Balancing strength and toughness of calcium-silicate-hydrate via random nanovoids and particle inclusions: Atomistic modeling and statistical analysis

NASA Astrophysics Data System (ADS)

Zhang, Ning; Shahsavari, Rouzbeh

2016-11-01

As the most widely used manufactured material on Earth, concrete poses serious societal and environmental concerns which call for innovative strategies to develop greener concrete with improved strength and toughness, properties that are exclusive in man-made materials. Herein, we focus on calcium silicate hydrate (C-S-H), the major binding phase of all Portland cement concretes, and study how engineering its nanovoids and portlandite particle inclusions can impart a balance of strength, toughness and stiffness. By performing an extensive +600 molecular dynamics simulations coupled with statistical analysis tools, our results provide new evidence of ductile fracture mechanisms in C-S-H - reminiscent of crystalline alloys and ductile metals - decoding the interplay between the crack growth, nanovoid/particle inclusions, and stoichiometry, which dictates the crystalline versus amorphous nature of the underlying matrix. We found that introduction of voids and portlandite particles can significantly increase toughness and ductility, specially in C-S-H with more amorphous matrices, mainly owing to competing mechanisms of crack deflection, voids coalescence, internal necking, accommodation, and geometry alteration of individual voids/particles, which together regulate toughness versus strength. Furthermore, utilizing a comprehensive global sensitivity analysis on random configuration-property relations, we show that the mean diameter of voids/particles is the most critical statistical parameter influencing the mechanical properties of C-S-H, irrespective of stoichiometry or crystalline or amorphous nature of the matrix. This study provides new fundamental insights, design guidelines, and de novo strategies to turn the brittle C-S-H into a ductile material, impacting modern engineering of strong and tough concrete infrastructures and potentially other complex brittle materials.

Bioactive calcium phosphate–based glasses and ceramics and their biomedical applications: A review

PubMed Central

Islam, Md Towhidul; Felfel, Reda M; Abou Neel, Ensanya A; Grant, David M; Ahmed, Ifty; Hossain, Kazi M Zakir

2017-01-01

An overview of the formation of calcium phosphate under in vitro environment on the surface of a range of bioactive materials (e.g. from silicate, borate, and phosphate glasses, glass-ceramics, bioceramics to metals) based on recent literature is presented in this review. The mechanism of bone-like calcium phosphate (i.e. hydroxyapatite) formation and the test protocols that are either already in use or currently being investigated for the evaluation of the bioactivity of biomaterials are discussed. This review also highlights the effect of chemical composition and surface charge of materials, types of medium (e.g. simulated body fluid, phosphate-buffered saline and cell culture medium) and test parameters on their bioactivity performance. Finally, a brief summary of the biomedical applications of these newly formed calcium phosphate (either in the form of amorphous or apatite) is presented. PMID:28794848

Spinodal decomposition in amorphous metal-silicate thin films: Phase diagram analysis and interface effects on kinetics

NASA Astrophysics Data System (ADS)

Kim, H.; McIntyre, P. C.

2002-11-01

Among several metal silicate candidates for high permittivity gate dielectric applications, the mixing thermodynamics of the ZrO2-SiO2 system were analyzed, based on previously published experimental phase diagrams. The driving force for spinodal decomposition was investigated in an amorphous silicate that was treated as a supercooled liquid solution. A subregular model was used for the excess free energy of mixing of the liquid, and measured invariant points were adopted for the calculations. The resulting simulated ZrO2-SiO2 phase diagram matched the experimental results reasonably well and indicated that a driving force exists for amorphous Zr-silicate compositions between approx40 mol % and approx90 mol % SiO2 to decompose into a ZrO2-rich phase (approx20 mol % SiO2) and SiO2-rich phase (>98 mol % SiO2) through diffusional phase separation at a temperature of 900 degC. These predictions are consistent with recent experimental reports of phase separation in amorphous Zr-silicate thin films. Other metal-silicate systems were also investigated and composition ranges for phase separation in amorphous Hf, La, and Y silicates were identified from the published bulk phase diagrams. The kinetics of one-dimensional spinodal decomposition normal to the plane of the film were simulated for an initially homogeneous Zr-silicate dielectric layer. We examined the effects that local stresses and the capillary driving force for component segregation to the interface have on the rate of spinodal decomposition in amorphous metal-silicate thin films.

Thermochemistry of amorphous and crystalline zirconium and hafnium silicates.

NASA Astrophysics Data System (ADS)

Ushakov, S.; Brown, C. E.; Navrotsky, Alexandra; Boatner, L. A.; Demkov, A. A.; Wang, C.; Nguyen, B.-Y.

2003-03-01

Calorimetric investigation of amorphous and crystalline zirconium and hafnium silicates was performed as part of a research program on thermochemistry of alternative gate dielectrics. Amorphous hafnium and zirconium silicates with varying SiO2 content were synthesized by a sol-gel process. Crystalline zirconium and hafnium silicates (zircon and hafnon) were synthesized by solid state reaction at 1450 °C from amorphous gels and grown as single crystals from flux. High temperature oxide melt solution calorimetry in lead borate (2PbO.B2O3) solvent at 800 oC was used to measure drop solution enthalpies for amorphous and crystalline zirconium and hafnium silicates and corresponding oxides. Applying appropriate thermochemical cycles, formation enthalpy of crystalline ZrSiO4 (zircon) from binary oxides (baddeleite and quartz) at 298 K was calculated as -23 +/-2 kJ/mol and enthalpy difference between amorphous and crystalline zirconium silicate (vitrification enthalpy) was found to be 61 +/-3 kJ/mol. Crystallization onset temperatures of amorphous zirconium and hafnium silicates, as measured by differential scanning calorimetry (DSC), increased with silica content. The resulting crystalline phases, as characterized by X-ray diffraction (XRD), were tetragonal HfO2 and ZrO2. Critical crystallite size for tetragonal to monoclinic transformation of HfO2 in the gel was estimated as 6 +/-2 nm from XRD data Crystallization enthalpies per mole of hafnia and zirconia in gels decrease slightly together with crystallite size with increasing silica content, for example from -22 to -15 +/-1 kJ per mol of HfO2 crystallized at 740 and 1006 °C from silicates with 10 and 70 mol Applications of thermal analyses and solution calorimetry techniques together with first-principles density functional calculations to estimate interface and surface energies are discussed.

COHESION OF AMORPHOUS SILICA SPHERES: TOWARD A BETTER UNDERSTANDING OF THE COAGULATION GROWTH OF SILICATE DUST AGGREGATES

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

Kimura, Hiroshi; Wada, Koji; Senshu, Hiroki

2015-10-10

Adhesion forces between submicrometer-sized silicate grains play a crucial role in the formation of silicate dust agglomerates, rocky planetesimals, and terrestrial planets. The surface energy of silicate dust particles is the key to their adhesion and rolling forces in a theoretical model based on contact mechanics. Here we revisit the cohesion of amorphous silica spheres by compiling available data on the surface energy for hydrophilic amorphous silica in various circumstances. It turned out that the surface energy for hydrophilic amorphous silica in a vacuum is a factor of 10 higher than previously assumed. Therefore, the previous theoretical models underestimated themore » critical velocity for the sticking of amorphous silica spheres, as well as the rolling friction forces between them. With the most plausible value of the surface energy for amorphous silica spheres, theoretical models based on the contact mechanics are in harmony with laboratory experiments. Consequently, we conclude that silicate grains with a radius of 0.1 μm could grow to planetesimals via coagulation in a protoplanetary disk. We argue that the coagulation growth of silicate grains in a molecular cloud is advanced either by organic mantles rather than icy mantles or, if there are no mantles, by nanometer-sized grain radius.« less

Tableting properties of silica aerogel and other silicates.

PubMed

Hentzschel, C M; Alnaief, M; Smirnova, I; Sakmann, A; Leopold, C S

2012-04-01

In solid oral dosage forms silicates are commonly used as glidants in low concentration. However, due to their large specific surface area, silicates may also be used as carrier materials for drugs. Moreover, silicates allow amorphisation of drugs by co-grinding or processing with supercritical fluids. The aim of this study was to investigate the physical and the tableting properties of Silica Aerogel (special type of silica with an extremely large specific surface area), Neusilin(®) US2 (magnesium aluminometasilicate), Florite(®) (calcium silicate) and Aerosil(®) 200 (colloidal silica). Powder blends of Avicel(®) PH102 (microcrystalline cellulose) and different amounts of the respective silicate were compacted and analyzed for their tabletability (tensile strength vs. compaction pressure) as well as their Heckel plot. With Neusilin(®) the tabletability appeared to be independent of the silicate concentration, whereas with Florite(®) an increasing silicate concentration led to a higher tensile strength. In contrast, the addition of Silica Aerogel and Aerosil(®) resulted in a decrease of the tensile strength. With Aerosil(®) a maximum tolerable concentration of 20% [w/w] was determined. Plastic deformation of all powder blends decreased with increasing silicate concentration. This effect was most pronounced with Aerosil(®) and least with Florite(®). Tablets with acceptable tensile strength were obtained with all plain silicates except for Aerosil(®). Therefore, these silicates may be used in tablet formulations, e.g. as carrier materials for liquid or amorphous drugs.

Early Age Carbonation Heat and Products of Tricalcium Silicate Paste Subject to Carbon Dioxide Curing

PubMed Central

Li, Zhen; He, Zhen; Shao, Yixin

2018-01-01

This paper presents a study on the carbonation reaction heat and products of tricalcium silicate (C3S) paste exposed to carbon dioxide (CO2) for rapid curing. Reaction heat was measured using a retrofitted micro-calorimeter. The highest heat flow of a C3S paste subject to carbonation curing was 200 times higher than that by hydration, and the cumulative heat released by carbonation was three times higher. The compressive strength of a C3S paste carbonated for 2 h and 24 h was 27.5 MPa and 62.9 MPa, respectively. The 24-h carbonation strength had exceeded the hydration strength at 28 days. The CO2 uptake of a C3S paste carbonated for 2 h and 24 h was 17% and 26%, respectively. The X-ray diffraction (XRD), transmission electron microscope coupled with energy dispersive spectrometer (TEM-EDS), and 29Si magic angle spinning–nuclear magnetic resonance (29Si MAS-NMR) results showed that the products of a carbonated C3S paste were amorphous silica (SiO2) and calcite crystal. There was no trace of calcium silicate hydrate (C–S–H) or other polymorphs of calcium carbonate (CaCO3) detected. PMID:29734681

Measurement of the efficacy of calcium silicate for the protection and repair of dental enamel.

PubMed

Parker, Alexander S; Patel, Anisha N; Al Botros, Rehab; Snowden, Michael E; McKelvey, Kim; Unwin, Patrick R; Ashcroft, Alexander T; Carvell, Mel; Joiner, Andrew; Peruffo, Massimo

2014-06-01

To investigate the formation of hydroxyapatite (HAP) from calcium silicate and the deposition of calcium silicate onto sound and acid eroded enamel surfaces in order to investigate its repair and protective properties. Calcium silicate was mixed with phosphate buffer for seven days and the resulting solids analysed for crystalline phases by Raman spectroscopy. Deposition studies were conducted on bovine enamel surfaces. Acid etched regions were produced on the enamel surfaces using scanning electrochemical cell microscopy (SECCM) with acid filled pipettes and varying contact times. Following treatment with calcium silicate, the deposition was visualised with FE-SEM and etch pit volumes were measured by AFM. A second set of bovine enamel specimens were pre-treated with calcium silicate and fluoride, before acid exposure with the SECCM. The volumes of the resultant acid etched pits were measured using AFM and the intrinsic rate constant for calcium loss was calculated. Raman spectroscopy confirmed that HAP was formed from calcium silicate. Deposition studies demonstrated greater delivery of calcium silicate to acid eroded than sound enamel and that the volume of acid etched enamel pits was significantly reduced following one treatment (p<0.05). In the protection study, the intrinsic rate constant for calcium loss from enamel was 0.092 ± 0.008 cm/s. This was significantly reduced, 0.056 ± 0.005 cm/s, for the calcium silicate treatments (p<0.0001). Calcium silicate can transform into HAP and can be deposited on acid eroded and sound enamel surfaces. Calcium silicate can provide significant protection of sound enamel from acid challenges. Calcium silicate is a material that has potential for a new approach to the repair of demineralised enamel and the protection of enamel from acid attacks, leading to significant dental hard tissue benefits. © 2014 Elsevier Ltd. All rights reserved.

21 CFR 182.2122 - Aluminum calcium silicate.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Aluminum calcium silicate. 182.2122 Section 182.2122 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED....2122 Aluminum calcium silicate. (a) Product. Aluminum calcium silicate. (b) Tolerance. 2 percent. (c...

21 CFR 182.2122 - Aluminum calcium silicate.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Aluminum calcium silicate. 182.2122 Section 182.2122 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED....2122 Aluminum calcium silicate. (a) Product. Aluminum calcium silicate. (b) Tolerance. 2 percent. (c...

21 CFR 582.2122 - Aluminum calcium silicate.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 6 2011-04-01 2011-04-01 false Aluminum calcium silicate. 582.2122 Section 582.2122 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED....2122 Aluminum calcium silicate. (a) Product. Aluminum calcium silicate. (b) Tolerance. 2 percent. (c...

21 CFR 582.2122 - Aluminum calcium silicate.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Aluminum calcium silicate. 582.2122 Section 582.2122 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED....2122 Aluminum calcium silicate. (a) Product. Aluminum calcium silicate. (b) Tolerance. 2 percent. (c...

21 CFR 582.2227 - Calcium silicate.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Calcium silicate. 582.2227 Section 582.2227 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Calcium silicate. (a) Product. Calcium silicate. (b) Tolerance. 2 percent and 5 percent. (c) Limitations...

21 CFR 582.2227 - Calcium silicate.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 6 2011-04-01 2011-04-01 false Calcium silicate. 582.2227 Section 582.2227 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Calcium silicate. (a) Product. Calcium silicate. (b) Tolerance. 2 percent and 5 percent. (c) Limitations...

21 CFR 582.2122 - Aluminum calcium silicate.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 21 Food and Drugs 6 2012-04-01 2012-04-01 false Aluminum calcium silicate. 582.2122 Section 582.2122 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED....2122 Aluminum calcium silicate. (a) Product. Aluminum calcium silicate. (b) Tolerance. 2 percent. (c...

21 CFR 582.2227 - Calcium silicate.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 6 2014-04-01 2014-04-01 false Calcium silicate. 582.2227 Section 582.2227 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Calcium silicate. (a) Product. Calcium silicate. (b) Tolerance. 2 percent and 5 percent. (c) Limitations...

