than one hundredth to that at pure DLPC monolayers as the mole fraction of PDIBMA increased. The free area model was used to interpret the probe diffusion retardation. Translational diffusion constants of a probe molecule, 4-octadecylamino-7-nitrobenzo-2-oxa-1,3-diazole (C18-NBD), in thin polyisoprene (PI) and polydimethyl siloxane (PDMS) films, spin coated on methylated and propylyaminated silicon wafers, are studied by the FRAP method as a function of film thickness. Reduction of the diffusion constant is observed as thickness of the films is decreased. Two empirical models, the two-layer model and the continuous layer model are proposed to account for the diffusion constant dependence on the film thickness vs. thickness. It was observed that the diffusion profiles in the films are dependet on the nature of the substrate surfaces. Self-assembled patterns of magnetic particles were made and fixed by applying magnetic field on the particles dispersed at the air/liquid interface, followed by gelling of the liquid subphase. With this method, the large patterns with controllable lattice constant can be made. The fixation of the subphase enhances the stability of the patterns. Further, three-dimensional self-assembled patterns can be made by this method when the fixation process is incorporated.
Code of Federal Regulations, 2010 CFR
2010-10-01
... methyl bromide or methyl chloride mixtures, etc. 173.193 Section 173.193 Transportation Other Regulations... bromide, chloropicrin and methyl bromide or methyl chloride mixtures, etc. (a) Bromoacetone must be...) Bromoacetone, methyl bromide, chloropicrin and methyl bromide mixtures, chloropicrin and methyl chloride...
Structural Interplay - Tuning Mechanics in Peptide-Polyurea Hybrids
NASA Astrophysics Data System (ADS)
Korley, Lashanda
Utilizing cues from natural materials, we have been inspired to explore the hierarchical arrangement critical to energy absorption and mechanical enhancement in synthetic systems. Of particular interest is the soft domain ordering proposed as a contributing element to the observed toughness in spider silk. Multiblock copolymers, are ideal and dynamic systems in which to explore this approach via variations in secondary structure of nature's building blocks - peptides. We have designed a new class of polyurea hybrids that incorporate peptidic copolymers as the soft segment. The impact of hierarchical ordering on the thermal, mechanical, and morphological behavior of these bio-inspired polyurethanes with a siloxane-based, peptide soft segment was investigated. These peptide-polyurethane/urea hybrids were microphase segregated, and the beta-sheet secondary structure of the soft segment was preserved during polymerization and film casting. Toughness enhancement at low strains was achieved, but the overall extensibility of the peptide-incorporated systems was reduced due to the unique hard domain organization. To decouple the secondary structure influence in the siloxane-peptide soft segment from mechanics dominated by the hard domain, we also developed non-chain extended peptide-polyurea hybrids in which the secondary structure (beta sheet vs. alpha helix) was tuned via choice of peptide and peptide length. It was shown that this structural approach allowed tailoring of extensibility, toughness, and modulus. The sheet-dominant hybrid materials were typically tougher and more elastic due to intermolecular H-bonding facilitating load distribution, while the helical-prevalent systems generally exhibited higher stiffness. Recently, we have explored the impact of a molecular design strategy that overlays a covalent and physically crosslinked architecture in these peptide-polyurea hybrids, demonstrating that physical constraints in the network hybrids influences peptide hydrogen bonding and morphology. These structural features correlated well with systematic changes in modulus, extensibility, and hysteresis. Complementary to this effort is the design of PEG-based peptide-polyurea hybrids with tunable and responsive as structural and injectable hydrogels. The authors acknowledge funding support from the National Science Foundation (CAREER DMR-0953236).
Mundry, T; Surmann, P; Schurreit, T
2000-12-01
The siliconization of pharmaceutical glass containers is an industrially frequently applied procedure. It is done by spreading an aqueous silicone oil emulsion film on the inner surface and successive heat curing treatment at temperatures above 300 degrees C for 10-30 min. It was often proposed that a covalent bonding of PDMS to the glass or branching of the linear PDMS occurs during heat treatment. The present study was performed for a detailed investigation of the glass and silicone (polydimethylsiloxane = PDMS) chemical state before and after heat-curing treatment and analysis of the bond nature. Combined X-ray excited photoelectron (XPS) and Auger electron spectroscopy as well as angle resolved XPS-measurements were used for analysis of the glass samples. The silicon surface atoms of the borosilicate container glass were transformed to a quartz-like compound whereas the former linear PDMS had a branched, two-dimensional structure after the heat curing treatment. It was concluded that the branching indicates the formation of new siloxane bonds to the glass surface via hydroxyl groups. Further evidence for the presence of bonded PDMS at the glass surface can be found in the valence band spectra of the siliconized and untreated samples. However, this bond could not be detected directly due to its very similar nature to the siloxane bonds of the glass matrix and the organosilicon backbone of PDMS. Due to the high variation of data from the siliconized samples it was concluded, that the silicone film is not homogeneous. Previously raised theories of reactions during heat-curing glass siliconization are supported by the XPS data of this investigation. Yet, the postulation of fixing or baking the silicone on the glass surface is only partially true since the bonded layer is very thin and most of the silicone originally on the surface after heat curing can be removed by suitable solvents. This fraction can therefore still interact with drug products being in contact to the siliconized container wall.
NASA Astrophysics Data System (ADS)
Richardson, J. A.; Rementer, C. W.; Bruder, Jan M.; Hoffman-Kim, D.
2011-08-01
Biomimetic replicas of cellular topography have been utilized to direct neurite outgrowth. Here, we cultured postnatal rat dorsal root ganglion (DRG) explants in the presence of Schwann cell (SC) topography to determine the influence of SC topography on neurite outgrowth. Four distinct poly(dimethyl siloxane) conduits were fabricated within which DRG explants were cultured. To determine the contribution of SC topographical features to neurite guidance, the extent of neurite outgrowth into unpatterned conduits, conduits with randomly oriented SC replicas, and conduits with SC replicas parallel or perpendicular to the conduit long axis was measured. Neurite directionality and outgrowth from DRG were also quantified on two-dimensional SC replicas with orientations corresponding to the four conduit conditions. Additionally, live SC migration and neurite extension from DRG on SC replicas were examined as a first step toward quantification of the interactions between live SC and navigating neurites on SC replicas. DRG neurite outgrowth and morphology within conduits and on two-dimensional SC replicas were directed by the underlying SC topographical features. Maximal neurite outgrowth and alignment to the underlying features were observed into parallel conduits and on parallel two-dimensional substrates, whereas the least extent of outgrowth was observed into perpendicular conduits and on perpendicular two-dimensional replica conditions. Additionally, neurites on perpendicular conditions turned to extend along the direction of underlying SC topography. Neurite outgrowth exceeded SC migration in the direction of the underlying anisotropic SC replica after two days in culture. This finding confirms the critical role that SC have in guiding neurite outgrowth and suggests that the mechanism of neurite alignment to SC replicas depends on direct contact with cellular topography. These results suggest that SC topographical replicas may be used to direct and optimize neurite alignment, and emphasize the importance of SC features in neurite guidance.
NASA Astrophysics Data System (ADS)
Hashemi, Adeleh; Bahari, Ali; Ghasemi, Shahram
2017-09-01
In this work, povidone/silica nanocomposite dielectric layers were deposited on the n-type Si (100) substrates for application in n-type silicon field-effect transistors (FET). Thermogravimetric analysis (TGA) indicated that strong chemical interactions between polymer and silica nanoparticles were created. In order to examine the effect of annealing temperatures on chemical interactions and nanostructure properties, annealing process was done at 423-513 K. Atomic force microscopy (AFM) images show the very smooth surfaces with very low surface roughness (0.038-0.088 nm). The Si2p and C1s core level photoemission spectra were deconvoluted to the chemical environments of Si and C atoms respectively. The obtained results of deconvoluted X-ray photoelectron spectroscopy (XPS) spectra revealed a high percentage of silanol hydrogen bonds in the sample which was not annealed. These bonds were inversed to stronger covalence bonds (siloxan bonds) at annealing temperature of 423 K. By further addition of temperature, siloxan bonds were shifted to lower binding energy of about 1 eV and their intensity were abated at annealing temperature of 513 K. The electrical characteristics were extracted from current-Voltage (I-V) and capacitance-voltage (C-V) measurements in metal-insulator-semiconductor (MIS) structure. The all n-type Si transistors showed very low threshold voltages (-0.24 to 1 V). The formation of the strongest cross-linking at nanostructure of dielectric film annealed at 423 K caused resulted in an un-trapped path for the transport of charge carriers yielding the lowest threshold voltage (0.08 V) and the highest electron mobility (45.01 cm2/V s) for its FET. By increasing the annealing temperature (473 and 513 K) on the nanocomposite dielectric films, the values of the average surface roughness, the capacitance and the FET threshold voltage increased and the value of FET electron field-effect mobility decreased.