21 CFR 182.2122 - Aluminum calcium silicate.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Aluminum calcium silicate. 182.2122 Section 182.2122 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED....2122 Aluminum calcium silicate. (a) Product. Aluminum calcium silicate. (b) Tolerance. 2 percent. (c...

21 CFR 582.2122 - Aluminum calcium silicate.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 6 2014-04-01 2014-04-01 false Aluminum calcium silicate. 582.2122 Section 582.2122 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED....2122 Aluminum calcium silicate. (a) Product. Aluminum calcium silicate. (b) Tolerance. 2 percent. (c...

21 CFR 582.2227 - Calcium silicate.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 21 Food and Drugs 6 2012-04-01 2012-04-01 false Calcium silicate. 582.2227 Section 582.2227 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Calcium silicate. (a) Product. Calcium silicate. (b) Tolerance. 2 percent and 5 percent. (c) Limitations...

21 CFR 582.2122 - Aluminum calcium silicate.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 21 Food and Drugs 6 2013-04-01 2013-04-01 false Aluminum calcium silicate. 582.2122 Section 582.2122 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED....2122 Aluminum calcium silicate. (a) Product. Aluminum calcium silicate. (b) Tolerance. 2 percent. (c...

21 CFR 182.2227 - Calcium silicate.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Calcium silicate. 182.2227 Section 182.2227 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) SUBSTANCES GENERALLY RECOGNIZED AS SAFE Anticaking Agents § 182.2227 Calcium silicate. (a) Product. Calcium silicate...

21 CFR 582.2227 - Calcium silicate.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 21 Food and Drugs 6 2013-04-01 2013-04-01 false Calcium silicate. 582.2227 Section 582.2227 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Calcium silicate. (a) Product. Calcium silicate. (b) Tolerance. 2 percent and 5 percent. (c) Limitations...

21 CFR 182.2122 - Aluminum calcium silicate.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Aluminum calcium silicate. 182.2122 Section 182...) SUBSTANCES GENERALLY RECOGNIZED AS SAFE Anticaking Agents § 182.2122 Aluminum calcium silicate. (a) Product. Aluminum calcium silicate. (b) Tolerance. 2 percent. (c) Limitations, restrictions, or explanation. This...

21 CFR 182.2122 - Aluminum calcium silicate.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Aluminum calcium silicate. 182.2122 Section 182.2122 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED....2122 Aluminum calcium silicate. (a) Product. Aluminum calcium silicate. (b) Tolerance. 2 percent. (c...

Amorphous Silicate Smokes as Catalysts for the Production of Complex Organic Species in the Primitive Solar Nebula

NASA Technical Reports Server (NTRS)

Nuth, J. A., III; Hill, H. G. M.

2002-01-01

Amorphous Mg-silicates are excellent Fischer-Tropsch catalysts that convert H2 and CO into hydrocarbons almost as well as Fe-silicates. Mg-silicates do not catalyze formation of ammonia. N is incorporated into the organics if CO, N2 and H2 are used. Additional information is contained in the original extended abstract.

21 CFR 182.2227 - Calcium silicate.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Calcium silicate. 182.2227 Section 182.2227 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR... Calcium silicate. (a) Product. Calcium silicate. (b) Tolerance. 2 percent and 5 percent. (c) Limitations...

21 CFR 182.2227 - Calcium silicate.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Calcium silicate. 182.2227 Section 182.2227 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR... Calcium silicate. (a) Product. Calcium silicate. (b) Tolerance. 2 percent and 5 percent. (c) Limitations...

21 CFR 182.2227 - Calcium silicate.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Calcium silicate. 182.2227 Section 182.2227 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR... Calcium silicate. (a) Product. Calcium silicate. (b) Tolerance. 2 percent and 5 percent. (c) Limitations...

21 CFR 182.2227 - Calcium silicate.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Calcium silicate. 182.2227 Section 182.2227 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR... Calcium silicate. (a) Product. Calcium silicate. (b) Tolerance. 2 percent and 5 percent. (c) Limitations...

Mineralogical Characterization of Fe-Bearing AGB and Supernova Silicate Grains From the Queen Alexandra Range 99177 Meteorite

NASA Technical Reports Server (NTRS)

Nguyen, A. N.; Keller, L. P.; Messenger, S.; Rahman, Z.

2017-01-01

Spectroscopic observations of the circumstellar envelopes of evolved O-rich stars indicate the dust is mostly amorphous silicate with olivine-like compositions. Spectral modeling suggests these grains are Fe-rich [Mg/(Mg+Fe) 0.5], but it is not known whether the Fe is distributed within the silicate matrix or exists as metal inclusions. In contrast, the crystalline silicates are inferred to be extremely Mg-rich [Mg/(Mg+Fe) > 0.95]. The mineralogies and chemical compositions of dust in supernova (SN) remnants are not as well constrained, but abundant silicates of olivine-like and enstatite-like compositions have been fit to the infrared emission features. Silicates in the interstellar medium (ISM) are >99% amor-phous and Fe-bearing. The dearth of crystalline silicates in the ISM requires that some amorphization or destruction mechanisms process these grains.

Calcium silicate-based drug delivery systems.

PubMed

Zhu, Ying-Jie; Guo, Xiao-Xuan; Sham, Tsun-Kong

2017-02-01

Compared with other inorganic materials such as silica, metal oxides, noble metals and carbon, calcium silicate-based materials, especially nanostructured calcium silicate materials, have high biocompatibility, bioactivity and biodegradability, high specific surface area, nanoporous/hollow structure, high drug-loading capacity, pH-responsive drug release behavior and desirable drug release properties, and thus they are promising for the application in drug delivery. Calcium silicate-based drug delivery systems have a long drug-release time, which can significantly prolong the therapeutic effect of drugs. Another advantage of calcium silicate-based drug delivery systems is their pH-responsive drug release property, which can act as an ideal platform for targeted drug delivery. Areas covered: In recent years, studies have been carried out on calcium silicate-based drug delivery systems, and important results and insights have been documented. This article is not intended to offer a comprehensive review on the research on calcium silicate-based drug delivery systems, but presents some examples reported in the literature, and includes new insights obtained by tracking the interactions between drug molecules and calcium silicate carriers on the molecular level using the synchrotron-based X-ray spectroscopy. Expert opinion: Finally, our opinions on calcium silicate-based drug delivery systems are provided, and several research directions for the future studies are proposed.

More Evidence of the Importance of Amorphous Silicates in CM Carbonaceous Chondrites: New Observations from a Fine-Grained Rim in the CM2 Chondrite, TIL 91722

NASA Astrophysics Data System (ADS)

Brearley, A. J.; Le Guillou, C.

2015-07-01

A fine-grained rim in TIL 91722 contains abundant amorphous silicate material containing nanophase sulfides. Phyllosilicates are rare. The amorphous material has a high ferric iron content indicative of oxidation coupled with hydration.

The Mineralogy of Circumstellar Silicates Preserved in Cometary Dust

NASA Technical Reports Server (NTRS)

Keller, L. P.; Messenger, S.

2010-01-01

Interplanetary dust particles (IDPs) contain a record of the building blocks of the solar system including presolar grains, molecular cloud material, and materials formed in the early solar nebula. Cometary IDPs have remained relatively unaltered since their accretion because of the lack of parent body thermal and aqueous alteration. We are using coordinated transmission electron microscope (TEM) and ion microprobe studies to establish the origins of the various components within cometary IDPs. Of particular interest is the nature and abundance of presolar silicates in these particles because astronomical observations suggest that crystalline and amorphous silicates are the dominant grain types produced in young main sequence stars and evolved O-rich stars. Five circumstellar grains have been identified including three amorphous silicate grains and two polycrystalline aggregates. All of these grains are between 0.2 and 0.5 micrometers in size. The isotopic compositions of all five presolar silicate grains fall within the range of presolar oxides and silicates, having large (17)O-enrichments and normal (18)O/(16)O ratios (Group 1 grains from AGB and RG stars). The amorphous silicates are chemically heterogeneous and contain nanophase FeNi metal and FeS grains in a Mg-silicate matrix. Two of the amorphous silicate grains are aggregates with subgrains showing variable Mg/Si ratios in chemical maps. The polycrystalline grains show annealed textures (equilibrium grains boundaries, uniform Mg/Fe ratios), and consist of 50-100 nm enstatite and pyrrhotite grains with lesser forsterite. One of the polycrystalline aggregates contains a subgrain of diopside. The polycrystalline aggregates form by subsolidus annealing of amorphous precursors. The bulk compositions of the five grains span a wide range in Mg/Si ratios from 0.4 to 1.2 (avg. 0.86). The average Fe/Si (0.40) and S/Si (0.21) ratios show a much narrower range of values and are approximately 50% of their solar abundances. The latter observation may indicate a decoupling of the silicate and sulfide components in grains that condense in stellar outflows. The amorphous silicate grains described here were not extensively affected by irradiation, sputtering, or thermal processing and may represent relatively pristine circumstellar grains. They are strong candidates for the "dirty silicates" in astronomical observations of circumstellar dust shells. The polycrystalline grains were originally amorphous silicate grains that were likely annealed in the early solar nebula but the processing was not sufficient to erase their anomalous oxygen isotopic compositions.

Gas/solid carbon branching ratios in surface-mediated reactions and the incorporation of carbonaceous material into planetesimals

PubMed Central

Nuth, Joseph A.; Johnson, Natasha M.; Ferguson, Frank T.; Carayon, Alicia

2018-01-01

We report the ratio of the initial carbon available as CO that forms gas-phase compounds compared to the fraction that deposits as a carbonaceous solid (the gas/solid branching ratio) as a function of time and temperature for iron, magnetite, and amorphous iron silicate smoke catalysts during surface-mediated reactions in an excess of hydrogen and in the presence of N2. This fraction varies from more than 99% for an amorphous iron silicate smoke at 673 K to less than 40% for a magnetite catalyst at 873 K. The CO not converted into solids primarily forms methane, ethane, water, and CO2, as well as a very wide range of organic molecules at very low concentration. Carbon deposits do not form continuous coatings on the catalytic surfaces, but instead form extremely high surface area per unit volume “filamentous” structures. While these structures will likely form more slowly but over much longer times in protostellar nebulae than in our experiments due to the much lower partial pressure of CO, such fluffy coatings on the surfaces of chondrules or calcium aluminum inclusions could promote grain–grain sticking during low-velocity collisions. PMID:29563766

Gas/Solid Carbon Branching Ratios in Surface Mediated Reactions and the Incorporation of Carbonaceous Material into Planetesimals

NASA Technical Reports Server (NTRS)

Nuth, Joseph A.; Johnson, Natasha M.; Ferguson, Frank T.; Carayon, Alicia

2016-01-01

We report the ratio of the initial carbon available as CO that forms gas-phase compounds compared to the fraction that deposits as a carbonaceous solid (the gas solid branching ratio) as a function of time and temperature for iron, magnetite, and amorphous iron silicate smoke catalysts during surface-mediated reactions in an excess of hydrogen and in the presence of N2. This fraction varies from more than 99 for an amorphous iron silicate smoke at 673 K to less than 40% for a magnetite catalyst at 873 K. The CO not converted into solids primarily forms methane, ethane, water, and CO2, as well as a very wide range of organic molecules at very low concentration. Carbon deposits do not form continuous coatings on the catalytic surfaces, but instead form extremely high surface area per unit volume filamentous structures. While these structures will likely form more slowly but over much longer times in protostellar nebulae than in our experiments due to the much lower partial pressure of CO, such fluffy coatings on the surfaces of chondrules or calcium aluminum inclusions could promote grain-grain sticking during low-velocity collisions.

Effect of temperature on hydration kinetics and polymerization of tricalcium silicate in stirred suspensions of CaO-saturated solutions

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

Grant, Steven A.; Boitnott, Ginger E.; Korhonen, Charles J.

2006-04-15

Tricalcium silicate was hydrated at 274, 278, 283, 298, and 313 K in stirred suspensions of saturated CaO solutions under a nitrogen-gas atmosphere until the end of deceleratory period. The suspension conductivities and energy flows were measured continuously. The individual reaction rates for tricalcium silicate dissolution, calcium silicate hydrate precipitation, and calcium hydroxide precipitation were calculated from these measurements. The results suggest that the proportion of tricalcium silicate dissolved was determined by the rate of tricalcium silicate dissolution and the time to very rapid calcium hydroxide precipitation. The time to very rapid calcium hydroxide precipitation was more sensitive to changesmore » in temperature than was the rate of tricalcium silicate dissolution, so that the proportion of tricalcium silicate hydration dissolved by the deceleratory period increased with decreasing temperature. The average chain length of the calcium silicate hydrate ascertained by magic-angle spinning nuclear magnetic resonance spectroscopy increased with increasing temperature.« less

40 CFR 721.10018 - Calcium hydroxide oxide silicate (Ca6(OH)2O2(Si2O5)3).

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Calcium hydroxide oxide silicate (Ca6... New Uses for Specific Chemical Substances § 721.10018 Calcium hydroxide oxide silicate (Ca6(OH)2O2... substance identified as calcium hydroxide oxide silicate (Ca6(OH)2O2(Si2O5)3) (PMN P-01-442; CAS No. 13169...

40 CFR 721.10018 - Calcium hydroxide oxide silicate (Ca6(OH)2O2(Si2O5)3).

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Calcium hydroxide oxide silicate (Ca6... New Uses for Specific Chemical Substances § 721.10018 Calcium hydroxide oxide silicate (Ca6(OH)2O2... substance identified as calcium hydroxide oxide silicate (Ca6(OH)2O2(Si2O5)3) (PMN P-01-442; CAS No. 13169...

40 CFR 721.10018 - Calcium hydroxide oxide silicate (Ca6(OH)2O2(Si2O5)3).

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Calcium hydroxide oxide silicate (Ca6... New Uses for Specific Chemical Substances § 721.10018 Calcium hydroxide oxide silicate (Ca6(OH)2O2... substance identified as calcium hydroxide oxide silicate (Ca6(OH)2O2(Si2O5)3) (PMN P-01-442; CAS No. 13169...

40 CFR 721.10018 - Calcium hydroxide oxide silicate (Ca6(OH)2O2(Si2O5)3).

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Calcium hydroxide oxide silicate (Ca6... New Uses for Specific Chemical Substances § 721.10018 Calcium hydroxide oxide silicate (Ca6(OH)2O2... substance identified as calcium hydroxide oxide silicate (Ca6(OH)2O2(Si2O5)3) (PMN P-01-442; CAS No. 13169...