Hoods-Moonsammy, Vyonne J; Owen, Peter; Howes, Dale G
2014-01-01
The purpose of this study was to compare the capacity of different impression materials to accurately reproduce the positions of five implant analogs on a master model by comparing the resulting cast with the stainless steel master model. The study was motivated by the knowledge that distortions can occur during impression making and the pouring of casts and that this distortion may produce inaccuracies of subsequent restorations, especially long-span castings for implant superstructures. The master model was a stainless steel model with five implant analogs. The impression materials used were impression plaster (Plastogum, Harry J Bosworth), a polyether (Impregum Penta, 3M ESPE), and two polyvinyl siloxane (PVS) materials (Aquasil Monophase and Aquasil putty with light-body wash, Dentsply). Five impressions were made with each impression material and cast in die stone under strictly controlled laboratory conditions. The positions of the implants on the master model, the impression copings, and the implant analogs in the subsequent casts were measured using a coordinate measuring machine that measures within 4 μm of accuracy. Statistical analyses indicated that distortion occurred in all of the impression materials, but inconsistently. The PVS monophase material reproduced the master model most accurately. Although there was no significant distortion between the impressions and the master model or between the impressions and their casts, there were distortions between the master model and the master casts, which highlighted the cumulative effects of the distortions. The polyether material proved to be the most reliable in terms of predictability. The impression plaster displayed cumulative distortion, and the PVS putty with light body showed the least reliability. Some of the distortions observed are of clinical significance and likely to contribute to a lack of passive fit of any superstructure. The inaccuracy of these analog materials and procedures suggested that greater predictability may lie in digital technology.
Salazar Gómez, J I; Lohmann, H; Krassowski, J
2016-06-01
Characterisation of biogases is normally dedicated to the online monitoring of the major components methane and carbon dioxide and, to a lesser extent, to the determination of ammonia and hydrogen sulphide. For the case of Volatile Organic Compounds (VOCs), much less attention is usually paid, since such compounds are normally removed during gas conditioning and with exception of sulphur compounds and siloxanes represent a rather low risk to conventional downstream devices but could be a hindrance for fuel cells. However, there is very little information in the literature about the type of substances found in biogases generated from biowaste or co-fermentation plants and their concentration fluctuations. The main aim of this study was to provide information about the time dependencies of the VOCs in three biogas plants spread out through Germany from autumn until summer, which have different process control, in order to assess their potential as biofuels. Additionally, this study was an attempt to establish a correlation between the nature of the substrates used in the biogas plants and the composition of the VOCs present in the gas phase. Significant time-dependent variations in concentration were observed for most VOCs but only small changes in composition were observed. In general, terpenes and ketones appeared as the predominant VOCs in biogas. Although for substances such as esters, sulphur-organic compounds and siloxanes the average concentrations observed were rather low, they exhibited significant concentration peaks. The second biogas plant which operates with dry fermentation was found to contain the highest levels of VOCs. The amount of total volatile organic compounds (TVOCs) for the first, second and third biogas plants ranged from 35 to 259 mg Nm(-3), 291-1731 mg Nm(-3) and 84-528 mg Nm(-3), respectively. Copyright © 2016 Elsevier Ltd. All rights reserved.
Thomaidi, Vasiliki S; Stasinakis, Athanasios S; Borova, Viola L; Thomaidis, Nikolaos S
2016-04-01
Greece was used as case study and the environmental risk associated with the existence of 99 emerging organic contaminants (EOCs) in sludge-amended soil was estimated using risk quotient (RQ) approach. Data on the concentration levels of EOCs in sewage sludge was collected after literature review. Chemical analyses were also conducted for 50 pharmaceuticals and illicit drugs in sludge samples from Athens Sewage Treatment Plant. Risk assessment was based on both terrestrial and aquatic acute toxicity data, using both the maximum and the average measured concentrations of the target compounds. EC50/LC50 values were collected through literature review or using the ECOSAR program in cases that experimental values were not available. Triclosan seems to pose an environmental risk on the soil environment, as its RQ values exceeded 1, both in terrestrial and aquatic toxicity data based risk assessment. Calculations based on aquatic toxicity data showed that another eleven compounds had RQs higher than 1, most of them belonging to the classes of synthetic phenolic compounds and siloxanes. Tetradecamethylhexasiloxane presented the highest RQ, while high RQs were also calculated for decamethylcyclopentasiloxane and caffeine. No environmental risk for the terrestrial environment is expected due to the individual action of illicit drugs, perfluorinated compounds and benzotriazoles. The sludge source and the day of sampling affected the estimated threat due to nonylphenolic compounds; however these factors did not affect the estimated risk for siloxanes, caffeine and ofloxacin. Calculation of RQ values for the mixture of EOCs, using either the maximum or the average concentrations, far exceeded 1 (253 and 209, respectively), indicating a presumable threat for the terrestrial environment due to the baseline toxicity of these compounds. Countries that reuse sludge for agricultural purposes should include specific EOCs in national monitoring campaigns and study more thoroughly on their effects to the terrestrial environment. Copyright © 2016 Elsevier B.V. All rights reserved.
NASA Astrophysics Data System (ADS)
Jeena, M. T.; Bok, Taesoo; Kim, Si Hoon; Park, Sooham; Kim, Ju-Young; Park, Soojin; Ryu, Ja-Hyoung
2016-04-01
The electrochemical performance of Li-ion batteries (LIBs) can be highly tuned by various factors including the morphology of the anode material, the nature of the electrolyte, the binding material, and the percentage of conducting materials. Binding materials have been of particular interest to researchers over the decades as a means to further improve the cycle durability and columbic efficiency of LIBs. Such approaches include the introduction of different polymeric binders such as poly(acrylic acid) (PAA), carboxymethyl cellulose (CMC), and alginic acid (Alg) into the Si anode of LIBs. To achieve a better efficiency of LIBs, herein, we introduce a novel copolymer, poly(tert-butyl acrylate-co-triethoxyvinylsilane) (TBA-TEVS), as an efficient binder with stable cycle retention and excellent specific capacity. The binder forms a highly interconnected three-dimensional network upon thermal treatment as a result of de-protection of the tert-butyl group and the consequent inter-intra condensation reaction, which minimizes pulverization of the Si nanoparticles. Moreover, the siloxane group is expected to promote the formation of stable solid-electrolyte-interface (SEI) layers. A series of random copolymers were synthesized by varying the molar ratio of tert-butyl acrylate and triethoxyvinylsilane. Twenty-one percent of TEVS in the TBS-TEVS copolymer gave rise to a superior performance as a binder for Si anodes, where the anodes showed a stable specific capacity of 2551 mA h g-1 over hundreds of cycles and an initial columbic efficiency (ICE) of 81.8%.The electrochemical performance of Li-ion batteries (LIBs) can be highly tuned by various factors including the morphology of the anode material, the nature of the electrolyte, the binding material, and the percentage of conducting materials. Binding materials have been of particular interest to researchers over the decades as a means to further improve the cycle durability and columbic efficiency of LIBs. Such approaches include the introduction of different polymeric binders such as poly(acrylic acid) (PAA), carboxymethyl cellulose (CMC), and alginic acid (Alg) into the Si anode of LIBs. To achieve a better efficiency of LIBs, herein, we introduce a novel copolymer, poly(tert-butyl acrylate-co-triethoxyvinylsilane) (TBA-TEVS), as an efficient binder with stable cycle retention and excellent specific capacity. The binder forms a highly interconnected three-dimensional network upon thermal treatment as a result of de-protection of the tert-butyl group and the consequent inter-intra condensation reaction, which minimizes pulverization of the Si nanoparticles. Moreover, the siloxane group is expected to promote the formation of stable solid-electrolyte-interface (SEI) layers. A series of random copolymers were synthesized by varying the molar ratio of tert-butyl acrylate and triethoxyvinylsilane. Twenty-one percent of TEVS in the TBS-TEVS copolymer gave rise to a superior performance as a binder for Si anodes, where the anodes showed a stable specific capacity of 2551 mA h g-1 over hundreds of cycles and an initial columbic efficiency (ICE) of 81.8%. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr01559j
Multifunctional iron oxide nanoparticles for biomedical applications
NASA Astrophysics Data System (ADS)
Bloemen, M.; Denis, C.; Van Stappen, T.; De Meester, L.; Geukens, N.; Gils, A.; Verbiest, T.