40 CFR 721.10018 - Calcium hydroxide oxide silicate (Ca6(OH)2O2(Si2O5)3).

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Calcium hydroxide oxide silicate (Ca6... New Uses for Specific Chemical Substances § 721.10018 Calcium hydroxide oxide silicate (Ca6(OH)2O2... substance identified as calcium hydroxide oxide silicate (Ca6(OH)2O2(Si2O5)3) (PMN P-01-442; CAS No. 13169...

Production of geopolymers using glass produced from DC plasma treatment of air pollution control (APC) residues.

PubMed

Kourti, Ioanna; Rani, D Amutha; Deegan, D; Boccaccini, A R; Cheeseman, C R

2010-04-15

Air pollution control (APC) residues are the hazardous waste produced from cleaning gaseous emissions at energy-from-waste (EfW) facilities processing municipal solid waste (MSW). APC residues have been blended with glass-forming additives and treated using DC plasma technology to produce a high calcium alumino-silicate glass. This research has investigated the optimisation and properties of geopolymers prepared from this glass. Work has shown that high strength geopolymers can be formed and that the NaOH concentration of the activating solution significantly affects the properties. The broad particle size distribution of the APC residue glass used in these experiments results in a microstructure that contains unreacted glass particles included within a geopolymer binder phase. The high calcium content of APC residues may cause the formation of some amorphous calcium silicate hydrate (C-S-H) gel. A mix prepared with S/L=3.4, Si/Al=2.6 and [NaOH]=6M in the activating solution, produced high strength geopolymers with compressive strengths of approximately 130 MPa. This material had high density (2070 kg/m(3)) and low porosity. The research demonstrates for the first time that glass derived from DC plasma treatment of APC residues can be used to form high strength geopolymer-glass composites that have potential for use in a range of applications. 2009 Elsevier B.V. All rights reserved.

A comparative study of the continuum and emission characteristics of comet dust. 1: Are the silicates in Comet Halley and Kohoutek amorphous or crystalline

NASA Technical Reports Server (NTRS)

Nansheng, Zhao; Greenberg, J. Mayo; Hage, J. I.

1989-01-01

A continuum emission was subtracted from the 10 micron emission observed towards comets Halley and Kohoutek. The 10 micron excess emissions were compared with BN absorption and laboratory amorphous silicates. The results show that cometary silicates are predominantly amorphous which is consistent with the interstellar dust model of comets. It is concluded that cometary silicates are predominantly similar to interstellar silicates. For a periodic comet like Comet Halley, it is to be expected that some of the silicate may have been heated enough to convert to crystalline form. But apparently, this is only a small fraction of the total. A comparison of Comet Halley silicates with a combination of the crystalline forms observed in interplanetary dust particles (IPDs) seemed reasonable at first sight (Walker 1988, Brownlee 1988). But, if true, it would imply that the total silicate mass in Comet Halley dust is lower than that given by mass spectrometry data of Kissel and Krueger (1987). They estimated m sub org/m sub sil = 0.5 while using crystalline silicate to produce the 10 micron emission would give m sub org/m sub sil = 5 (Greenberg et al. 1988). This is a factor of 10 too high.

The utilization of waste by-products for removing silicate from mineral processing wastewater via chemical precipitation.

PubMed

Kang, Jianhua; Sun, Wei; Hu, Yuehua; Gao, Zhiyong; Liu, Runqing; Zhang, Qingpeng; Liu, Hang; Meng, Xiangsong

2017-11-15

This study investigates an environmentally friendly technology that utilizes waste by-products (waste acid and waste alkali liquids) to treat mineral processing wastewater. Chemical precipitation is used to remove silicate from scheelite (CaWO 4 ) cleaning flotation wastewater and the waste by-products are used as a substitute for calcium chloride (CaCl 2 ). A series of laboratory experiments is conducted to explain the removal of silicate and the characterization and formation mechanism of calcium silicate. The results show that silicate removal reaches 90% when the Ca:Si molar ratio exceeds 1.0. The X-ray diffraction (XRD) results confirm the characterization and formation of calcium silicate. The pH is the key factor for silicate removal, and the formation of polysilicic acid with a reduction of pH can effectively improve the silicate removal and reduce the usage of calcium. The economic analysis shows that the treatment costs with waste acid (0.63 $/m 3 ) and waste alkali (1.54 $/m 3 ) are lower than that of calcium chloride (2.38 $/m 3 ). The efficient removal of silicate is confirmed by industrial testing at a plant. The results show that silicate removal reaches 85% in the recycled water from tailings dam. Copyright © 2017 Elsevier Ltd. All rights reserved.

Interaction of Nanostructured Calcium Silicate Hydrate with Ibuprofen Drug Molecules: X-ray Absorption Near Edge Structure (XANES) Study at the Ca, Si and O K-edge

NASA Astrophysics Data System (ADS)

Guo, X. X.; Sham, T. K.; Zhu, Y. J.; Hu, Y. F.

2013-04-01

Mesoporous calcium silicate hydrate (CSH) nanostructure has been proven to be bioactive and biocompatible, and has a bright future in the application of bone treatment among other applications. X-ray absorption near edge structure (XANES) is a powerful tool for the study of the interactions of calcium silicate hydrates with drug molecules because it is element specific and it probes the unoccupied electronic states. Herein, we report the use of the calcium, silicon and oxygen K-edge XANES spectroscopy to identify how drug molecules interact with different groups in calcium silicate hydrate mesoporous nano-carriers with different morphologies. Significant changes are observed in XANES spectra after drug loading into the calcium silicate hydrate system, especially at the Si and O K-edge. The implications of these findings are discussed.

Catalytic crystallization of ices by small silicate smokes at temperatures less than 20K

NASA Technical Reports Server (NTRS)

Moore, M.; Ferrante, R.; Hudson, R.; Tanabe, T.; Nuth, J.

1993-01-01

Samples of methanol and water ices condensed from the vapor onto aluminum substrates at low temperatures (below approximately 80 K) form amorphous ices; annealing at temperatures in excess of 140-155 K is usually required to convert such amorphous samples to crystalline ices. However, we have found that when either methanol or water vapor is deposited on to aluminum substrates that have been coated with a thin (0.1-0.5 mm) layer of amorphous silicate smoke, the ices condense in crystalline form. We believe that crystalline ice forms as the result of energy liberated at the ice/silicate interface perhaps due to weak bonding of the ice at defect sites on the grains and the very high surface to volume ratio and defect density of these smokes. Annealing of amorphous water ice mixed with more volatile components such as methane, carbon monoxide, etc., has been suggested as an efficient way to produce clatherates in the outer solar nebula and thus explain the volatile content of comets and icy satellites of the outer planets. This hypothesis may need to be re-examined if amorphous ice does not form on cold silicate grains.

Simultaneous Production of Reduced Nitrogen Compounds and Hydrocarbons Using Amorphous Iron Silicate Smokes as a Catalyst

NASA Technical Reports Server (NTRS)

Nuth, Joseph A., III; Hill, Hugh G. M.

2001-01-01

Amorphous iron silicates efficiently catalyze formation of hydrocarbons and ammonia under conditions similar to that found in the solar nebula. Preliminary data and rates will be discussed, and much further experimentation is required. Additional information is contained in the original extended abstract.

Transformation of silicate gels during heat treatment in air and in argon - Spectroscopic studies

NASA Astrophysics Data System (ADS)

Rokita, M.; Mozgawa, W.; Adamczyk, A.

2014-07-01

The sol-gel method offers the possibility of obtaining silicate materials with different chemical compositions. When using TEOS or other organic precursor to silica capable of hydrolysis and poly-condensation, it is possible to use inorganic or organic precursors to produce other ingredients. This paper presents results of studying two series of silicate sols with the addition of calcium, in which the molar ratio of calcium to silicon was Ca/Si = x/(100 - x), where x was, respectively, 0-40 (x = 0-control sample). The resulting gels were subjected to heat treatment, wherein the heating was carried out simultaneously in air or in argon. To study the various stages of transformation of the gels, IR spectroscopy was used as the main research method to observe gradual disappearance of bands associated with bonds typical of organic materials and formation of bands characteristic of Si-O-Si bridging bonds. Due to the amorphous or fine crystalline nature of the resulting material, as confirmed in XRD studies, the different bands on the IR spectra were characterized by large full width at half maximum, hence an attempt was made to decompose the spectra into component bands. The analytic parameters of the resulting bands warranted the conclusion that there had been structural changes caused by the varying synthesis parameters. A comparison of the sol spectra after heat treatment in air and in argon at different temperatures showed a clear decrease in the full width at half maximum in the case of bands of samples with calcium content x ⩾ 30. The resulting spectra were compared with spectra of crystalline tobermorite, quartz and pseudowollastonite, which suggested the possibility of existence of areas with quartz-like ordering in the case of materials with calcium content x ⩾ 20 for the samples heated in argon and areas with pseudowollastonite-like ordering in the case of materials with calcium content x ⩾ 10 for the samples heated in air atmosphere. The conclusions drawn on the basis of infrared spectra were confirmed by XRD - prolonged heating of gels at 700 °C allowed us to obtain fine quartz and pseudowollastonite.

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

Nguyen, Ann N.; Keller, Lindsay P.; Messenger, Scott, E-mail: lan-anh.n.nguyen@nasa.gov

We report the chemical and structural analysis of nine presolar silicate grains and one presolar oxide grain from the ungrouped chondrite Acfer 094 and the CR chondrite Queen Alexandra Range 99177. Oxygen isotopic analyses indicate that five of these grains condensed in the outflows of asymptotic giant branch (AGB) stars, four have supernova (SN) origins, and one grain likely has a nova origin. Transmission electron microscopy studies show that most of the grains are amorphous with widely varying non-stoichiometric chemical compositions. Three crystalline AGB grains were identified: a clinoenstatite-containing grain assemblage, a Fe-rich olivine grain, and a nanocrystalline enstatite grainmore » encased in an amorphous silicate shell. An amorphous stoichiometric enstatite (MgSiO{sub 3}) SN grain likely condensed as a crystal and was later rendered amorphous. We do not observe a systematic difference in the chemistries and mineralogies of presolar silicates from different stellar sources, suggesting that the grains formed under a similar range of conditions.« less

Comment on "The shape and composition of interstellar silicate grains"

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

Bradley, J P; Ishii, H

2007-09-27

In the paper entitled 'The shape and composition of interstellar silicate grains' (A & A, 462, 667-676 (2007)), Min et al. explore non-spherical grain shape and composition in modeling the interstellar 10 and 20 {micro}m extinction features. This progression towards more realistic models is vitally important to enabling valid comparisons between dust observations and laboratory measurements. Min et al. proceed to compare their model results with GEMS (glass with embedded metals and sulfides) from IDPs (interplanetary dust particles) and to discuss the nature and origin of GEMS. Specifically, they evaluate the hypothesis of Bradley (1994) that GEMS are interstellar (IS)more » amorphous silicates. From a comparison of the mineralogy, chemical compositions, and infrared (IR) spectral properties of GEMS with their modeling results, Min et al. conclude: 'GEMS are, in general, not unprocessed leftovers from the diffuse ISM'. This conclusion is based, however, on erroneous and incomplete GEMS data. It is important to clarify first that Bradley (1994) never proposed that GEMS are unprocessed leftovers from the diffuse ISM, nor did he suggest that individual subnanogram mass GEMS are a representative sampling of the enormous mass of silicates in the diffuse ISM. Bradley (1994) simply showed that GEMS properties are consistent with those of IS amorphous silicates. It is widely accepted that circumstellar outflows are important sources of IS silicates, and whether GEMS are processed or not, the circumstellar heritage of some has been rigorously confirmed through measurements of non-solar oxygen (O) isotope abundances (Messenger et al., 2003; Floss et al., 2006). Keller et al. (2000) assert that even GEMS without detectable O isotope anomalies are probably also extrasolar IS silicates because they are embedded in carbonaceous material with non-solar D/H isotopic composition. (Much of the silicate dust in the ISM may be isotopically homogenized (Zhukovska et al., 2007)). Recent measurements show that the elemental compositions of GEMS with non-solar isotopic compositions are 'remarkably similar' to those with solar isotopic compositions (Keller & Messenger, 2007). About 80% of all isotopically anomalous IS silicates identified to date are GEMS with detectable and variable O isotopic memories of a circumstellar ancestry (Messenger, 2007). Bradley (1999) proposed that GEMS are IS silicates from 'a presolar interstellar molecular cloud, presumably the local molecular cloud from which the solar system formed'. Although based on incorrect data (detailed below), Min et al. propose that most GEMS actually formed in the presolar molecular cloud, and they further propose that none of them are IS silicates. IS silicate sources include molecular clouds, circumstellar outflows, supernovae, and even recently discovered black hole winds (Molster & Waters; 2003; Jones, 2005; Zhukovska et al. 2007; Markwick-Kemper et al. 2007). The average IS 10 {micro}m extinction feature observed along lines of sight towards the galactic center (modeled by Min et al.) presumably provides a good average for IS silicates, but it cannot distinguish amorphous silicates originating in the presolar molecular cloud from amorphous silicates originating in other interstellar molecular clouds or indeed other sources of amorphous IS silicates. Even if most GEMS accreted in the presolar molecular cloud, then they must also be representatives of some portion of the IS amorphous silicate population. Laboratory heating experiments indicate it is highly unlikely that GEMS were modified in a protoplanetary accretion disk environment (Brownlee et al. 2005). In summary, Min et al. conclude from their modeling of the shape and composition of IS silicates that the properties of GEMS are generally inconsistent with those of IS silicates. First, it has been rigorously confirmed via ion microprobe measurements that some GEMS are indeed presolar IS silicates. Second, regardless of whether GEMS, or components of GEMS, originated in presolar circumstellar outflows or a presolar molecular cloud they are all IS silicates. Third, key GEMS data reported in Min et al. are inaccurate. Had complete isotopic, chemical, mineralogical and infrared (IR) spectral properties of GEMS been considered, Min et al. may have concluded that the properties of GEMS, although not an exact match, are generally consistent with those of amorphous silicates in the ISM.« less

Catalysis, nanostructure and macroscopic property triangle in bioactive calcium-containing ceramic systems.

PubMed

Meiszterics, Anikó; Havancsák, Károly; Sinkó, Katalin

2013-04-01

Calcium silicate ceramics are intended for application as long-term implant materials. In the present work, attention was paid to understand the correlations between the nanostructure (aggregate size, crystallinity, porosity) and the macroscopic properties (solubility in water and simulated body fluids, SBF; hardness) varying the chemical composition. Varying the catalyst (from a base to various acids) during the chemical synthesis was shown to significantly impact on the pore size, crystallinity and mechanical properties. The basic catalyst yields the ceramics with the highest mechanical strength. Ammonia used in 1.0 or 10.0 molar ratio results in bulk ceramics with parameters required for a biomedical application, good hardness (180-200 HV) and low solubility (1-3%) in water and in SBF. The fine porosity (~50 nm) and homogeneous amorphous structure induce good mechanical character. Copyright © 2012 Elsevier B.V. All rights reserved.