2015-03-01
Multifunctional nanoparticles have attracted a lot of attention since they can combine interesting properties like magnetism, fluorescence or plasmonic effects. As a core material, iron oxide nanoparticles have been the subject of intensive research. These cost-effective and non-toxic particles are used nowadays in many applications. We developed a heterobifunctional PEG ligand that can be used to introduce functional groups (carboxylic acids) onto the surface of the NP. Via click chemistry, a siloxane functionality was added to this ligand, for a subsequent covalent ligand exchange reaction. The functionalized nanoparticles have an excellent colloidal stability in complex environments like buffers and serum or plasma. Antibodies were coupled to the introduced carboxylic acids and these NP-antibody bioconjugates were brought into contact with Legionella bacteria for magnetic separation experiments.
Pervaporative stripping of acetone, butanol and ethanol to improve ABE fermentation.
Jitesh, K; Pangarkar, V G; Niranjan, K
2000-01-01
Acetone-butanol-ethanol fermentation by anaerobic bacterium C. acetobutylicum is a potential source for feedstock chemicals. The problem of product induced inhibition makes this fermentation economically infeasible. Pervaporation is studied as an effective separation technique to remove the toxic inhibitory products. Various membranes like Styrene Butadiene Rubber (SBR), Ethylene Propylene Diene Rubber (EPDM), plain Poly Dimethyl Siloxane (PDMS) and silicalite filled PDMS were studied for the removal of acetone, butanol and ethanol, from binary aqueous mixtures and from a quaternary mixture. It was found that the overall performance of PDMS filled with 15% w/w of silicalite was the best for removal of butanol in binary mixture study. SBR performance was best for the quaternary mixture studied.
Labruyère, Céline; Monteverde, Fabien; Alexandre, Michaël; Dubois, Philippe
2009-04-01
Poly(dimethylsiloxane) (PDMS)/montmorillonite (MMT) composites have been prepared using a newly synthesized omega-ammonium functionalized poly(dimethylsiloxane) compatibilizer coupled with a dispersion technique in water. The organoclay containing the new siloxane surfactant was characterized by TGA and XRD. For the first time, a nanoscopic dispersion of MMT nanoplatelets in the PDMS composite cured by hydrosilylation and a good compatibility between clay layers and matrix were obtained. The beneficial effect of both the surfactant and the water onto clay nanoplatelet dispersion was evaluated by different microscopy techniques and by measuring different properties such as the viscosity of the uncured PDMS/MMT nanodispersions, and the swelling rate and Young's modulus of the cured PDMS/MMT nanocomposites.
Selective Deposition of SiO2 on Ion Conductive Area of Soda-lime Glass Surface
Sakai, Daisuke; Harada, Kenji; Hara, Yuichiro; Ikeda, Hiroshi; Funatsu, Shiro; Uraji, Keiichiro; Suzuki, Toshio; Yamamoto, Yuichi; Yamamoto, Kiyoshi; Ikutame, Naoki; Kawaguchi, Keiga; Kaiju, Hideo; Nishii, Junji
2016-01-01
Selective deposition of SiO2 nanoparticles was demonstrated on a soda-lime glass surface with a periodic sodium deficient pattern formed using the electrical nanoimprint. Positively charged SiO2 particles generated using corona discharge in a cyclic siloxane vapor, were selectively deposited depending on the sodium pattern. For such phenomena to occur, the sodium ion migration to the cathode side was indispensable to the electrical charge compensation on the glass surface. Therefore, the deposition proceeded preferentially outside the alkali-deficient area. Periodic SiO2 structures with 424 nm and 180 nm heights were obtained using one-dimensional (6 μm period) and two-dimensional (500 nm period) imprinted patterns. PMID:27291796
Free silanols and ionic liquids as their suppressors in liquid chromatography.
Buszewska-Forajta, Magdalena; Markuszewski, Michał J; Kaliszan, Roman
2018-07-20
In this review, we will firstly discuss the types and the general properties of silica, focusing on the silica support used in chromatography and capillary electrophoresis. Additionally, the characterization of functional groups (silanols and siloxanes) will be considered in terms of activity of the stationary phases. We will then discuss physical chemistry of the stationary phases applied in liquid chromatography and capillary electrophoresis. The use of ionic liquids as a silanols' suppressors will be presented in the next parts of the study, along with the examples of specific applications. The review is completed with conclusions and an outlook for the future developments in the area of analytical applications of ionic liquids. Copyright © 2018 Elsevier B.V. All rights reserved.
Tuning polarity and improving charge transport in organic semiconductors
NASA Astrophysics Data System (ADS)
Oh, Joon Hak; Han, A.-Reum; Yu, Hojeong; Lee, Eun Kwang; Jang, Moon Jeong
2013-09-01
Although state-of-the-art ambipolar polymer semiconductors have been extensively reported in recent years, highperformance ambipolar polymers with tunable dominant polarity are still required to realize on-demand, target-specific, high-performance organic circuitry. Herein, dithienyl-diketopyrrolopyrrole (TDPP)-based polymer semiconductors with engineered side-chains have been synthesized, characterized and employed in ambipolar organic field-effect transistors, in order to achieve controllable and improved electrical properties. Thermally removable tert-butoxycarbonyl (t-BOC) groups and hybrid siloxane-solubilizing groups are introduced as the solubilizing groups, and they are found to enable the tunable dominant polarity and the enhanced ambipolar performance, respectively. Such outstanding performance based on our molecular design strategies makes these ambipolar polymer semiconductors highly promising for low-cost, large-area, and flexible electronics.
[Studies on organic protective coatings for anti-atomic oxygen effects by spectrum analysis].
Zhang, Lei
2004-11-01
This paper describes organic protective coatings on space material for anti-AO effects and the experiments to assess properties of the coatings. Organic protection was analyzed after exposures to ground state fast atomic (AO) radiation in the atomic oxygen beam facility for ground simulation experiments. The tests results have been analyzed with advanced FTIR, XPS and SEM. The test indicated that epoxy, alkyd and urethane organic coatings were highly reactive to AO with a strong degradation and changed in morphology of the surface layer. It is evident that siloxane coatings have excellent properties for anti-AO effects. The erosion product has SiO2 left on the surface, thus providing protection from further attack by the energetic oxygen atoms.
New generation of α-MnO2 nanowires @PDMS composite as a hydrogen gas sensor
NASA Astrophysics Data System (ADS)
Hamidi, Seyedeh Mehri; Mosivand, Alireza; Mahboubi, Mina; Arabi, Hadi; Azad, Narin; Jamal, Murtada Riyadh
2018-03-01
New hydrogen gas sensor has been prepared by α-MnO2 nanowires in polydimethylsiloxane matrix. For this purpose, the high aspect ratio α-MnO2 nanowires has been prepared by the aid of hydrothermal method and then dispersed into poly-dimethyl siloxane polymer media. For gas sensing, the samples have been exposed under different gas concentrations from 0 to 5%. The sensor responses have been examined by normalized ellipsometric parameter with respect to the chamber filled with N2 Gas. Our results indicate linear behavior of resonance wavelength in ellipsometric parameter as a function of gas concentrations which can open a new insight for the sample's capability to hydrogen gas sensing applications.
Adsorption of poly(ethylene oxide) on smectite: Effect of layer charge.
Su, Chia-Chi; Shen, Yun-Hwei
2009-04-01
The adsorption of polymers on clay is important in many applications. However the mechanisms of poly(ethylene oxide) (PEO) adsorption on smectite is not well elucidated at present. The aim of this study was to investigate the effect of layer charge density on the adsorption of PEO by smectite. The results indicated that both the hydrophobic interaction (between CH(2)CH(2) groups and siloxane surface) and the hydrogen bonding (between ether oxygen of PEO and structure OH of smectite) lead to PEO preferential adsorption on the surface of low-charge smectite. In addition, the delamination of low-charge smectite in water is enhanced upon PEO adsorption presumably due to the hydrophilic ether oxygen of adsorbed PEO.
Patterning methods for polymers in cell and tissue engineering.
Kim, Hong Nam; Kang, Do-Hyun; Kim, Min Sung; Jiao, Alex; Kim, Deok-Ho; Suh, Kahp-Yang
2012-06-01
Polymers provide a versatile platform for mimicking various aspects of physiological extracellular matrix properties such as chemical composition, rigidity, and topography for use in cell and tissue engineering applications. In this review, we provide a brief overview of patterning methods of various polymers with a particular focus on biocompatibility and processability. The materials highlighted here are widely used polymers including thermally curable polydimethyl siloxane, ultraviolet-curable polyurethane acrylate and polyethylene glycol, thermo-sensitive poly(N-isopropylacrylamide) and thermoplastic and conductive polymers. We also discuss how micro- and nanofabricated polymeric substrates of tunable elastic modulus can be used to engineer cell and tissue structure and function. Such synergistic effect of topography and rigidity of polymers may be able to contribute to constructing more physiologically relevant microenvironment.
Federal Register 2010, 2011, 2012, 2013, 2014
2013-05-29
... assessment of exposures and risks associated with methyl 5-(dimethylamino)-2-methyl-5-oxopentanoate follows... received and the nature of the adverse effects caused by methyl 5-(dimethylamino)-2-methyl-5- oxopentanoate... treatment with methyl 5-(dimethylamino)-2-methyl-5-oxopentanoate. A Mammalian Erythrocyte Micronucleus Test...
Jiang, Qun; Li, Qi; Yu, Hong; Kong, Lingfeng
2016-02-01
DNA methylation is an important epigenetic mechanism that could be responsive to environmental changes indicating a potential role in natural selection and adaption. In order to evaluate an evolutionary role of DNA methylation, it is essential to first gain a better insight into inheritability. To address this question, this study investigated DNA methylation variation from parents to offspring in the Pacific oyster Crassostrea gigas using fluorescent-labeled methylation-sensitive amplified polymorphism (F-MSAP) analysis. Most of parental methylated loci were stably transmitted to offspring segregating following Medelian expectation. However, methylated loci deviated more often than non-methylated loci and offspring showed a few de novo methylated loci indicating DNA methylation changes from parents to offspring. Interestingly, some male-specific methylated loci were found in this study which might help to explore sex determination in oyster. Despite environmental stimuli, genomic stresses such as polyploidization also can induce methylation changes. This study also compared global DNA methylation level and individual methylated loci between diploid and triploid oysters. Results showed no difference in global methylation state but a few ploidy-specific loci were detected. DNA methylation variation during polyploidization was less than autonomous methylation variation from parents to offspring.
Kawasaki, Takako; Ohnishi, Mutsuko; Nosho, Katsuhiko; Suemoto, Yuko; Kirkner, Gregory J; Meyerhardt, Jeffrey A; Fuchs, Charles S; Ogino, Shuji
2008-03-01
The CpG island methylator phenotype (CIMP or CIMP-high) with widespread promoter methylation is a distinct phenotype in colorectal cancer. However, the concept of CIMP-low with less extensive CpG island methylation is still evolving. Our aim is to examine whether density of methylation in individual CpG islands was different between CIMP-low and CIMP-high tumors. Utilizing MethyLight technology and 889 population-based colorectal cancers, we quantified DNA methylation (methylation index, percentage of methylated reference) at 14 CpG islands, including 8 CIMP-high-specific loci (CACNA1G, CDKN2A (p16), CRABP1, IGF2, MLH1, NEUROG1, RUNX3 and SOCS1). Methylation positivity in each locus was defined as methylation index>4. Low-level methylation (methylation index>0, <20) in each CIMP-high-specific locus was significantly more common in 340 CIMP-low tumors (1/8-5/8 methylation-positive loci) than 133 CIMP-high tumors (> or =6/8 methylation-positive loci) and 416 CIMP-0 tumors (0/8 methylation-positive loci) (P< or =0.002). In the other six loci (CHFR, HIC1, IGFBP3, MGMT, MINT31 and WRN), which were not highly specific for CIMP-high, low-level methylation, was not persistently more prevalent in CIMP-low tumors. In conclusion, compared to CIMP-high and CIMP-0 tumors, CIMP-low colorectal cancers show not only few methylated CIMP-high-specific CpG islands, but also more frequent low-level methylation at individual loci. Our data may provide supporting evidence for a difference in pathogenesis of DNA methylation between CIMP-low and CIMP-high tumors.
McCarthy, David; Pulverer, Walter; Weinhaeusel, Andreas; Diago, Oscar R; Hogan, Daniel J; Ostertag, Derek; Hanna, Michelle M
2016-06-01
Development of a sensitive method for DNA methylation profiling and associated mutation detection in clinical samples. Formalin-fixed and paraffin-embedded tumors received by clinical laboratories often contain insufficient DNA for analysis with bisulfite or methylation sensitive restriction enzymes-based methods. To increase sensitivity, methyl-CpG DNA capture and Coupled Abscription PCR Signaling detection were combined in a new assay, MethylMeter(®). Gliomas were analyzed for MGMT methylation, glioma CpG island methylator phenotype and IDH1 R132H. MethylMeter had 100% assay success rate measuring all five biomarkers in formalin-fixed and paraffin-embedded tissue. MGMT methylation results were supported by survival and mRNA expression data. MethylMeter is a sensitive and quantitative method for multitarget DNA methylation profiling and associated mutation detection. The MethylMeter-based GliomaSTRAT assay measures methylation of four targets and one mutation to simultaneously grade gliomas and predict their response to temozolomide. This information is clinically valuable in management of gliomas.
Hart-Smith, Gene; Yagoub, Daniel; Tay, Aidan P.; Pickford, Russell; Wilkins, Marc R.
2016-01-01
All large scale LC-MS/MS post-translational methylation site discovery experiments require methylpeptide spectrum matches (methyl-PSMs) to be identified at acceptably low false discovery rates (FDRs). To meet estimated methyl-PSM FDRs, methyl-PSM filtering criteria are often determined using the target-decoy approach. The efficacy of this methyl-PSM filtering approach has, however, yet to be thoroughly evaluated. Here, we conduct a systematic analysis of methyl-PSM FDRs across a range of sample preparation workflows (each differing in their exposure to the alcohols methanol and isopropyl alcohol) and mass spectrometric instrument platforms (each employing a different mode of MS/MS dissociation). Through 13CD3-methionine labeling (heavy-methyl SILAC) of Saccharomyces cerevisiae cells and in-depth manual data inspection, accurate lists of true positive methyl-PSMs were determined, allowing methyl-PSM FDRs to be compared with target-decoy approach-derived methyl-PSM FDR estimates. These results show that global FDR estimates produce extremely unreliable methyl-PSM filtering criteria; we demonstrate that this is an unavoidable consequence of the high number of amino acid combinations capable of producing peptide sequences that are isobaric to methylated peptides of a different sequence. Separate methyl-PSM FDR estimates were also found to be unreliable due to prevalent sources of false positive methyl-PSMs that produce high peptide identity score distributions. Incorrect methylation site localizations, peptides containing cysteinyl-S-β-propionamide, and methylated glutamic or aspartic acid residues can partially, but not wholly, account for these false positive methyl-PSMs. Together, these results indicate that the target-decoy approach is an unreliable means of estimating methyl-PSM FDRs and methyl-PSM filtering criteria. We suggest that orthogonal methylpeptide validation (e.g. heavy-methyl SILAC or its offshoots) should be considered a prerequisite for obtaining high confidence methyl-PSMs in large scale LC-MS/MS methylation site discovery experiments and make recommendations on how to reduce methyl-PSM FDRs in samples not amenable to heavy isotope labeling. Data are available via ProteomeXchange with the data identifier PXD002857. PMID:26699799
Transcription and chromatin determinants of de novo DNA methylation timing in oocytes.
Gahurova, Lenka; Tomizawa, Shin-Ichi; Smallwood, Sébastien A; Stewart-Morgan, Kathleen R; Saadeh, Heba; Kim, Jeesun; Andrews, Simon R; Chen, Taiping; Kelsey, Gavin
2017-01-01
Gametogenesis in mammals entails profound re-patterning of the epigenome. In the female germline, DNA methylation is acquired late in oogenesis from an essentially unmethylated baseline and is established largely as a consequence of transcription events. Molecular and functional studies have shown that imprinted genes become methylated at different times during oocyte growth; however, little is known about the kinetics of methylation gain genome wide and the reasons for asynchrony in methylation at imprinted loci. Given the predominant role of transcription, we sought to investigate whether transcription timing is rate limiting for de novo methylation and determines the asynchrony of methylation events. Therefore, we generated genome-wide methylation and transcriptome maps of size-selected, growing oocytes to capture the onset and progression of methylation. We find that most sequence elements, including most classes of transposable elements, acquire methylation at similar rates overall. However, methylation of CpG islands (CGIs) is delayed compared with the genome average and there are reproducible differences amongst CGIs in onset of methylation. Although more highly transcribed genes acquire methylation earlier, the major transitions in the oocyte transcriptome occur well before the de novo methylation phase, indicating that transcription is generally not rate limiting in conferring permissiveness to DNA methylation. Instead, CGI methylation timing negatively correlates with enrichment for histone 3 lysine 4 (H3K4) methylation and dependence on the H3K4 demethylases KDM1A and KDM1B, implicating chromatin remodelling as a major determinant of methylation timing. We also identified differential enrichment of transcription factor binding motifs in CGIs acquiring methylation early or late in oocyte growth. By combining these parameters into multiple regression models, we were able to account for about a fifth of the variation in methylation timing of CGIs. Finally, we show that establishment of non-CpG methylation, which is prevalent in fully grown oocytes, and methylation over non-transcribed regions, are later events in oogenesis. These results do not support a major role for transcriptional transitions in the time of onset of DNA methylation in the oocyte, but suggest a model in which sequences least dependent on chromatin remodelling are the earliest to become permissive for methylation.