The physical properties and ion release of CPP-ACP-modified calcium silicate-based cements.

PubMed

Dawood, A E; Manton, D J; Parashos, P; Wong, Rhk; Palamara, Jea; Stanton, D P; Reynolds, E C

2015-12-01

This study investigated the physical properties and ion release of casein phosphopeptide-amorphous calcium phosphate (CPP-ACP)-modified calcium silicate-based cements (CSCs) and compared the properties of a trial mineral trioxide aggregate (MTA) with two commercially available CSCs, Biodentine(™) and Angelus(®) MTA. The setting time, solubility, compressive strength and Vickers surface microhardness of the three CSCs incorporated with 0%, 0.5%, 1.0%, 2.0% and 3.0% (w/w) CPP-ACP were investigated. Release of calcium (Ca(2+) ), phosphate ions (Pi ) and pH of the test cements were measured after 24, 72, 168 and 336 h of storage. The addition of up to 1.0% CPP-ACP into Biodentine(™) and 0.5% into the other cements did not adversely affect their physical properties except for the setting time. The addition of 0.5% CPP-ACP increased Ca(2+) released from Biodentine(™) (after 168 and 336 h), Angelus(®) MTA (after 168 h) and the trial MTA (after 72 h). The addition of 1.0-3.0% CPP-ACP increased Ca(2+) and Pi released from all the cements. Biodentine(™) released more Ca(2+) particularly in the early stages and showed shorter setting time and higher mechanical properties than the other cements. The mechanical properties of Angelus(®) MTA and the trial MTA were similar. All the cements produced highly alkaline storage solutions. Up to 1.0% CPP-ACP in Biodentine(™) improves Ca(2+) and Pi release and 0.5% CPP-ACP in Angelus(®) MTA and the trial MTA improves Ca(2+) release without altering the mechanical properties and solubility. The addition of CPP-ACP into CSCs prolonged the setting time. © 2015 Australian Dental Association.

Microcrystals and Amorphous Material in Comets and Primitive Meteorites: Keys to Understanding Processes in the Early Solar System

NASA Technical Reports Server (NTRS)

Nuth, J. A.; Brearley, A. J.; Scott, E. R. D.

2004-01-01

Comets, fine-grained matrices of chondrites, and chondritic interplanetary dust particles (IDPs) are each composed of both crystalline and amorphous silicates. The primitive solar nebula, in which comets and asteroids accreted, was formed from the collapsed core of a Giant Molecular Cloud, that, in turn, condensed from materials present in the interstellar medium (ISM). Despite observations that reveal the presence of crystalline magnesium silicate minerals in the shells of very high mass-loss-rate stars [1,2], typical silicate grains in the ISM are most likely to be amorphous, given their relatively long residence time in such a high radiation environment. An upper limit of 3% crystalline grains can be derived from their non-detection in spectra of ISM solids [3]. If the vast majority of grains that enter the primitive solar nebula are amorphous, then the observation of crystalline dust in comets and primitive chondrite matrices indicates the action of specific processes required to transform the amorphous starting materials into the crystals that are observed.

Low-temperature MIR to submillimeter mass absorption coefficient of interstellar dust analogues. II. Mg and Fe-rich amorphous silicates

NASA Astrophysics Data System (ADS)

Demyk, K.; Meny, C.; Leroux, H.; Depecker, C.; Brubach, J.-B.; Roy, P.; Nayral, C.; Ojo, W.-S.; Delpech, F.

2017-10-01

Context. To model the cold dust emission observed in the diffuse interstellar medium, in dense molecular clouds or in cold clumps that could eventually form new stars, it is mandatory to know the physical and spectroscopic properties of this dust and to understand its emission. Aims: This work is a continuation of previous studies aiming at providing astronomers with spectroscopic data of realistic cosmic dust analogues for the interpretation of observations. The aim of the present work is to extend the range of studied analogues to iron-rich silicate dust analogues. Methods: Ferromagnesium amorphous silicate dust analogues were produced by a sol-gel method with a mean composition close to Mg1-xFexSiO3 with x = 0.1, 0.2, 0.3, 0.4. Part of each sample was annealed at 500 °C for two hours in a reducing atmosphere to modify the oxidation state of iron. We have measured the mass absorption coefficient (MAC) of these eight ferromagnesium amorphous silicate dust analogues in the spectral domain 30-1000 μm for grain temperature in the range 10-300 K and at room temperature in the 5-40 μm range. Results: The MAC of ferromagnesium samples behaves in the same way as the MAC of pure Mg-rich amorphous silicate samples. In the 30-300 K range, the MAC increases with increasing grain temperature whereas in the range 10-30 K, we do not see any change of the MAC. The MAC cannot be described by a single power law in λ- β. The MAC of the samples does not show any clear trend with the iron content. However the annealing process has, on average, an effect on the MAC that we explain by the evolution of the structure of the samples induced by the processing. The MAC of all the samples is much higher than the MAC calculated by dust models. Conclusions: The complex behavior of the MAC of amorphous silicates with wavelength and temperature is observed whatever the exact silicate composition (Mg vs. Fe amount). It is a universal characteristic of amorphous materials, and therefore of amorphous cosmic silicates, that should be taken into account in astronomical modeling. The enhanced MAC of the measured samples compared to the MAC calculated for cosmic dust model implies that dust masses are overestimated by the models. The tabulated mass absorption coefficients are only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/606/A50

Characterizing Amorphous Silicates in Extraterrestrial Materials

NASA Astrophysics Data System (ADS)

Fu, X.; Wang, A.; Krawczynski, M. J.

2015-12-01

Amorphous silicates are common in extraterrestrial materials. They are seen in the matrix of carbonaceous chondrites as well as in planetary materials. Tagish Lake is one of the most primitive carbonaceous meteorites in which TEM and XRD analyses found evidence for poorly crystalline phyllosilicate-like species; Raman spectra revealed amorphous silicates with variable degree of polymerization and low crystallinity. On Mars, CheMin discovered amorphous phases in all analyzed samples, and poorly crystalline smectite in mudstone samples. These discoveries pose questions on the crystallinity of phyllosilicates found by remote sensing on Mars, which is directly relevant to aqueous alteration during geologic history of Mars. Our goal is to use spectroscopy to better characterize amorphous silicates. We use three approaches: (1) using silicate glasses synthesized with controlled chemistry to study the effects of silicate polymerization and (2) using phyllosilicates synthesized with controlled hydrothermal treatment to study the effect of crystallinity on vibrational spectroscopy, finally (3) to use the developed correlations in above two steps to study amorphous phases in meteorites, and those found in future missions to Mars. In the 1st step, silicate glasses were synthesized from pure oxides in a range of NBO/T ratios (from 0 to 4). Depending on the targeted NBO/T and composition of mixed oxides, temperatures for each experiment fell in a range from 1260 to 1520 °C, run for ~ 4 hrs. The melt was quenched in liquid N2 or water. Homogeneity of glass was checked under optical microscopy. Raman spectra were taken over 100 spots on small chips free of bubbles and crystals. We have observed that accompanying an increase of NBO/T, there is a strengthening and a position shift of the Raman peak near 1000 cm-1 (Si-Onon-bridging stretching mode), and the weakening of broad Raman peaks near 500 cm-1 (ring breathing mode) and 700cm-1 (Si-Obridging-Si mode). We are building the correlation between peak area ratio, A(500+700)/A1000, and NBO/T. In the 2nd step, we are synthesizing Mg-saponite using a sol-gel method. The crystallinity of sol-gel starting materials will be increased by a controlled hydrothermal treatment. The products will be characterized using XRD/TEM/Raman/NIR. The results will be reported at the conference.

Calcium silicates synthesised from industrial residues with the ability for CO2 sequestration.

PubMed

Morales-Flórez, Victor; Santos, Alberto; López, Antonio; Moriña, Isabel; Esquivias, Luis

2014-12-01

This work explored several synthesis routes to obtain calcium silicates from different calcium-rich and silica-rich industrial residues. Larnite, wollastonite and calcium silicate chloride were successfully synthesised with moderate heat treatments below standard temperatures. These procedures help to not only conserve natural resources, but also to reduce the energy requirements and CO2 emissions. In addition, these silicates have been successfully tested as carbon dioxide sequesters, to enhance the viability of CO2 mineral sequestration technologies using calcium-rich industrial by-products as sequestration agents. Two different carbon sequestration experiments were performed under ambient conditions. Static experiments revealed carbonation efficiencies close to 100% and real-time resolved experiments characterised the dynamic behaviour and ability of these samples to reduce the CO2 concentration within a mixture of gases. The CO2 concentration was reduced up to 70%, with a carbon fixation dynamic ratio of 3.2 mg CO2 per g of sequestration agent and minute. Our results confirm the suitability of the proposed synthesis routes to synthesise different calcium silicates recycling industrial residues, being therefore energetically more efficient and environmentally friendly procedures for the cement industry. © The Author(s) 2014.

Increased calcium absorption from synthetic stable amorphous calcium carbonate: Double-blind randomized crossover clinical trial in post-menopausal women

USDA-ARS?s Scientific Manuscript database

Calcium supplementation is a widely recognized strategy for achieving adequate calcium intake. We designed this blinded, randomized, crossover interventional trial to compare the bioavailability of a new stable synthetic amorphous calcium carbonate (ACC) with that of crystalline calcium carbonate (C...

The mineral phase in the cuticles of two species of Crustacea consists of magnesium calcite, amorphous calcium carbonate, and amorphous calcium phosphate.

PubMed

Becker, Alexander; Ziegler, Andreas; Epple, Matthias

2005-05-21

The cuticules (shells) of the woodlice Porcellio scaber and Armadillidium vulgare were analysed with respect to their content of inorganic material. It was found that the cuticles consist of crystalline magnesium calcite, amorphous calcium carbonate (ACC), and amorphous calcium phosphate (ACP), besides small amounts of water and an organic matrix. It is concluded that the cuticle, which constitutes a mineralized protective organ, is chemically adapted to the biological requirements by this combination of different materials.

Hard X-ray irradiation of cosmic silicate analogs: structural evolution and astrophysical implications

NASA Astrophysics Data System (ADS)

Gavilan, L.; Jäger, C.; Simionovici, A.; Lemaire, J. L.; Sabri, T.; Foy, E.; Yagoubi, S.; Henning, T.; Salomon, D.; Martinez-Criado, G.

2016-03-01

Context. Protoplanetary disks, interstellar clouds, and active galactic nuclei contain X-ray-dominated regions. X-rays interact with the dust and gas present in such environments. While a few laboratory X-ray irradiation experiments have been performed on ices, X-ray irradiation experiments on bare cosmic dust analogs have been scarce up to now. Aims: Our goal is to study the effects of hard X-rays on cosmic dust analogs via in situ X-ray diffraction. By using a hard X-ray synchrotron nanobeam, we seek to simulate cumulative X-ray exposure on dust grains during their lifetime in these astrophysical environments and provide an upper limit on the effect of hard X-rays on dust grain structure. Methods: We prepared enstatite (MgSiO3) nanograins, which are analogs to cosmic silicates, via the melting-quenching technique. These amorphous grains were then annealed to obtain polycrystalline grains. These were characterized via scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (HRTEM) before irradiation. Powder samples were prepared in X-ray transparent substrates and were irradiated with hard X-rays nanobeams (29.4 keV) provided by beamline ID16B of the European Synchrotron Radiation Facility (Grenoble). X-ray diffraction images were recorded in transmission mode, and the ensuing diffractograms were analyzed as a function of the total X-ray exposure time. Results: We detected the amorphization of polycrystalline silicates embedded in an organic matrix after an accumulated X-ray exposure of 6.4 × 1027 eV cm-2. Pure crystalline silicate grains (without resin) do not exhibit amorphization. None of the amorphous silicate samples (pure and embedded in resin) underwent crystallization. We analyze the evolution of the polycrystalline sample embedded in an organic matrix as a function of X-ray exposure. Conclusions: Loss of diffraction peak intensity, peak broadening, and the disappearance of discrete spots and arcs reveal the amorphization of the resin embedded (originally polycrystalline) silicate sample. We explore the astrophysical implications of this laboratory result as an upper limit to the effect of X-rays on the structure of cosmic silicates.

Preparation, characterization and in vivo evaluation of amorphous atorvastatin calcium nanoparticles using supercritical antisolvent (SAS) process.

PubMed

Kim, Min-Soo; Jin, Shun-Ji; Kim, Jeong-Soo; Park, Hee Jun; Song, Ha-Seung; Neubert, Reinhard H H; Hwang, Sung-Joo

2008-06-01

In this work, amorphous atorvastatin calcium nanoparticles were successfully prepared using the supercritical antisolvent (SAS) process. The effect of process variables on particle size and distribution of atorvastatin calcium during particle formation was investigated. Solid state characterization, solubility, intrinsic dissolution, powder dissolution studies and pharmacokinetic study in rats were performed. Spherical particles with mean particle size ranging between 152 and 863 nm were obtained by varying process parameters such as precipitation vessel pressure and temperature, drug solution concentration and feed rate ratio of CO2/drug solution. XRD, TGA, FT-IR, FT-Raman, NMR and HPLC analysis indicated that atorvastatin calcium existed as anhydrous amorphous form and no degradation occurred after SAS process. When compared with crystalline form (unprocessed drug), amorphous atorvastatin calcium nanoparticles were of better performance in solubility and intrinsic dissolution rate, resulting in higher solubility and faster dissolution rate. In addition, intrinsic dissolution rate showed a good correlation with the solubility. The dissolution rates of amorphous atorvastatin calcium nanoparticles were highly increased in comparison with unprocessed drug by the enhancement of intrinsic dissolution rate and the reduction of particle size resulting in an increased specific surface area. The absorption of atorvastatin calcium after oral administration of amorphous atorvastatin calcium nanoparticles to rats was markedly increased.

Ionic Substitutions in Non-Apatitic Calcium Phosphates

PubMed Central

Laskus, Aleksandra; Kolmas, Joanna

2017-01-01

Calcium phosphate materials (CaPs) are similar to inorganic part of human mineralized tissues (i.e., bone, enamel, and dentin). Owing to their high biocompatibility, CaPs, mainly hydroxyapatite (HA), have been investigated for their use in various medical applications. One of the most widely used ways to improve the biological and physicochemical properties of HA is ionic substitution with trace ions. Recent developments in bioceramics have already demonstrated that introducing foreign ions is also possible in other CaPs, such as tricalcium phosphates (amorphous as well as α and β crystalline forms) and brushite. The purpose of this paper is to review recent achievements in the field of non-apatitic CaPs substituted with various ions. Particular attention will be focused on tricalcium phosphates (TCP) and “additives” such as magnesium, zinc, strontium, and silicate ions, all of which have been widely investigated thanks to their important biological role. This review also highlights some of the potential biomedical applications of non-apatitic substituted CaPs. PMID:29186932

The flame photometric determination of calcium in phosphate, carbonate, and silicate rocks

USGS Publications Warehouse

Kramer, H.