Function and Evolution of DNA Methylation in Nasonia vitripennis
Wang, Xu; Wheeler, David; Avery, Amanda; Rago, Alfredo; Choi, Jeong-Hyeon; Colbourne, John K.; Clark, Andrew G.; Werren, John H.
2013-01-01
The parasitoid wasp Nasonia vitripennis is an emerging genetic model for functional analysis of DNA methylation. Here, we characterize genome-wide methylation at a base-pair resolution, and compare these results to gene expression across five developmental stages and to methylation patterns reported in other insects. An accurate assessment of DNA methylation across the genome is accomplished using bisulfite sequencing of adult females from a highly inbred line. One-third of genes show extensive methylation over the gene body, yet methylated DNA is not found in non-coding regions and rarely in transposons. Methylated genes occur in small clusters across the genome. Methylation demarcates exon-intron boundaries, with elevated levels over exons, primarily in the 5′ regions of genes. It is also elevated near the sites of translational initiation and termination, with reduced levels in 5′ and 3′ UTRs. Methylated genes have higher median expression levels and lower expression variation across development stages than non-methylated genes. There is no difference in frequency of differential splicing between methylated and non-methylated genes, and as yet no established role for methylation in regulating alternative splicing in Nasonia. Phylogenetic comparisons indicate that many genes maintain methylation status across long evolutionary time scales. Nasonia methylated genes are more likely to be conserved in insects, but even those that are not conserved show broader expression across development than comparable non-methylated genes. Finally, examination of duplicated genes shows that those paralogs that have lost methylation in the Nasonia lineage following gene duplication evolve more rapidly, show decreased median expression levels, and increased specialization in expression across development. Methylation of Nasonia genes signals constitutive transcription across developmental stages, whereas non-methylated genes show more dynamic developmental expression patterns. We speculate that loss of methylation may result in increased developmental specialization in evolution and acquisition of methylation may lead to broader constitutive expression. PMID:24130511
Trimarchi, Michael P.; Yan, Pearlly; Groden, Joanna; Bundschuh, Ralf; Goodfellow, Paul J.
2017-01-01
Background DNA methylation is a stable epigenetic mark that is frequently altered in tumors. DNA methylation features are attractive biomarkers for disease states given the stability of DNA methylation in living cells and in biologic specimens typically available for analysis. Widespread accumulation of methylation in regulatory elements in some cancers (specifically the CpG island methylator phenotype, CIMP) can play an important role in tumorigenesis. High resolution assessment of CIMP for the entire genome, however, remains cost prohibitive and requires quantities of DNA not available for many tissue samples of interest. Genome-wide scans of methylation have been undertaken for large numbers of tumors, and higher resolution analyses for a limited number of cancer specimens. Methods for analyzing such large datasets and integrating findings from different studies continue to evolve. An approach for comparison of findings from a genome-wide assessment of the methylated component of tumor DNA and more widely applied methylation scans was developed. Methods Methylomes for 76 primary endometrial cancer and 12 normal endometrial samples were generated using methylated fragment capture and second generation sequencing, MethylCap-seq. Publically available Infinium HumanMethylation 450 data from The Cancer Genome Atlas (TCGA) were compared to MethylCap-seq data. Results Analysis of methylation in promoter CpG islands (CGIs) identified a subset of tumors with a methylator phenotype. We used a two-stage approach to develop a 13-region methylation signature associated with a “hypermethylator state.” High level methylation for the 13-region methylation signatures was associated with mismatch repair deficiency, high mutation rate, and low somatic copy number alteration in the TCGA test set. In addition, the signature devised showed good agreement with previously described methylation clusters devised by TCGA. Conclusion We identified a methylation signature for a “hypermethylator phenotype” in endometrial cancer and developed methods that may prove useful for identifying extreme methylation phenotypes in other cancers. PMID:28278225
Lysine Methylation of Nuclear Co-repressor Receptor Interacting Protein 140
Huq, MD Mostaqul; Ha, Sung Gil; Barcelona, Helene; Wei, Li-Na
2009-01-01
Receptor interacting protein 140 (RIP140) undergoes extensive posttranslational modifications (PTMs), including phosphorylation, acetylation, arginine methylation, and pyridoxylation. PTMs affect its sub-cellular distribution, protein-protein interaction, and biological activity in adipocyte differentiation. Arginine methylation on Arg240, Arg650, and Arg948 suppresses the repressive activity of RIP140. Here we find that endogenous RIP140 in differentiated 3T3-L1 cells is also modified by lysine methylation. Three lysine residues, Lys591, Lys653, and Lys757 are mapped as potential methylation sites by mass spectrometry. Site-directed mutagenesis study shows that lysine methylation enhances its gene repressive activity. Mutation of lysine methylation sites enhances arginine methylation, while mutation on arginine methylation sites has little effect on its lysine methylation, suggesting a relationship between lysine methylation and arginine methylation. Kinetic analysis of PTMs of endogenous RIP140 in differentiated 3T3-L1 cells demonstrates sequential modifications on RIP140, initiated from constitutive lysine methylation, followed by increased arginine methylation later in differentiation. This study reveals a potential hierarchy of modifications, at least for lysine and arginine methylation, which bi-directionally regulate the functionality of a non-histone protein. PMID:19216533
McCarthy, David; Pulverer, Walter; Weinhaeusel, Andreas; Diago, Oscar R; Hogan, Daniel J; Ostertag, Derek; Hanna, Michelle M
2016-01-01
Aim: Development of a sensitive method for DNA methylation profiling and associated mutation detection in clinical samples. Materials & methods: Formalin-fixed and paraffin-embedded tumors received by clinical laboratories often contain insufficient DNA for analysis with bisulfite or methylation sensitive restriction enzymes-based methods. To increase sensitivity, methyl-CpG DNA capture and Coupled Abscription PCR Signaling detection were combined in a new assay, MethylMeter®. Gliomas were analyzed for MGMT methylation, glioma CpG island methylator phenotype and IDH1 R132H. Results: MethylMeter had 100% assay success rate measuring all five biomarkers in formalin-fixed and paraffin-embedded tissue. MGMT methylation results were supported by survival and mRNA expression data. Conclusion: MethylMeter is a sensitive and quantitative method for multitarget DNA methylation profiling and associated mutation detection. The MethylMeter-based GliomaSTRAT assay measures methylation of four targets and one mutation to simultaneously grade gliomas and predict their response to temozolomide. This information is clinically valuable in management of gliomas. PMID:27337298
Genetic and DNA Methylation Changes in Cotton (Gossypium) Genotypes and Tissues
Osabe, Kenji; Clement, Jenny D.; Bedon, Frank; Pettolino, Filomena A.; Ziolkowski, Lisa; Llewellyn, Danny J.; Finnegan, E. Jean; Wilson, Iain W.
2014-01-01
In plants, epigenetic regulation is important in normal development and in modulating some agronomic traits. The potential contribution of DNA methylation mediated gene regulation to phenotypic diversity and development in cotton was investigated between cotton genotypes and various tissues. DNA methylation diversity, genetic diversity, and changes in methylation context were investigated using methylation-sensitive amplified polymorphism (MSAP) assays including a methylation insensitive enzyme (BsiSI), and the total DNA methylation level was measured by high-performance liquid chromatography (HPLC). DNA methylation diversity was greater than the genetic diversity in the selected cotton genotypes and significantly different levels of DNA methylation were identified between tissues, including fibre. The higher DNA methylation diversity (CHG methylation being more diverse than CG methylation) in cotton genotypes suggest epigenetic regulation may be important for cotton, and the change in DNA methylation between fibre and other tissues hints that some genes may be epigenetically regulated for fibre development. The novel approach using BsiSI allowed direct comparison between genetic and epigenetic diversity, and also measured CC methylation level that cannot be detected by conventional MSAP. PMID:24465864
Genetic and DNA methylation changes in cotton (Gossypium) genotypes and tissues.
Osabe, Kenji; Clement, Jenny D; Bedon, Frank; Pettolino, Filomena A; Ziolkowski, Lisa; Llewellyn, Danny J; Finnegan, E Jean; Wilson, Iain W
2014-01-01
In plants, epigenetic regulation is important in normal development and in modulating some agronomic traits. The potential contribution of DNA methylation mediated gene regulation to phenotypic diversity and development in cotton was investigated between cotton genotypes and various tissues. DNA methylation diversity, genetic diversity, and changes in methylation context were investigated using methylation-sensitive amplified polymorphism (MSAP) assays including a methylation insensitive enzyme (BsiSI), and the total DNA methylation level was measured by high-performance liquid chromatography (HPLC). DNA methylation diversity was greater than the genetic diversity in the selected cotton genotypes and significantly different levels of DNA methylation were identified between tissues, including fibre. The higher DNA methylation diversity (CHG methylation being more diverse than CG methylation) in cotton genotypes suggest epigenetic regulation may be important for cotton, and the change in DNA methylation between fibre and other tissues hints that some genes may be epigenetically regulated for fibre development. The novel approach using BsiSI allowed direct comparison between genetic and epigenetic diversity, and also measured CC methylation level that cannot be detected by conventional MSAP.
Yang, Jin-Lan; Liu, Li-Wang; Gong, Yi-Qin; Huang, Dan-Qiong; Wang, Feng; He, Ling-Li
2007-06-01
The level of cytosine methylation induced by cadmium in radish (Raphanus sativus L.) genome was analysed using the technique of methylation-sensitive amplified polymorphism (MSAP). The MSAP ratios in radish seedling exposed to cadmium chloride at the concentration of 50, 250 and 500 mg/L were 37%, 43% and 51%, respectively, and the control was 34%; the full methylation levels (C(m)CGG in double strands) were at 23%, 25% and 27%, respectively, while the control was 22%. The level of increase in MSAP and full methylation indicated that de novo methylation occurred in some 5'-CCGG sites under Cd stress. There was significant positive correlation between increase of total DNA methylation level and CdCl(2) concentration. Four types of MSAP patterns: de novo methylation, de-methylation, atypical pattern and no changes of methylation pattern were identified among CdCl(2) treatments and the control. DNA methylation alteration in plants treated with CdCl(2) was mainly through de novo methylation.
Zhang, Qingzhu; Wang, Dong; Lang, Zhaobo; He, Li; Yang, Lan; Zeng, Liang; Li, Yanqiang; Zhao, Cheng; Huang, Huan; Zhang, Heng; Zhang, Huiming; Zhu, Jian-Kang
2016-01-01
DNA methylation is a conserved epigenetic mark in plants and many animals. How parental alleles interact in progeny to influence the epigenome is poorly understood. We analyzed the DNA methylomes of Arabidopsis Col and C24 ecotypes, and their hybrid progeny. Hybrids displayed nonadditive DNA methylation levels, termed methylation interactions, throughout the genome. Approximately 2,500 methylation interactions occurred at regions where parental DNA methylation levels are similar, whereas almost 1,000 were at differentially methylated regions in parents. Methylation interactions were characterized by an abundance of 24-nt small interfering RNAs. Furthermore, dysfunction of the RNA-directed DNA methylation pathway abolished methylation interactions but did not affect the increased biomass observed in hybrid progeny. Methylation interactions correlated with altered genetic variation within the genome, suggesting that they may play a role in genome evolution. PMID:27382183
2012-01-01
Background DNA cytosine methylation is an epigenetic modification that has been implicated in many biological processes. However, large-scale epigenomic studies have been applied to very few plant species, and variability in methylation among specialized tissues and its relationship to gene expression is poorly understood. Results We surveyed DNA methylation from seven distinct tissue types (vegetative bud, male inflorescence [catkin], female catkin, leaf, root, xylem, phloem) in the reference tree species black cottonwood (Populus trichocarpa). Using 5-methyl-cytosine DNA immunoprecipitation followed by Illumina sequencing (MeDIP-seq), we mapped a total of 129,360,151 36- or 32-mer reads to the P. trichocarpa reference genome. We validated MeDIP-seq results by bisulfite sequencing, and compared methylation and gene expression using published microarray data. Qualitative DNA methylation differences among tissues were obvious on a chromosome scale. Methylated genes had lower expression than unmethylated genes, but genes with methylation in transcribed regions ("gene body methylation") had even lower expression than genes with promoter methylation. Promoter methylation was more frequent than gene body methylation in all tissues except male catkins. Male catkins differed in demethylation of particular transposable element categories, in level of gene body methylation, and in expression range of genes with methylated transcribed regions. Tissue-specific gene expression patterns were correlated with both gene body and promoter methylation. Conclusions We found striking differences among tissues in methylation, which were apparent at the chromosomal scale and when genes and transposable elements were examined. In contrast to other studies in plants, gene body methylation had a more repressive effect on transcription than promoter methylation. PMID:22251412
On the presence and role of human gene-body DNA methylation
Jjingo, Daudi; Conley, Andrew B.; Yi, Soojin V.; Lunyak, Victoria V.; Jordan, I. King
2012-01-01
DNA methylation of promoter sequences is a repressive epigenetic mark that down-regulates gene expression. However, DNA methylation is more prevalent within gene-bodies than seen for promoters, and gene-body methylation has been observed to be positively correlated with gene expression levels. This paradox remains unexplained, and accordingly the role of DNA methylation in gene-bodies is poorly understood. We addressed the presence and role of human gene-body DNA methylation using a meta-analysis of human genome-wide methylation, expression and chromatin data sets. Methylation is associated with transcribed regions as genic sequences have higher levels of methylation than intergenic or promoter sequences. We also find that the relationship between gene-body DNA methylation and expression levels is non-monotonic and bell-shaped. Mid-level expressed genes have the highest levels of gene-body methylation, whereas the most lowly and highly expressed sets of genes both have low levels of methylation. While gene-body methylation can be seen to efficiently repress the initiation of intragenic transcription, the vast majority of methylated sites within genes are not associated with intragenic promoters. In fact, highly expressed genes initiate the most intragenic transcription, which is inconsistent with the previously held notion that gene-body methylation serves to repress spurious intragenic transcription to allow for efficient transcriptional elongation. These observations lead us to propose a model to explain the presence of human gene-body methylation. This model holds that the repression of intragenic transcription by gene-body methylation is largely epiphenomenal, and suggests that gene-body methylation levels are predominantly shaped via the accessibility of the DNA to methylating enzyme complexes. PMID:22577155
Guntrum, Megan; Vlasova, Ekaterina; Davis, Tamara L
2017-01-01
Differential DNA methylation plays a critical role in the regulation of imprinted genes. The differentially methylated state of the imprinting control region is inherited via the gametes at fertilization, and is stably maintained in somatic cells throughout development, influencing the expression of genes across the imprinting cluster. In contrast, DNA methylation patterns are more labile at secondary differentially methylated regions which are established at imprinted loci during post-implantation development. To investigate the nature of these more variably methylated secondary differentially methylated regions, we adopted a hairpin linker bisulfite mutagenesis approach to examine CpG dyad methylation at differentially methylated regions associated with the murine Dlk1/Gtl2 imprinting cluster on both complementary strands. We observed homomethylation at greater than 90% of the methylated CpG dyads at the IG-DMR, which serves as the imprinting control element. In contrast, homomethylation was only observed at 67-78% of the methylated CpG dyads at the secondary differentially methylated regions; the remaining 22-33% of methylated CpG dyads exhibited hemimethylation. We propose that this high degree of hemimethylation could explain the variability in DNA methylation patterns at secondary differentially methylated regions associated with imprinted loci. We further suggest that the presence of 5-hydroxymethylation at secondary differentially methylated regions may result in hemimethylation and methylation variability as a result of passive and/or active demethylation mechanisms.
Methylation of zebularine investigated using density functional theory calculations.