1957-01-01

A flame photometric method of determining calcium in phosphate, carbonate, and silicate locks has been developed Aluminum and phosphate interference was overcome by the addition of a large excess of magnesium. The method is rapid and suitable for routine analysis Results obtained are within ?? 2% of the calcium oxide content. ?? 1957.

Mineralogical Studies of a Highly O-17-Depleted and an O-17-Rich Presolar Grain from the Acfer 094 Meteorite

NASA Technical Reports Server (NTRS)

Nguyen, A. N.; Keller, L. P.; Rahman, Z.; Messenger, S.

2012-01-01

Silicate grains are the most abundant condensate around O-rich evolved stars, including red giants, supernovae (SNe) and binary systems. These grains have been identified in abundance in primitive meteorites and interplanetary dust particles [1,2]. Astronomical observations of the silicate spectroscopic features around circumstellar disks indicate that most silicates are amorphous olivine-like grains, though some sources show a large crystalline portion [3]. Fewer astronomical observations of SN and nova silicates exist, but amorphous Mg-rich grains predominate [4,5]. The laboratory analysis of presolar silicates by transmission electron microscopy (TEM) offers more details on the structure and chemistry of individual grains. These studies provide information on the physical and chemical conditions of the parent stellar atmosphere during grain condensation. Moreover, be-cause silicates are susceptible to secondary alteration, processing events succeeding condensation can be traced. Thus far, similar microstructures have been observed for silicates that condensed in SN outflows and in the envelopes of asymptotic giant branch (AGB) stars, but not as many of the comparatively rare SN grains have been analyzed. Here we examine the mineralogies of two presolar silicate grains having different origins.

High Pressure Response of Siliceous Materials

DTIC Science & Technology

2013-02-01

iron-containing soda lime silicate glass, opal (a hydrated silicate glass), ROBAX glass ceramic, and others were single crystal (α-quartz) and...10 2.6. Opal (hydrated amorphous silica...Raman spectrum as a function of stress for opal (hydrated silica) glass. ................... 29 4.9. Raman spectrum as a function of stress for

Amorphous Calcium Carbonate Based-Microparticles for Peptide Pulmonary Delivery.

PubMed

Tewes, Frederic; Gobbo, Oliviero L; Ehrhardt, Carsten; Healy, Anne Marie

2016-01-20

Amorphous calcium carbonate (ACC) is known to interact with proteins, for example, in biogenic ACC, to form stable amorphous phases. The control of amorphous/crystalline and inorganic/organic ratios in inhalable calcium carbonate microparticles may enable particle properties to be adapted to suit the requirements of dry powders for pulmonary delivery by oral inhalation. For example, an amorphous phase can immobilize and stabilize polypeptides in their native structure and amorphous and crystalline phases have different mechanical properties. Therefore, inhalable composite microparticles made of inorganic (i.e., calcium carbonate and calcium formate) and organic (i.e., hyaluronan (HA)) amorphous and crystalline phases were investigated for peptide and protein pulmonary aerosol delivery. The crystalline/amorphous ratio and polymorphic form of the inorganic component was altered by changing the microparticle drying rate and by changing the ammonium carbonate and HA initial concentration. The bioactivity of the model peptide, salmon calcitonin (sCT), coprocessed with alpha-1-antitrypsin (AAT), a model protein with peptidase inhibitor activity, was maintained during processing and the microparticles had excellent aerodynamic properties, making them suitable for pulmonary aerosol delivery. The bioavailability of sCT after aerosol delivery as sCT and AAT-loaded composite microparticles to rats was 4-times higher than that of sCT solution.

Fluoride-containing nanoporous calcium-silicate MTA cements for endodontics and oral surgery: early fluorapatite formation in a phosphate-containing solution.

PubMed

Gandolfi, M G; Taddei, P; Siboni, F; Modena, E; Ginebra, M P; Prati, C

2011-10-01

To test the chemical-physical properties and apatite-forming ability of experimental fluoride-doped calcium silicate cements designed to create novel bioactive materials for use in endodontics and oral surgery. A thermally treated calcium silicate cement (wTC) containing CaCl(2) 5%wt was modified by adding NaF 1%wt (FTC) or 10%wt (F10TC). Cements were analysed by environmental scanning electron microscopy with energy-dispersive X-ray analysis, IR and micro-Raman spectroscopy in wet conditions immediately after preparation or after ageing in a phosphate-containing solution (Dulbecco's phosphate-buffered saline). Calcium and fluoride release and pH of the storage solution were measured. The results obtained were analysed statistically (Tukey's HSD test and two-way anova). The formation of calcium phosphate precipitates (spherulites) was observed on the surface of 24 h-aged cements and the formation of a thick bone-like B-type carbonated apatite layer (biocoating) on 28 day-aged cements. The rate of apatite formation was FTC>F10TC>wTC. Fluorapatite was detected on FTC and F10TC after 1 day of ageing, with a higher fluoride content on F10TC. All the cements released calcium ions. At 5 and 24 h, the wTC had the significantly highest calcium release (P<0.001) that decreased significantly over the storage time. At 3-28 days, FTC and F10TC had significantly higher calcium release than wTC (P<0.05). The F10TC had the significantly highest fluoride release at all times (P<0.01) that decreased significantly over storage time. No significant differences were observed between FTC and wTC. All the cements had a strong alkalinizing activity (OH(-) release) that remained after 28 days of storage. The addition of sodium fluoride accelerated apatite formation on calcium silicate cements. Fluoride-doped calcium silicate cements had higher bioactivity and earlier formation of fluorapatite. Sodium fluoride may be introduced in the formulation of mineral trioxide aggregate cements to enhance their biological behaviour. F-doped calcium silicate cements are promising bone cements for clinical endodontic use. © 2011 International Endodontic Journal.

Determine the Compressive Strength of Calcium Silicate Bricks by Combined Nondestructive Method

PubMed Central

2014-01-01

The paper deals with the application of combined nondestructive method for assessment of compressive strength of calcium silicate bricks. In this case, it is a combination of the rebound hammer method and ultrasonic pulse method. Calibration relationships for determining compressive strength of calcium silicate bricks obtained from nondestructive parameter testing for the combined method as well as for the L-type Schmidt rebound hammer and ultrasonic pulse method are quoted here. Calibration relationships are known for their close correlation and are applicable in practice. The highest correlation between parameters from nondestructive measurement and predicted compressive strength is obtained using the SonReb combined nondestructive method. Combined nondestructive SonReb method was proved applicable for determination of compressive strength of calcium silicate bricks at checking tests in a production plant and for evaluation of bricks built in existing masonry structures. PMID:25276864

Calcium silicate-based cements and functional impacts of various constituents

PubMed Central

SAGHIRI, Mohammad Ali; ORANGI, Jafar; ASATOURIAN, Armen; GUTMANN, James L.; Garcia-Godoy, Franklin; LOTFI, Mehrdad; SHEIBANI, Nader

2016-01-01

Calcium silicate-based cements have superior sealing ability, bioactivity, and marginal adaptation, which make them suitable for different dental treatment applications. However, they exhibit some drawbacks such as long setting time and poor handling characteristics. To overcome these limitations calcium silicates are engineered with various constituents to improve specific characteristics of the base material, and are the focus of this review. An electronic search of the PubMed, MEDLINE, and EMBASE via OVID databases using appropriate terms and keywords related to the use, application, and properties of calcium silicate-based cements was conducted. Two independent reviewers obtained and analyzed the full texts of the selected articles. Although the effects of various constituents and additives to the base Portland cement-like materials have been investigated, there is no one particular ingredient that stands out as being most important. Applying nanotechnology and new synthesis methods for powders most positively affected the cement properties. PMID:27773894

Decreased water flowing from a forest amended with calcium silicate

Treesearch

Mark B. Green; Amey S. Bailey; Scott W. Bailey; John J. Battles; John L. Campbell; Charles T. Driscoll; Timothy J. Fahey; Lucie C. Lepine; Gene E. Likens; Scott V. Ollinger; Paul G. Schaberg

2013-01-01

Acid deposition during the 20th century caused widespread depletion of available soil calcium (Ca) throughout much of the industrialized world. To better understand how forest ecosystems respond to changes in a component of acidification stress, an 11.8-ha watershed was amended with wollastonite, a calcium silicate mineral, to restore available soil Ca to preindustrial...

Mineralogenic characteristics of osteogenic lineage-committed human dental pulp stem cells following their exposure to a discoloration-free calcium aluminosilicate cement.

PubMed

Niu, Li-Na; Pei, Dan-Dan; Morris, Matthew; Jiao, Kai; Huang, Xue-Qing; Primus, Carolyn M; Susin, Lisiane F; Bergeron, Brian E; Pashley, David H; Tay, Franklin R

2016-10-01

An experimental discoloration-free calcium aluminosilicate cement has been developed with the intention of maximizing the beneficial attributes of tricalcium silicate cements and calcium aluminate cements. The present study examined the effects of this experimental cement (Quick-Set2) on the mineralogenic characteristics of osteogenic lineage-committed human dental pulp stem cells (hDPSCs), by comparing the cellular responses with a commercially available tricalcium silicate cement (white mineral trioxide aggregate (ProRoot(®) MTA); WMTA). The osteogenic potential of hDPSCs exposed to the cements was examined using qRT-PCR for osteogenic gene expressions, Western blot for osteogenic-related protein expressions, alkaline phosphatase enzyme activity, Alizarin red S staining, Fourier transform infrared spectroscopy and transmission electron microscopy of extracellular calcium deposits. Results of the six assays indicated that osteogenic differentiation of hDPSCs was significantly enhanced after exposure to the tricalcium silicate cement or the experimental calcium aluminosilicate cement, with the former demonstrating better mineralogenic stimulation capacity. The better osteogenic stimulating effect of the tricalcium silicate cement on hDPSCs may be due to its relatively higher silicate content, or higher OH(-) and Ca(2+) release. Further investigations with the use of in vivo animal models are required to validate the potential augmenting osteogenic effects of the experimental discoloration-free calcium aluminosilicate cement. Published by Elsevier Ltd.

Origins of GEMS Grains

NASA Technical Reports Server (NTRS)

Messenger, S.; Walker, R. M.

2012-01-01

Interplanetary dust particles (IDPs) collected in the Earth s stratosphere contain high abundances of submicrometer amorphous silicates known as GEMS grains. From their birth as condensates in the outflows of oxygen-rich evolved stars, processing in interstellar space, and incorporation into disks around new stars, amorphous silicates predominate in most astrophysical environments. Amorphous silicates were a major building block of our Solar System and are prominent in infrared spectra of comets. Anhydrous interplanetary dust particles (IDPs) thought to derive from comets contain abundant amorphous silicates known as GEMS (glass with embedded metal and sulfides) grains. GEMS grains have been proposed to be isotopically and chemically homogenized interstellar amorphous silicate dust. We evaluated this hypothesis through coordinated chemical and isotopic analyses of GEMS grains in a suite of IDPs to constrain their origins. GEMS grains show order of magnitude variations in Mg, Fe, Ca, and S abundances. GEMS grains do not match the average element abundances inferred for ISM dust containing on average, too little Mg, Fe, and Ca, and too much S. GEMS grains have complementary compositions to the crystalline components in IDPs suggesting that they formed from the same reservoir. We did not observe any unequivocal microstructural or chemical evidence that GEMS grains experienced prolonged exposure to radiation. We identified four GEMS grains having O isotopic compositions that point to origins in red giant branch or asymptotic giant branch stars and supernovae. Based on their O isotopic compositions, we estimate that 1-6% of GEMS grains are surviving circumstellar grains. The remaining 94-99% of GEMS grains have O isotopic compositions that are indistinguishable from terrestrial materials and carbonaceous chondrites. These isotopically solar GEMS grains either formed in the Solar System or were completely homogenized in the interstellar medium (ISM). However, the chemical compositions of GEMS grains are extremely heterogeneous and seem to rule out this possibility. Based on their solar isotopic compositions and their non-solar elemental compositions we propose that most GEMS grains formed in the nebula as late-stage non-equilibrium condensates.

High Pressure Response of Siliceous Materials

DTIC Science & Technology

2013-02-01

quartz, Starphire soda lime silicate glass, hydrated Starphire, BOROFLOAT borosilicate glass, an iron-containing soda lime silicate glass, opal (a hydrated... Opal (hydrated amorphous silica). .............................................................................. 10 2.7. ROBAX glass ceramic...spectrum as a function of stress for BOROFLOAT borosilicate glass. .......... 29 4.8. Raman spectrum as a function of stress for opal (hydrated

Silicate Crystal Formation in the Disk of an Erupting Star Artist Concept

NASA Image and Video Library

2009-05-13

This artist's concept illustrates how silicate crystals like those found in comets can be created by an outburst from a growing star. The image shows a young sun-like star encircled by its planet-forming disk of gas and dust. The silicate that makes up most of the dust would have begun as non-crystallized, amorphous particles. Streams of material are seen spiraling from the disk onto the star increasing its mass and causing the star to brighten and heat up dramatically. The outburst causes temperatures to rise in the star's surrounding disk. The animation (figure 1) zooms into the disk to show close-ups of silicate particles. When the disk warms from the star's outburst, the amorphous particles of silicate melt. As they cool off, they transform into forsterite (figure 2), a type of silicate crystal often found in comets in our solar system. In April 2008, NASA's Spitzer Space Telescope detected evidence of this process taking place on the disk of a young sun-like star called EX Lupi. http://photojournal.jpl.nasa.gov/catalog/PIA12008

Low-temperature crystallization of silicate dust in circumstellar disks.

PubMed

Molster, F J; Yamamura, I; Waters, L B; Tielens, A G; de Graauw, T; de Jong, T; de Koter, A; Malfait, K; van den Ancker, M E; van Winckel, H; Voors, R H; Waelkens, C

1999-10-07

Silicate dust in the interstellar medium is observed to be amorphous, yet silicate dust in comets and interplanetary dust particles is sometimes partially crystalline. The dust in disks that are thought to be forming planets around some young stars also appears to be partially crystalline. These observations suggest that as the dust goes from the precursor clouds to a planetary system, it must undergo some processing, but the nature and extent of this processing remain unknown. Here we report observations of highly crystalline silicate dust in the disks surrounding binary red-giant stars. The dust was created in amorphous form in the outer atmospheres of the red giants, and therefore must be processed in the disks to become crystalline. The temperatures in these disks are too low for the grains to anneal; therefore, some low-temperature process must be responsible. As the physical properties of the disks around young stars and red giants are similar, our results suggest that low-temperature crystallization of silicate grains also can occur in protoplanetary systems.

Transparent amorphous oxide semiconductors for organic electronics: Application to inverted OLEDs

PubMed Central

Hosono, Hideo; Toda, Yoshitake; Kamiya, Toshio; Watanabe, Satoru

2017-01-01

Efficient electron transfer between a cathode and an active organic layer is one key to realizing high-performance organic devices, which require electron injection/transport materials with very low work functions. We developed two wide-bandgap amorphous (a-) oxide semiconductors, a-calcium aluminate electride (a-C12A7:e) and a-zinc silicate (a-ZSO). A-ZSO exhibits a low work function of 3.5 eV and high electron mobility of 1 cm2/(V · s); furthermore, it also forms an ohmic contact with not only conventional cathode materials but also anode materials. A-C12A7:e has an exceptionally low work function of 3.0 eV and is used to enhance the electron injection property from a-ZSO to an emission layer. The inverted electron-only and organic light-emitting diode (OLED) devices fabricated with these two materials exhibit excellent performance compared with the normal type with LiF/Al. This approach provides a solution to the problem of fabricating oxide thin-film transistor-driven OLEDs with both large size and high stability. PMID:28028243

Structural and chemical alteration of crystalline olivine under low energy He+ irradiation

NASA Astrophysics Data System (ADS)

Demyk, K.; Carrez, Ph.; Leroux, H.; Cordier, P.; Jones, A. P.; Borg, J.; Quirico, E.; Raynal, P. I.; d'Hendecourt, L.

2001-03-01

We present the results of irradiation experiments on crystalline olivine with He+ ions at energies of 4 and 10 keV and fluences varying from 5 1016 to 1018 ions/cm2. The aim of these experiments is to simulate ion implantation into interstellar grains in shocks in the ISM. Irradiated samples were analysed by transmission electron microscopy (TEM). The irradiation causes the amorphization of the olivine, at all He+ fluences considered. The thickness of the amorphized region is 40 +/- 15 nm and 90 +/- 10 nm for the 4 keV and 10 keV experiments, respectively. The amorphization of the olivine occurs in conjunction with an increase in the porosity of the material due to the formation of bubbles. In addition, the amorphized layer is deficient in oxygen and magnesium. We find that the O/Si and Mg/Si ratios decrease as the He+ fluence increases. These experiments show that the irradiation of dust in supernova shocks can efficiently alter the dust structure and composition. Our result are consistent with the lack of crystalline silicates in the interstellar medium and also with the compositional evolution observed from olivine-type silicates around evolved stars to pyroxene-type silicates around protostars.

Silicate Phases on the Surfaces of Trojan Asteroids

NASA Astrophysics Data System (ADS)

Martin, Audrey; Emery, Joshua P.; Lindsay, Sean S.

2017-10-01

Determining the origin of asteroids provides an effective means of constraining the solar system’s dynamic past. Jupiter Trojan asteroids (hereafter Trojans) may help in determining the amount of radial mixing that occurred during giant planet migration. Previous studies aimed at characterizing surface composition show that Trojans have low albedo surfaces and are spectrally featureless in the near infrared. The thermal infrared (TIR) wavelength range has advantages for detecting silicates on low albedo asteroids such as Trojans. The 10 μm region exhibits strong features due to the Si-O fundamental molecular vibrations. Silicates that formed in the inner solar system likely underwent thermal annealing, and thus are crystalline, whereas silicates that accreted in the outer solar system experienced less thermal processing, and therefore are more likely to have remained in an amorphous phase. We hypothesize that the Trojans formed in the outer solar system (i.e., the Kuiper Belt), and therefore will have a more dominant amorphous spectral silicate component. With TIR spectra from the Spitzer Space Telescope, we identify mineralogical features from the surface of 11 Trojan asteroids. Fine-grain mixtures of crystalline pyroxene and olivine exhibit a 10 μm feature with sharp cutoffs between about 9 μm and 12 μm, which create a broad flat plateau. Amorphous phases, when present, smooth the sharp emission features, resulting in a dome-like shape. Preliminary results indicate that the surfaces of analyzed Trojans contain primarily amorphous silicates. Emissivity spectra of asteroids 1986 WD and 4709 Ennomos include small peaks in the 10 μm region, diagnostic of small amounts of crystalline olivine. One explanation is that Trojans formed in the same region as Kuiper Belt objects, and when giant planet migration ensued, they were swept into Jupiter’s stable Lagrange points where they are found today. As such, it is possible that an ancestral group of Kuiper Belt objects were separated from Trojans during large planet migration.

Synthesis and characterization of Fe(III)-silicate precipitation tubes

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

Parmar, K.; Pramanik, A.K.; Bandyopadhya, N.R.

2010-09-15

Fe(III)-silicate precipitation tubes synthesized through 'silica garden' route have been characterized using a number of analytical techniques including X-ray diffraction, infrared spectroscopy, atomic force microscopy, scanning and transmission electron microscopy. These tubes are brittle and amorphous and are hierarchically built from smaller tubes of 5-10 nm diameters. They remain amorphous at least up to 650 {sup o}C. Crystobalite and hematite are the major phases present in Fe(III)-silicate tubes heated at 850 {sup o}C. Morphology and chemical compositions at the external and internal walls of these tubes are remarkably different. These tubes are porous with high BET surface area of 291.2more » m{sup 2}/g. Fe(III)-silicate tubes contain significant amount of physically and chemically bound moisture. They show promise as an adsorbent for Pb(II), Zn(II), and Cr(III) in aqueous medium.« less

Enamel-like apatite crown covering amorphous mineral in a crayfish mandible

PubMed Central

Bentov, Shmuel; Zaslansky, Paul; Al-Sawalmih, Ali; Masic, Admir; Fratzl, Peter; Sagi, Amir; Berman, Amir; Aichmayer, Barbara

2012-01-01

Carbonated hydroxyapatite is the mineral found in vertebrate bones and teeth, whereas invertebrates utilize calcium carbonate in their mineralized organs. In particular, stable amorphous calcium carbonate is found in many crustaceans. Here we report on an unusual, crystalline enamel-like apatite layer found in the mandibles of the arthropod Cherax quadricarinatus (freshwater crayfish). Despite their very different thermodynamic stabilities, amorphous calcium carbonate, amorphous calcium phosphate, calcite and fluorapatite coexist in well-defined functional layers in close proximity within the mandible. The softer amorphous minerals are found primarily in the bulk of the mandible whereas apatite, the harder and less soluble mineral, forms a wear-resistant, enamel-like coating of the molar tooth. Our findings suggest a unique case of convergent evolution, where similar functional challenges of mastication led to independent developments of structurally and mechanically similar, apatite-based layers in the teeth of genetically remote phyla: vertebrates and crustaceans. PMID:22588301

Amorphous surface layer versus transient amorphous precursor phase in bone - A case study investigated by solid-state NMR spectroscopy.

PubMed

Von Euw, Stanislas; Ajili, Widad; Chan-Chang, Tsou-Hsi-Camille; Delices, Annette; Laurent, Guillaume; Babonneau, Florence; Nassif, Nadine; Azaïs, Thierry

2017-09-01

The presence of an amorphous surface layer that coats a crystalline core has been proposed for many biominerals, including bone mineral. In parallel, transient amorphous precursor phases have been proposed in various biomineralization processes, including bone biomineralization. Here we propose a methodology to investigate the origin of these amorphous environments taking the bone tissue as a key example. This study relies on the investigation of a bone tissue sample and its comparison with synthetic calcium phosphate samples, including a stoichiometric apatite, an amorphous calcium phosphate sample, and two different biomimetic apatites. To reveal if the amorphous environments in bone originate from an amorphous surface layer or a transient amorphous precursor phase, a combined solid-state nuclear magnetic resonance (NMR) experiment has been used. The latter consists of a double cross polarization 1 H→ 31 P→ 1 H pulse sequence followed by a 1 H magnetization exchange pulse sequence. The presence of an amorphous surface layer has been investigated through the study of the biomimetic apatites; while the presence of a transient amorphous precursor phase in the form of amorphous calcium phosphate particles has been mimicked with the help of a physical mixture of stoichiometric apatite and amorphous calcium phosphate. The NMR results show that the amorphous and the crystalline environments detected in our bone tissue sample belong to the same particle. The presence of an amorphous surface layer that coats the apatitic core of bone apatite particles has been unambiguously confirmed, and it is certain that this amorphous surface layer has strong implication on bone tissue biogenesis and regeneration. Questions still persist on the structural organization of bone and biomimetic apatites. The existing model proposes a core/shell structure, with an amorphous surface layer coating a crystalline bulk. The accuracy of this model is still debated because amorphous calcium phosphate (ACP) environments could also arise from a transient amorphous precursor phase of apatite. Here, we provide an NMR spectroscopy methodology to reveal the origin of these ACP environments in bone mineral or in biomimetic apatite. The 1 H magnetization exchange between protons arising from amorphous and crystalline domains shows unambiguously that an ACP layer coats the apatitic crystalline core of bone et biomimetic apatite platelets. Copyright © 2017 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Synthesis and characterisation of composite based biohydroxyapatite bovine bone mandible waste (BHAp) doped with 10 wt % amorphous SiO{sub 2} from rice husk by solid state reaction

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

Asmi, Dwi, E-mail: dwiasmi82@yahoo.com, E-mail: dwi.asmi@fmipa.unila.ac.id; Sulaiman, Ahmad, E-mail: ahmadsulaiman@yahoo.co.id; Oktavia, Irene Lucky, E-mail: ireneluckyo@gmail.com

Effect of 10 wt% amorphous SiO{sub 2} from rice husk addition on the microstructures of biohydroxyapatite (BHAp) obtained from bovine bone was synthesized by solid state reaction. In this study, biohydroxyapatite powder was obtained from bovine bone mandible waste heat treated at 800 °C for 5 h and amorphous SiO{sub 2} powder was extracted from citric acid leaching of rice husk followed by combustion at 700°C for 5 h. The composite powder then mixed and sintered at 1200 °C for 3 h. X-ray diffraction (XRD), Fourier transformed infrared (FTIR) spectroscopy and Scanning electron microscopy (SEM) techniques are utilized to characterize the phase relations,more » functional group present and morphology of the sample. The study has revealed that the processing procedures played an important role in microstructural development of BHAp-10 wt% SiO{sub 2} composite. The XRD study of the raw material revealed that the primary phase material in the heat treated of bovine bone mandible waste is hydroxyapatite and in the combustion of rice husk is amorphous SiO{sub 2}. However, in the composite the hydroxyapatite, β-tricalcium phosphate, and calcium phosphate silicate were observed. The FTIR result show that the hydroxyl stretching band in the composite decrease compared with those of hydroxyapatite spectra and the evolution of morphology was occurred in the composite.« less

Synthesis and characterisation of composite based biohydroxyapatite bovine bone mandible waste (BHAp) doped with 10 wt % amorphous SiO2 from rice husk by solid state reaction

NASA Astrophysics Data System (ADS)

Asmi, Dwi; Sulaiman, Ahmad; Oktavia, Irene Lucky; Badaruddin, Muhammad; Zulfia, Anne

2016-04-01

Effect of 10 wt% amorphous SiO2 from rice husk addition on the microstructures of biohydroxyapatite (BHAp) obtained from bovine bone was synthesized by solid state reaction. In this study, biohydroxyapatite powder was obtained from bovine bone mandible waste heat treated at 800 °C for 5 h and amorphous SiO2 powder was extracted from citric acid leaching of rice husk followed by combustion at 700°C for 5 h. The composite powder then mixed and sintered at 1200 °C for 3 h. X-ray diffraction (XRD), Fourier transformed infrared (FTIR) spectroscopy and Scanning electron microscopy (SEM) techniques are utilized to characterize the phase relations, functional group present and morphology of the sample. The study has revealed that the processing procedures played an important role in microstructural development of BHAp-10 wt% SiO2 composite. The XRD study of the raw material revealed that the primary phase material in the heat treated of bovine bone mandible waste is hydroxyapatite and in the combustion of rice husk is amorphous SiO2. However, in the composite the hydroxyapatite, β-tricalcium phosphate, and calcium phosphate silicate were observed. The FTIR result show that the hydroxyl stretching band in the composite decrease compared with those of hydroxyapatite spectra and the evolution of morphology was occurred in the composite.

SINTERING AND SULFATION OF CALCIUM SILICATE-ALUMINATE

EPA Science Inventory

The effect of sintering on the reactivity of solids at high temperature was studied. The nature of the interaction was studied with calcium silicate-aluminate reacting with SO2 between 665 and 800 C. The kinetics of the sintering and sulfation processes were measured independentl...

Remineralisation effect of a dual-phase calcium silicate/phosphate gel combined with calcium silicate/phosphate toothpaste on acid-challenged enamel in situ.

PubMed

Joiner, Andrew; Schäfer, Fred; Naeeni, Mojgan M; Gupta, Ashok K; Zero, Domenick T

2014-06-01

To test if a novel dual-phase gel system (calcium silicate and phosphate with 1450 ppmF, as NaF/MFP; TG) combined with a toothpaste (calcium silicate and sodium phosphate with 1450 ppmF, as MFP; TG) was able to re-harden previously acid-challenged enamel to a greater extent than other toothpastes. The study consisted of a double-blind, randomised, cross-over design with four 7-day treatment legs. In each leg, subjects wearing a partial denture holding four demineralised enamel specimens (25 min in 0.3% citric acid, pH3.8) used either the test regimen (TG+TP) or one of the three controls. (placebo TG+TP; Positive Control - placebo TG+marketed 1450 ppmF toothpaste; Negative Control - placebo TG+placebo TP). Enamel specimens were removed after 1, 2, 3 and 7 days. The gel systems were applied once per day for the first three days during which subjects also brushed with the corresponding toothpaste; this was followed by four days use of the toothpastes only. Toothpastes were used in the conventional way brushing twice per day throughout the seven days. The outcome variable was %Surface Microhardness Recovery calculated after three and seven days of in situ treatment. The results showed a statistically significant (p<0.001) re-hardening effect for all treatments compared to pre-treatment hardness. After three days and after seven days of in situ treatment significantly greater hardening (p<0.05) was found in the samples treated with calcium silicate/phosphate gel system plus calcium silicate/phosphate toothpaste than in the control groups. It is concluded that the test regimen based on the novel dual-phase gel system combined with toothpaste was able to re-harden acid-challenged tooth enamel to a greater extent than a normal fluoride toothpaste. The novel oral care products containing calcium silicate, sodium phosphate salts and fluoride is a new approach to the repair of demineralised enamel. © 2014 Elsevier Ltd. All rights reserved.