Selvam, Lalitha; Chen, Fang Fang; Wang, Feng
2011-07-30
Deoxyribonucleic acid (DNA) methylation is an epigenetic phenomenon, which adds methyl groups into DNA. This study reveals methylation of a nucleoside antibiotic drug 1-(β-D-ribofuranosyl)-2-pyrimidinone (zebularine or zeb) with respect to its methylated analog, 1-(β-D-ribofuranosyl)-5-methyl-2-pyrimidinone (d5) using density functional theory calculations in valence electronic space. Very similar infrared spectra suggest that zeb and d5 do not differ by types of the chemical bonds, but distinctly different Raman spectra of the nucleoside pair reveal that the impact caused by methylation of zeb can be significant. Further valence orbital-based information details on valence electronic structural changes caused by methylation of zebularine. Frontier orbitals in momentum space and position space of the molecules respond differently to methylation. Based on the additional methyl electron density concentration in d5, orbitals affected by the methyl moiety are classified into primary and secondary contributors. Primary methyl contributions include MO8 (57a), MO18 (47a), and MO37 (28a) of d5, which concentrates on methyl and the base moieties, suggest certain connection to their Frontier orbitals. The primary and secondary methyl affected orbitals provide useful information on chemical bonding mechanism of the methylation in zebularine. Copyright © 2011 Wiley Periodicals, Inc.
Mercury methylation in mine wastes collected from abandoned mercury mines in the USA
Gray, J.E.; Hines, M.E.; Biester, H.; Lasorsa, B.K.; ,
2003-01-01
Speciation and transformation of Hg was studied in mine wastes collected from abandoned Hg mines at McDermitt, Nevada, and Terlingua, Texas, to evaluate formation of methyl-Hg, which is highly toxic. In these mine wastes, we measured total Hg and methyl-Hg contents, identified various Hg compounds using a pyrolysis technique, and determined rates of Hg methylation and methyl-Hg demethylation using isotopic-tracer methods. Mine wastes contain total Hg contents as high as 14000 ??g/g and methyl-Hg concentrations as high as 88 ng/g. Mine wastes were found to contain variable amounts of cinnabar, metacinnabar, Hg salts, Hg0, and Hg0 and Hg2+ sorbed onto matrix particulates. Samples with Hg0 and matrix-sorbed Hg generally contained significant methyl-Hg contents. Similarly, samples containing Hg0 compounds generally produced significant Hg methylation rates, as much as 26%/day. Samples containing mostly cinnabar showed little or no Hg methylation. Mine wastes with high methyl-Hg contents generally showed low methyl-Hg demethylation, suggesting that Hg methylation was dominant. Methyl-Hg demethylation was by both oxidative and microbial pathways. The correspondence of mine wastes containing Hg0 compounds and measured Hg methylation suggests that Hg0 oxidizes to Hg2+, which is subsequently bioavailable for microbial Hg methylation.
Su, Chang; Wang, Chao; He, Lin; Yang, Chuanping; Wang, Yucheng
2014-01-01
DNA methylation plays a critical role in the regulation of gene expression. Most studies of DNA methylation have been performed in herbaceous plants, and little is known about the methylation patterns in tree genomes. In the present study, we generated a map of methylated cytosines at single base pair resolution for Betula platyphylla (white birch) by bisulfite sequencing combined with transcriptomics to analyze DNA methylation and its effects on gene expression. We obtained a detailed view of the function of DNA methylation sequence composition and distribution in the genome of B. platyphylla. There are 34,460 genes in the whole genome of birch, and 31,297 genes are methylated. Conservatively, we estimated that 14.29% of genomic cytosines are methylcytosines in birch. Among the methylation sites, the CHH context accounts for 48.86%, and is the largest proportion. Combined transcriptome and methylation analysis showed that the genes with moderate methylation levels had higher expression levels than genes with high and low methylation. In addition, methylated genes are highly enriched for the GO subcategories of binding activities, catalytic activities, cellular processes, response to stimulus and cell death, suggesting that methylation mediates these pathways in birch trees. PMID:25514241
CpG island methylator phenotype in colorectal cancer
Toyota, Minoru; Ahuja, Nita; Ohe-Toyota, Mutsumi; Herman, James G.; Baylin, Stephen B.; Issa, Jean-Pierre J.
1999-01-01
Aberrant methylation of promoter region CpG islands is associated with transcriptional inactivation of tumor-suppressor genes in neoplasia. To understand global patterns of CpG island methylation in colorectal cancer, we have used a recently developed technique called methylated CpG island amplification to examine 30 newly cloned differentially methylated DNA sequences. Of these 30 clones, 19 (63%) were progressively methylated in an age-dependent manner in normal colon, 7 (23%) were methylated in a cancer-specific manner, and 4 (13%) were methylated only in cell lines. Thus, a majority of CpG islands methylated in colon cancer are also methylated in a subset of normal colonic cells during the process of aging. In contrast, methylation of the cancer-specific clones was found exclusively in a subset of colorectal cancers, which appear to display a CpG island methylator phenotype (CIMP). CIMP+ tumors also have a high incidence of p16 and THBS1 methylation, and they include the majority of sporadic colorectal cancers with microsatellite instability related to hMLH1 methylation. We thus define a pathway in colorectal cancer that appears to be responsible for the majority of sporadic tumors with mismatch repair deficiency. PMID:10411935
Nonparametric Bayesian clustering to detect bipolar methylated genomic loci.
Wu, Xiaowei; Sun, Ming-An; Zhu, Hongxiao; Xie, Hehuang
2015-01-16
With recent development in sequencing technology, a large number of genome-wide DNA methylation studies have generated massive amounts of bisulfite sequencing data. The analysis of DNA methylation patterns helps researchers understand epigenetic regulatory mechanisms. Highly variable methylation patterns reflect stochastic fluctuations in DNA methylation, whereas well-structured methylation patterns imply deterministic methylation events. Among these methylation patterns, bipolar patterns are important as they may originate from allele-specific methylation (ASM) or cell-specific methylation (CSM). Utilizing nonparametric Bayesian clustering followed by hypothesis testing, we have developed a novel statistical approach to identify bipolar methylated genomic regions in bisulfite sequencing data. Simulation studies demonstrate that the proposed method achieves good performance in terms of specificity and sensitivity. We used the method to analyze data from mouse brain and human blood methylomes. The bipolar methylated segments detected are found highly consistent with the differentially methylated regions identified by using purified cell subsets. Bipolar DNA methylation often indicates epigenetic heterogeneity caused by ASM or CSM. With allele-specific events filtered out or appropriately taken into account, our proposed approach sheds light on the identification of cell-specific genes/pathways under strong epigenetic control in a heterogeneous cell population.
Keller, Thomas E; Han, Priscilla; Yi, Soojin V
2016-04-01
Genomes of invertebrates and vertebrates exhibit highly divergent patterns of DNA methylation. Invertebrate genomes tend to be sparsely methylated, and DNA methylation is mostly targeted to a subset of transcription units (gene bodies). In a drastic contrast, vertebrate genomes are generally globally and heavily methylated, punctuated by the limited local hypo-methylation of putative regulatory regions such as promoters. These genomic differences also translate into functional differences in DNA methylation and gene regulation. Although promoter DNA methylation is an important regulatory component of vertebrate gene expression, its role in invertebrate gene regulation has been little explored. Instead, gene body DNA methylation is associated with expression of invertebrate genes. However, the evolutionary steps leading to the differentiation of invertebrate and vertebrate genomic DNA methylation remain unresolved. Here we analyzed experimentally determined DNA methylation maps of several species across the invertebrate-vertebrate boundary, to elucidate how vertebrate gene methylation has evolved. We show that, in contrast to the prevailing idea, a substantial number of promoters in an invertebrate basal chordate Ciona intestinalis are methylated. Moreover, gene expression data indicate significant, epigenomic context-dependent associations between promoter methylation and expression in C. intestinalis. However, there is no evidence that promoter methylation in invertebrate chordate has been evolutionarily maintained across the invertebrate-vertebrate boundary. Rather, body-methylated invertebrate genes preferentially obtain hypo-methylated promoters among vertebrates. Conversely, promoter methylation is preferentially found in lineage- and tissue-specific vertebrate genes. These results provide important insights into the evolutionary origin of epigenetic regulation of vertebrate gene expression. © The Author(s) 2015. Published by Oxford University Press on behalf of the Society for Molecular Biology and Evolution.
Controlling DNA methylation: many roads to one modification.
Freitag, Michael; Selker, Eric U
2005-04-01
Genetic, biochemical and cytological studies on DNA methylation in several eukaryotic organisms have resulted in leaps of understanding in the past three years. Discoveries of mechanistic links between DNA methylation and histone methylation, and between these processes and RNA interference (RNAi) machineries have reinvigorated the field. The details of the connections between DNA methylation, histone modifications and RNA silencing remain to be elucidated, but it is already clear that no single pathway accounts for all DNA methylation found in eukaryotes. Rather, different taxa use one or more of several general mechanisms to control methylation. Despite recent progress, classic questions remain, including: What are the signals for DNA methylation? Are "de novo" and "maintenance" methylation truly separate processes? How is DNA methylation regulated?