Dissociation of sarin on a cement analogue surface: Effects of humidity and confined geometry

DOE PAGES

O’Brien, Christopher J.; Greathouse, Jeffery A.; Tenney, Craig M.

2016-11-22

Here, first-principles molecular dynamics simulations were used to investigate the dissociation of sarin (GB) on the calcium silicate hydrate (CSH) mineral tobermorite (TBM), a surrogate for cement. CSH minerals (including TBM) and amorphous materials of similar composition are the major components of Portland cement, the binding agent of concrete. Metadynamics simulations were used to investigate the effect of the TBM surface and confinement in a microscale pore on the mechanism and free energy of dissociation of GB. Our results indicate that both the adsorption site and the humidity of the local environment significantly affect the sarin dissociation energy. In particular,more » sarin dissociation in a low-water environment occurs via a dealkylation mechanism, which is consistent with previous experimental studies.« less

Mechanical properties of cement concrete composites containing nano-metakaolin

NASA Astrophysics Data System (ADS)

Supit, Steve Wilben Macquarie; Rumbayan, Rilya; Ticoalu, Adriana

2017-11-01

The use of nano materials in building construction has been recognized because of its high specific surface area, very small particle sizes and more amorphous nature of particles. These characteristics lead to increase the mechanical properties and durability of cement concrete composites. Metakaolin is one of the supplementary cementitious materials that has been used to replace cement in concrete. Therefore, it is interesting to investigate the effectiveness of metakaolin (in nano scale) in improving the mechanical properties including compressive strength, tensile strength and flexural strength of cement concretes. In this experiment, metakaolin was pulverized by using High Energy Milling before adding to the concrete mixes. The pozzolan Portland cement was replaced with 5% and 10% nano-metakaolin (by wt.). The result shows that the optimum amount of nano-metakaolin in cement concrete mixes is 10% (by wt.). The improvement in compressive strength is approximately 123% at 3 days, 85% at 7 days and 53% at 28 days, respectively. The tensile and flexural strength results also showed the influence of adding 10% nano-metakaolin (NK-10) in improving the properties of cement concrete (NK-0). Furthermore, the Backscattered Electron images and X-Ray Diffraction analysis were evaluated to support the above findings. The results analysis confirm the pores modification due to nano-metakaolin addition, the consumption of calcium hydroxide (CH) and the formation of Calcium Silicate Hydrate (CSH) gel as one of the beneficial effects of amorphous nano-metakaolin in improving the mechanical properties and densification of microstructure of mortar and concrete.

Mineral abundances of comet 17P/Holmes derived from the mid-infrared spectrum

NASA Astrophysics Data System (ADS)

Shinnaka, Yoshiharu; Yamaguchi, MItsuru; Ootsubo, Takafumi; Kawakita, Hideyo; Sakon, Itsuki; Honda, Mitsuhiko; Watanabe, Jun-ichi

2017-10-01

Dust grains of crystalline silicate, which is rarely presented in an interstellar space, were found in cometary nuclei (Messenger et al. 1996, LPI, 27, 867; Wooden et al. 1999, ApJ, 517, 1058, references therein). It is thought that these crystalline silicates had formed by annealing or condensations of amorphous grains near the Sun in the solar nebula, and incorporated into a cometary nucleus in a cold region (farther than formation regions of the crystalline silicates) by radial transportation in the solar nebula. It is considered that transportation mechanisms to outside of the solar nebula were turbulent and/or X-wind. An abundance of the crystalline dust grains was therefore expected to be smaller as far from the Sun (Gail, 2001, A&A, 378, 192; Bockelée-Morvan et al. 2002, A&A, 384, 1107). Namely, the abundance ratio of the crystalline silicate in cometary dust grains relates a degree of mass transportation and a distance from the Sun when cometary nucleus formed in the Solar nebula. The mass ratio of crystalline silicates of dust grains is determined from by Si-O stretching vibrational bands of silicate grains around 10 μm using difference of spectral band features between crystalline and amorphous grains. We present the crystalline-to-amorphous mass ratio of silicate grains in the comet 17P/Holmes by using the thermal emission mode of the dust grains (Ootsubo et al. 2007, P&SS, 55, 1044) applied to the mid-infrared spectra of the comet. These spectra were taken by the COMICS mounted on the Subaru Telescope on 2007 October 25, 26, 27 and 28 immediately after the great outburst of the comet (started on October 23). We discuss about formation conditions of the nucleus of the comet based on the derived mass ratio of silicate grains of the comet.

Desulfurization of fuel gases in fluidized bed gasification and hot fuel gas cleanup systems

DOEpatents

Steinberg, M.; Farber, G.; Pruzansky, J.; Yoo, H.J.; McGauley, P.

1983-08-26

A problem with the commercialization of fluidized bed gasification is that vast amounts of spent sorbent are generated if the sorbent is used on a once-through basis, especially if high sulfur coals are burned. The requirements of a sorbent for regenerative service in the FBG process are: (1) it must be capable of reducing the sulfur containing gas concentration of the FBG flue gas to within acceptable environmental standards; (2) it must not lose its reactivity on cyclic sulfidation and regeneration; (3) it must be capable of regeneration with elimination of substantially all of its sulfur content; (4) it must have good attrition resistance; and, (5) its cost must not be prohibitive. It has now been discovered that calcium silicate pellets, e.g., Portland cement type III pellets meet the criteria aforesaid. Calcium silicate removes COS and H/sub 2/S according to the reactions given to produce calcium sulfide silicate. The sulfur containing product can be regenerated using CO/sub 2/ as the regenerant. The sulfur dioxide can be conveniently reduced to sulfur with hydrogen or carbon for market or storage. The basic reactions in the process of this invention are the reactions with calcium silicate given in the patent. A convenient and inexpensive source of calcium silicate is Portland cement. Portland cement is a readily available, widely used construction meterial.

Ultrasonic enhancing amorphization during synthesis of calcium phosphate.

PubMed

He, Kun; Xiao, Gui-Yong; Xu, Wen-Hua; Zhu, Rui-Fu; Lu, Yu-Peng

2014-03-01

Amorphous calcium phosphate (ACP) has great application potential in biomaterials field due to its non-cytotoxicity, high bioactivity, good cytocompatibility, and so on. The results of this research demonstrated that ultrasonic obviously enhanced amorphization during synthesis of calcium phosphate. The ACP phase was relatively ideal when the solvent of Ca(NO3)2·4H2O was ethanol and the solvent of (NH4)2HPO4 was a mixture of water and ethanol, under ultrasonic. In-situ crystallization of ACP could be observed by HRTEM. The mechanism on the effects of ultrasonic on amorphization of the synthesized calcium phosphate was discussed. It was suggested that ultrasonic synthesis might be a facile method to prepare pure and safe ACP related biomaterials. Copyright © 2013 Elsevier B.V. All rights reserved.

Apatite formation on bioactive calcium-silicate cements for dentistry affects surface topography and human marrow stromal cells proliferation.

PubMed

Gandolfi, Maria Giovanna; Ciapetti, Gabriela; Taddei, Paola; Perut, Francesca; Tinti, Anna; Cardoso, Marcio Vivan; Van Meerbeek, Bart; Prati, Carlo

2010-10-01

The effect of ageing in phosphate-containing solution of bioactive calcium-silicate cements on the chemistry, morphology and topography of the surface, as well as on in vitro human marrow stromal cells viability and proliferation was investigated. A calcium-silicate cement (wTC) mainly based on dicalcium-silicate and tricalcium-silicate was prepared. Alpha-TCP was added to wTC to obtain wTC-TCP. Bismuth oxide was inserted in wTC to prepare a radiopaque cement (wTC-Bi). A commercial calcium-silicate cement (ProRoot MTA) was tested as control. Cement disks were aged in DPBS for 5 h ('fresh samples'), 14 and 28 days, and analyzed by ESEM/EDX, SEM/EDX, ATR-FTIR, micro-Raman techniques and scanning white-light interferometry. Proliferation, LDH release, ALP activity and collagen production of human marrow stromal cells (MSC) seeded for 1-28 days on the cements were evaluated. Fresh samples exposed a surface mainly composed of calcium-silicate hydrates CSH (from the hydration of belite and alite), calcium hydroxide, calcium carbonate, and ettringite. Apatite nano-spherulites rapidly precipitated on cement surfaces within 5 h. On wTC-TCP the Ca-P deposits appeared thicker than on the other cements. Aged cements showed an irregular porous calcium-phosphate (Ca-P) coating, formed by aggregated apatite spherulites with interspersed calcite crystals. All the experimental cements exerted no acute toxicity in the cell assay system and allowed cell growth. Using biochemical results, the scores were: fresh cements>aged cements for cell proliferation and ALP activity (except for wTC-Bi), whereas fresh cements

21 CFR 573.260 - Calcium silicate.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 6 2011-04-01 2011-04-01 false Calcium silicate. 573.260 Section 573.260 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL DRUGS, FEEDS, AND RELATED PRODUCTS FOOD ADDITIVES PERMITTED IN FEED AND DRINKING WATER OF ANIMALS Food Additive...

21 CFR 573.260 - Calcium silicate.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Calcium silicate. 573.260 Section 573.260 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL DRUGS, FEEDS, AND RELATED PRODUCTS FOOD ADDITIVES PERMITTED IN FEED AND DRINKING WATER OF ANIMALS Food Additive...

21 CFR 573.260 - Calcium silicate.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 21 Food and Drugs 6 2012-04-01 2012-04-01 false Calcium silicate. 573.260 Section 573.260 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL DRUGS, FEEDS, AND RELATED PRODUCTS FOOD ADDITIVES PERMITTED IN FEED AND DRINKING WATER OF ANIMALS Food Additive...

21 CFR 573.260 - Calcium silicate.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 6 2014-04-01 2014-04-01 false Calcium silicate. 573.260 Section 573.260 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL DRUGS, FEEDS, AND RELATED PRODUCTS FOOD ADDITIVES PERMITTED IN FEED AND DRINKING WATER OF ANIMALS Food Additive...

21 CFR 573.260 - Calcium silicate.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 21 Food and Drugs 6 2013-04-01 2013-04-01 false Calcium silicate. 573.260 Section 573.260 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL DRUGS, FEEDS, AND RELATED PRODUCTS FOOD ADDITIVES PERMITTED IN FEED AND DRINKING WATER OF ANIMALS Food Additive...

Fischer-Tropsch-Type Production of Organic Materials in the Solar Nebula: Studies Using Graphite Catalysts and Measuring the Trapping of Noble Gases

NASA Technical Reports Server (NTRS)

Nuth, Joseph A., III; Ferguson, Frank T.; Lucas, Christopher; Kimura, Yuki; Hohenberg, Charles

2009-01-01

The formation of abundant carbonaceous material in meteorites is a long standing problem and an important factor in the debate on the potential for the origin of life in other stellar systems. The Fischer-Tropsch-type (FTT) catalytic reduction of CO by hydrogen was once the preferred model for production of organic materials in the primitive solar nebula. We have demonstrated that many grain surfaces can catalyze both FTT and HB-type reactions, including amorphous iron and magnesium silicates, pure silica smokes as well as several minerals. Graphite is not a particularly good FTT catalyst, especially compared to iron powder or to amorphous iron silicate. However, like other silicates that we have studied, it gets better with exposure to CO. N2 and H2 over time: e.g., after formation of a macromolecular carbonaceous layer on the surfaces of the underlying gains. While amorphous iron silicates required only 1 or 2 experimental runs to achieve steady state reaction rates, graphite only achieved steady state after 6 or more experiments. We will present results showing the catalytic action of graphite grains increasing with increasing number of experiments and will also discuss the nature of the final "graphite" grains aster completion of our experiments.

Annealing of Silicate Dust by Nebular Shocks at 10 AU

NASA Technical Reports Server (NTRS)

Harker, David E.; Desch, Steven J.; DeVincenzi, D. (Technical Monitor)

2001-01-01

Silicate dust grains in the interstellar medium are known to be mostly amorphous, yet crystalline silicate grains have been observed in many long-period comets and in protoplanetary disks. Annealing of amorphous silicate grains into crystalline grains requires temperatures greater than or approximately equal to 1000 K, but exposure of dust grains in comets to such high temperatures is apparently incompatible with the generally low temperatures experienced by comets. This has led to the proposal of models in which dust grains were thermally processed near the protoSun, then underwent considerable radial transport until they reached the gas giant planet region where the long-period comets originated. We hypothesize instead that silicate dust grains were annealed in situ, by shock waves triggered by gravitational instabilities. We assume a shock speed of 5 km/s, a plausible value for shocks driven by gravitational instabilities. We calculate the peak temperatures of pyroxene grains under conditions typical in protoplanetary disks at 5-10 AU. We show that in situ annealing of micron-sized dust grains can occur, obviating the need for large-scale radial transport.

MTA and F-doped MTA cements used as sealers with warm gutta-percha. Long-term study of sealing ability.

PubMed

Gandolfi, M G; Prati, C

2010-10-01

To evaluate the long-term sealing ability (up to 6 months) of two experimental calcium silicate MTA cements used as root canal sealers in association with warm gutta-percha. Calcium silicate (MTA) and calcium-fluoro-silicate powders were prepared. Sodium fluoride was included in FMTA (Fluoride-doped Mineral Trioxide Aggregate) as an expansive and retardant agent. Single-rooted teeth were instrumented with NiTi rotary instruments, filled with warm gutta-percha in association with one of the experimental sealers or with AH Plus as a control (n = 20 for each sealer) and stored at 37 °C. Sealing was assessed at 24, 48 h, 1, 2 weeks and 1, 3, 6 months by a fluid filtration method. Scanning electron microscopy with energy dispersive analysis (SEM/EDX) was used to study the dentine/sealer interface of roots stored for 6 months and the surface of cement disks stored for 24 h. All sealers revealed a statistically significant reduction (P < 0.05) in fluid filtration after the first 2 weeks. No statistically significant differences were observed between FMTA and AH Plus at all analysis times. At short times (24, 48-h), no statistically significant differences were found between the experimental cements and AH Plus. At long-term evaluations (1, 3, 6 months), FMTA and AH Plus sealed significantly better (P < 0.05) than MTA. FMTA was associated with lower fluid filtration rates, and the seal was stable from 48 h to 6 months, thus proving the most effective material. Scanning electron microscopy with energy dispersive analysis of root sections filled with calcium silicate sealers revealed the formation of a blend layer of gutta-percha and cement consequent to the warm gutta-percha condensation technique. Scanning electron microscopy with energy dispersive analysis of 24-h-stored disks identified a Ca-rich coating on the outer surface consisting of globular particles (calcium hydroxide and calcium carbonate), and a deeper internal Ca- and Si-rich region consisting of needle-like ettringite crystals and round formations of calcium silicate hydrate gel. Fluoride-doped MTA demonstrated stable sealing during a period of up to 6 months and significantly better than conventional calcium silicate MTA cements and comparable to AH Plus. The study supports the suitability of calcium silicate MTA cements as sealers in association with warm gutta-percha for root filling. © 2010 International Endodontic Journal.