Code of Federal Regulations, 2010 CFR
2010-07-01
...-; benzenamine, 4-chloro-2-methyl-, hydrochloride; and ben-zenamine, 2-chloro-6-methyl-. 721.1025 Section 721... Benzenamine, 4-chloro-2-methyl-; benzenamine, 4-chloro-2-methyl-, hydrochloride; and ben-zenamine, 2-chloro-6...-, hydrochloride (CAS Number 3165-93-3); and benzenamine, 2-chloro-6-methyl- (CAS Number 87-63-8) are subject to...
RF-plasma vapor deposition of siloxane on paper. Part 1: Physical evolution of paper surface
NASA Astrophysics Data System (ADS)
Sahin, Halil Turgut
2013-01-01
An alternative, new approach to improve the hydrophobicity and barrier properties of paper was evaluated by radio-frequency (RF) plasma octamethylcyclotetrasiloxane (OMCTSO) vapor treatment. The interaction between OMCTSO and paper, causing the increased hydophobicity, is likely through covalent bonding. The deposited thin silicone-like polymeric layer from OMCTSO plasma treatment possessed desirable hydrophobic properties. The SEM micrographs showed uniformly distributed grainy particles with various shapes on the paper surface. Deposition of the silicone polymer-like layer with the plasma treatment affects the distribution of voids in the network structure and increases the barrier against water intake and air. The water absorptivity was reduced by 44% for the OMCTSO plasma treated sheet. The highest resistance to air flow was an approximately 41% lower air permeability than virgin paper.
Patterning Methods for Polymers in Cell and Tissue Engineering
Kim, Hong Nam; Kang, Do-Hyun; Kim, Min Sung; Jiao, Alex; Kim, Deok-Ho; Suh, Kahp-Yang
2017-01-01
Polymers provide a versatile platform for mimicking various aspects of physiological extracellular matrix properties such as chemical composition, rigidity, and topography for use in cell and tissue engineering applications. In this review, we provide a brief overview of patterning methods of various polymers with a particular focus on biocompatibility and processability. The materials highlighted here are widely used polymers including thermally curable polydimethyl siloxane, ultraviolet-curable polyurethane acrylate and polyethylene glycol, thermo-sensitive poly(N-isopropylacrylamide) and thermoplastic and conductive polymers. We also discuss how micro- and nanofabricated polymeric substrates of tunable elastic modulus can be used to engineer cell and tissue structure and function. Such synergistic effect of topography and rigidity of polymers may be able to contribute to constructing more physiologically relevant microenvironment. PMID:22258887
Evaluation of advanced bladder technology
NASA Technical Reports Server (NTRS)
Christensen, M. V.; Pasternak, R. A.
1972-01-01
Research conducted during this period is reported. Studies presented include: (1) diffusion and permeation of CO2, O2, N2, and NO2 through polytetra fluoroethylene; (2) diffusion, permeation and solubility of simple gases (CO2, O2, N2, CH4, C2H6, C3H8, and C2H4) through a copolymer of hexafluoro propylene and tetrafluoro ethylene (FEP); (3) viscous flow and diffusion of gases throug small apertures; (4) diffusion and permeation of O2, N2, CO2, CH4, C2H6, and C3H8 through nitroso rubber; and (5) results of gas transport studies with carborane siloxane, nitroso rubber, silicone membrane, krytox coating on teflon, and FEP coated glass cloth. Publications generated under this program are listed.
3D Printed Silicones with Shape Memory
Wu, Amanda S.; Small IV, Ward; Bryson, Taylor M.; ...
2017-07-05
Direct ink writing enables the layer-by-layer manufacture of ordered, porous structures whose mechanical behavior is driven by architecture and material properties. Here, we incorporate two different gas filled microsphere pore formers to evaluate the effect of shell stiffness and T g on compressive behavior and compression set in siloxane matrix printed structures. The lower T g microsphere structures exhibit substantial compression set when heated near and above T g, with full structural recovery upon reheating without constraint. By contrast, the higher T g microsphere structures exhibit reduced compression set with no recovery upon reheating. Aside from their role in tuningmore » the mechanical behavior of direct ink write structures, polymer microspheres are good candidates for shape memory elastomers requiring structural complexity, with potential applications toward tandem shape memory polymers.« less
Survey of inorganic polymers. [for composite matrix resins
NASA Technical Reports Server (NTRS)
Gerber, A. H.; Mcinerney, E. F.
1979-01-01
A literature search was carried out in order to identify inorganic, metallo-organic, and hybrid inorganic-organic polymers that could serve as potential matrix resins for advanced composites. The five most promising candidates were critically reviewed and recommendations were made for the achievement of their potential in terms of performance and cost. These generic polymer classes comprise: (1) Poly(arylsil sesquioxanes); (2) Poly(silyl arylene siloxanes); (3) Poly(silarylenes); (4) Poly(silicon-linked ferrocenes); and (5) Poly(organo phosphazenes). No single candidate currently possesses the necessary combination of physicomechanical properties, thermal stability, processability, and favorable economics. The first three classes exhibit the best thermal performance. On the other hand, poly (organo phosphazenes), the most extensively studied polymer class, exhibit the best combination of structure-property control, processability, and favorable economics.
Nakagawa, Hiroyuki; Kitagawa, Shinya; Araki, Shuki; Ohtani, Hajime
2006-02-01
Several alkyl benzenes are separated by pressurized flow-driven capillary electrochromatography using a temperature-controlled capillary column packed with octadecyl siloxane-modified silica gel, and the effect of applied voltage on the retention is investigated. The van't Hoff plot shows good linearity at the column temperature between 305 and 330 K under applications from -6 to +6 kV. The applied voltage causes a relatively large variation in the enthalpy and the entropy of transfer of the solute from the mobile phase to the stationary phase (> 20%). However, the direction of variation in the enthalpy is almost opposite to that in the entropy, both of which might compensate each other. Therefore, the retention factor is not significantly varied (< 4%) by the application of voltage.
Molecular receptors in metal oxide sol-gel materials prepared via molecular imprinting
Sasaki, Darryl Y.; Brinker, C. Jeffrey; Ashley, Carol S.; Daitch, Charles E.; Shea, Kenneth J.; Rush, Daniel J.
2000-01-01
A method is provided for molecularly imprinting the surface of a sol-gel material, by forming a solution comprised of a sol-gel material, a solvent, an imprinting molecule, and a functionalizing siloxane monomer of the form Si(OR).sub.3-n X.sub.n, wherein n is an integer between zero and three and X is a functional group capable of reacting with the imprinting molecule, evaporating the solvent, and removing the imprinting molecule to form the molecularly imprinted metal oxide sol-gel material. The use of metal oxide sol-gels allows the material porosity, pore size, density, surface area, hardness, electrostatic charge, polarity, optical density, and surface hydrophobicity to be tailored and be employed as sensors and in catalytic and separations operations.
Intrinsic Hydrophobicity of Rammed Earth
NASA Astrophysics Data System (ADS)
Holub, M.; Stone, C.; Balintova, M.; Grul, R.
2015-11-01
Rammed earth is well known for its vapour diffusion properties, its ability to regulate humidity within the built environment. Rammed earth is also an aesthetically iconic material such as marble or granite and therefore is preferably left exposed. However exposed rammed earth is often coated with silane/siloxane water repellents or the structure is modified architecturally (large roof overhangs) to accommodate for the hydrophilic nature of the material. This paper sets out to find out optimal hydrophobicity for rammed earth based on natural composite fibres and surface coating without adversely affecting the vapour diffusivity of the material. The material is not required to be waterproof, but should resist at least driving rain. In order to evaluate different approaches to increase hydrophobicity of rammed earth surface, peat fibres and four types of repellents were used.
NASA Astrophysics Data System (ADS)
Tewari, Amit; Gandla, Srinivas; Pininti, Anil Reddy; Karuppasamy, K.; Böhm, Siva; Bhattacharyya, Arup R.; McNeill, Christopher R.; Gupta, Dipti
2015-09-01
This paper reports the fabrication of pentacene-based organic thin-film transistors using a dielectric material, Dynasylan ®SIVO110. The devices exhibit excellent performance characterized by a low threshold voltage of -1.4 V (operating voltage: 0 to -4 V) together with a mobility of 1.9 cm2 V-1s-1. These results are promising because it uses only a single layer of dielectric without performing any intermediate treatment. The reason is attributed to the high charge storage capacity of the dielectric (κ ˜ 20.02), a low interfacial trap density (2.56 × 1011cm-2), and favorable pentacene film morphology consisting of large and interconnected grains having an average size of 234 nm.