Crystal Structure and Chemical Composition of a Presolar Silicate from the Queen Elizabeth Range 99177 Meteorite

NASA Technical Reports Server (NTRS)

Nguyen, A. N.; Keller, L. P.; Rahman, Z.; Messenger, S.

2013-01-01

Mineral characterization of presolar silicate grains, the most abundant stardust phase, has provided valuable information about the formation conditions in circumstellar environments and in super-nova (SN) outflows. Spectroscopic observations of dust around evolved stars suggest a majority of amor-phous, Mg-rich olivine grains, but crystalline silicates, most of which are pyroxene, have also been observed [1]. The chemical compositions of hundreds of presolar silicates have been determined by Auger spectroscopy and reveal high Fe contents and nonstoichiometric compositions intermediate to olivine and pyroxene [2-6]. The unexpectedly high Fe contents can partly be attributed to secondary alteration on the meteorite parent bodies, as some grains have Fe isotopic anomalies from their parent stellar source [7]. Only about 35 presolar silicates have been studied for their mineral structures and chemical compositions by transmission electron microscopy (TEM). These grains display a wide range of compositions and structures, including crystalline forsterite, crystalline pyroxene, nanocrystalline grains, and a majority of amorphous nonstoichiometric grains. Most of these grains were identified in the primitive Acfer 094 meteorite. Presolar silicates from this meteorite show a wide range of Fe-contents, suggestive of secondary processing on the meteorite parent body. The CR chondrite QUE 99177 has not suffered as much alteration [8] and displays the highest presolar silicate abundance to date among carbonaceous chondrites [3, 6]. However, no mineralogical studies of presolar silicates from this meteorite have been performed. Here we examine the mineralogy of a presolar silicate from QUE 99177.

Radiation-induced amorphization of Ce-doped Mg2Y8(SiO4)6O2 silicate apatite

NASA Astrophysics Data System (ADS)

Zhou, Jianren; Yao, Tiankai; Lian, Jie; Shen, Yiqiang; Dong, Zhili; Lu, Fengyuan

2016-07-01

Ce-doped Mg2Y8(SiO4)6O2 silicate apatite (Ce = 0.05 and 0.5) were irradiated with 1 MeV Kr2+ ion beam irradiation at different temperatures and their radiation response and the cation composition dependence of the radiation-induced amorphization were studied by in situ TEM. The two Ce-doped Mg2Y8(SiO4)6O2 silicate apatites are sensitive to ion beam induced amorphization with a low critical dose (0.096 dpa) at room temperature, and exhibits significantly different radiation tolerance at elevated temperatures. Ce concentration at the apatite AI site plays a critical role in determining the radiation response of this silicate apatite, in which the Ce3+ rich Mg2Y7.5Ce0.5(SiO4)6O2 displays lower amorphization susceptibility than Mg2Y7.95Ce0.05(SiO4)6O2 with a lower Ce3+ occupancy at the AI sites. The critical temperature (Tc) and activation energy (Ea) change from 667.5 ± 33 K and 0.162 eV of Mg2Y7.5Ce0.5(SiO4)6O2 to 963.6 ± 64 K and 0.206 eV of Mg2Y7.95Ce0.05(SiO4)6O2. We demonstrate that the radiation tolerance can be controlled by varying the chemical composition, and enhanced radiation tolerance is achieved by increasing the Ce concentration at the AI site.

Evolution of trees and mycorrhizal fungi intensifies silicate mineral weathering.

PubMed

Quirk, Joe; Beerling, David J; Banwart, Steve A; Kakonyi, Gabriella; Romero-Gonzalez, Maria E; Leake, Jonathan R

2012-12-23

Forested ecosystems diversified more than 350 Ma to become major engines of continental silicate weathering, regulating the Earth's atmospheric carbon dioxide concentration by driving calcium export into ocean carbonates. Our field experiments with mature trees demonstrate intensification of this weathering engine as tree lineages diversified in concert with their symbiotic mycorrhizal fungi. Preferential hyphal colonization of the calcium silicate-bearing rock, basalt, progressively increased with advancement from arbuscular mycorrhizal (AM) to later, independently evolved ectomycorrhizal (EM) fungi, and from gymnosperm to angiosperm hosts with both fungal groups. This led to 'trenching' of silicate mineral surfaces by AM and EM fungi, with EM gymnosperms and angiosperms releasing calcium from basalt at twice the rate of AM gymnosperms. Our findings indicate mycorrhiza-driven weathering may have originated hundreds of millions of years earlier than previously recognized and subsequently intensified with the evolution of trees and mycorrhizas to affect the Earth's long-term CO(2) and climate history.

Physicochemical properties of calcium silicate cements associated with microparticulate and nanoparticulate radiopacifiers.

PubMed

Bosso-Martelo, Roberta; Guerreiro-Tanomaru, Juliane M; Viapiana, Raqueli; Berbert, Fabio Luiz C; Duarte, Marco Antonio Hungaro; Tanomaru-Filho, Mário

2016-01-01

The objective of this paper was to evaluate the physicochemical properties of calcium silicate cements with different chemical compositions, associated with radiopacifying agents. Mineral trioxide aggregate (MTA) Angelus, calcium silicate cement with additives (CSC), and resinous calcium silicate cement (CSCR) were evaluated, with the addition of the following radiopacifiers: microparticles (micro) or nanoparticles (nano) of zirconium oxide (ZrO(2)), niobium oxide (Nb(2)O(5)), bismuth oxide (Bi(2)O(3)), or calcium tungstate (CaWO(4)). Setting time was evaluated using Gilmore needles. Solubility was determined after immersion in water. The pH and calcium ion release were analyzed after 3, 12, and 24 h and 7, 14, and 21 days. The data obtained were submitted to analysis of variance and Tukey's test, at a level of significance of 5 %. CSC + CaWO(4) and CSCR + ZrO(2) micro, Nb(2)O(5) and CaWO(4) presented results similar to MTA, with a shorter final setting time than the other associations. CSC and CSCR+ ZrO(2) micro presented a higher degree of flow. All the cements evaluated presented low solubility. The materials presented alkaline pH and released calcium ions. ZrO(2) micro radiopacifier may be considered a potential substitute for Bi(2)O(3) when associated with CSC or CSCR. The proposed materials, especially when associated with ZrO(2), are potential materials for use as alternatives to MTA.

On the structure of amorphous calcium carbonate--a detailed study by solid-state NMR spectroscopy.

PubMed

Nebel, Holger; Neumann, Markus; Mayer, Christian; Epple, Matthias

2008-09-01

The calcium carbonate phases calcite, aragonite, vaterite, monohydrocalcite (calcium carbonate monohydrate), and ikaite (calcium carbonate hexahydrate) were studied by solid-state NMR spectroscopy ( (1)H and (13)C). Further model compounds were sodium hydrogencarbonate, potassium hydrogencarbonate, and calcium hydroxide. With the help of these data, the structure of synthetically prepared additive-free amorphous calcium carbonate (ACC) was analyzed. ACC contains molecular water (as H 2O), a small amount of mobile hydroxide, and no hydrogencarbonate. This supports the concept of ACC as a transient precursor in the formation of calcium carbonate biominerals.

Calcium-silicate mesoporous nanoparticles loaded with chlorhexidine for both anti- Enterococcus faecalis and mineralization properties.

PubMed

Fan, Wei; Li, Yanyun; Sun, Qing; Ma, Tengjiao; Fan, Bing

2016-10-21

In infected periapical tissues, Enterococcus faecalis is one of the most common dominant bacteria. Chlorhexidine has been proved to show strong antibacterial ability against E. faecalis but is ineffective in promoting mineralization for tissues around root apex. Mesoporous calcium-silicate nanoparticles are newly synthesized biomaterials with excellent ability to promote mineralization and carry-release bioactive molecules in a controlled manner. In this study, mesoporous calcium-silicate nanoparticles were functionalized with chlorhexidine and their releasing profile, antibacterial ability, effect on cell proliferation and in vitro mineralization property were evaluated. The chlorhexidine was successfully incorporated into mesoporous calcium-silicate nanoparticles by a mixing-coupling method. The new material could release chlorhexidine as well as Ca 2+ and SiO 3 2- in a sustained manner with an alkaline pH value under different conditions. The antimicrobial ability against planktonic E. faecalis was dramatically improved after chlorhexidine incorporation. The nanoparticles with chlorhexidine showed no negative effect on cell proliferation with low concentrations. On dentin slices, the new synthesized material demonstrated a similar inhibitory effect on E. faecalis as the chlorhexidine. After being immersed in SBF for 9 days, numerous apatite crystals could be observed on surfaces of the material tablets. Mesoporous calcium-silicate nanoparticles loaded with chlorhexidine exhibited release of ions and chlorhexidine, low cytotoxicity, excellent antibacterial ability and in vitro mineralization. This material could be developed into a new effective intra-canal medication in dentistry or a new bone defect filling material for infected bone defects.

Diffusion-driven D/H fractionation in silicates during hydration, dehydration and degassing

NASA Astrophysics Data System (ADS)

Roskosz, Mathieu; Laporte, Didier; Deloule, Etienne; Ingrin, Jannick; Remusat, Laurent; Depecker, Christophe; Leroux, Hugues

2017-04-01

Understanding how degassing occurs during accretion and differentiation is crucial to explain the water budget of planetary bodies. In this context, the hydrogen isotopic signature of water in mantle minerals and melts is particularly useful to trace reservoirs and their interactions. Nonetheless, little is known on the influence of mantle processes on the D/H signatures of silicates. In this study, we performed controlled hydration/dehydration experiments. We explore the possibility that diffusion-driven fractionation could affect the D/H signature of partially hydrated amorphous or molten silicates and nominally anhydrous minerals (NAMs). High purity synthetic fused silica samples were annealed at between 200 and 1000°C at 20 mbar water partial pressure for 1 to 30 days. Dehydration of initially hydrated silica was also performed at 1000°C for a few hours. A set of rhyolitic samples previously synthesized in order to study bubble nucleation during magma decompression was also analyzed. Finally a natural grossular monocrystal (Zillertaler Alps, Austria), partially dehydrated in air at 800°C for 10 hours was studied. Water content and speciation were measured both by Fourier-Transform Infra-Red and Raman spectroscopies. Isotopic analyses were performed with the IMS 1270 and 1280 ion microprobes. The silica samples, the rhyolitic glasses and the grossular monocrystal exhibit typical water concentration profiles. In all cases, water speciation does not change significantly along concentration profiles. Concerning D/H signatures, no isotopic variation is detectable across amorphous silica and rhyolitic glasses. The situation is however very different in the grossular monocrystal. A strong isotopic gradient appears correlated to the water concentration profile. Our data are interpreted in terms of diffusion mechanisms in both amorphous (and molten) silicates and NAMs. Hydration, dehydration and magma degassing are probably not able to promote large diffusion-driven fractionation of hydrogen in amorphous silicates. Conversely, the diffusion of water through the structure of NAMs affects the overall isotopic composition of dissolved water.

Amorphous calcium carbonate: A precursor phase for aragonite in shell disease of the pearl oyster.

PubMed

Huang, Jingliang; Liu, Chuang; Xie, Liping; Zhang, Rongqing

2018-02-26

Amorphous calcium carbonate (ACC) has long been shown to act as an important constituent or precursor phase for crystalline material in mollusks. However, the presence and the role of ACC in bivalve shell formation are not fully studied. In this study, we found that brown deposits containing heterogeneous calcium carbonates were precipitated when a shell disease occurred in the pearl oyster Pinctada fucata. Calcein-staining of the brown deposits indicated that numerous amorphous calcium deposits were present, which was further confirmed by Fourier-transform infrared spectroscopy (FTIR), Raman spectrum and X-ray difraction (XRD) analyses. So we speculate that ACC plays an important role in rapid calcium carbonate precipitation during shell repair process in diseased oysters. Copyright © 2018 Elsevier Inc. All rights reserved.

Spectral evidence for amorphous silicates in least-processed CO meteorites and their parent bodies

NASA Astrophysics Data System (ADS)

McAdam, Margaret M.; Sunshine, Jessica M.; Howard, Kieren T.; Alexander, Conel M.; McCoy, Timothy J.; Bus, Schelte J.

2018-05-01

Least-processed carbonaceous chondrites (carbonaceous chondrites that have experienced minimal aqueous alteration and thermal metamorphism) are characterized by their predominately amorphous iron-rich silicate interchondrule matrices and chondrule rims. This material is highly susceptible to destruction by the parent body processes of thermal metamorphism or aqueous alteration. The presence of abundant amorphous material in a meteorite indicates that the parent body, or at least a region of the parent body, experienced minimal processing since the time of accretion. The CO chemical group of carbonaceous chondrites has a significant number of these least-processed samples. We present visible/near-infrared and mid-infrared spectra of eight least-processed CO meteorites (petrologic type 3.0-3.1). In the visible/near-infrared, these COs are characterized by a broad weak feature that was first observed by Cloutis et al. (2012) to be at 1.3-μm and attributed to iron-rich amorphous silicate matrix materials. This feature is observed to be centered at 1.4-μm for terrestrially unweathered, least-processed CO meteorites. At mid-infrared wavelengths, a 21-μm feature, consistent with Si-O vibrations of amorphous materials and glasses, is also present. The spectral features of iron-rich amorphous silicate matrix are absent in both the near- and mid-infrared spectra of higher metamorphic grade COs because this material has recrystallized as crystalline olivine. Furthermore, spectra of least-processed primitive meteorites from other chemical groups (CRs, MET 00426 and QUE 99177, and C2-ungrouped Acfer 094), also exhibit a 21-μm feature. Thus, we conclude that the 1.4- and 21-μm features are characteristic of primitive least-processed meteorites from all chemical groups of carbonaceous chondrites. Finally, we present an IRTF + SPeX observation of asteroid (93) Minerva that has spectral similarities in the visible/near-infrared to the least-processed CO carbonaceous chondrites. While Minerva is not the only CO-like asteroid (e.g., Burbine et al., 2001), Minerva is likely the least-processed CO-like asteroid observed to date.

Preparation and Evaluation of Solid Dispersion Tablets by a Simple and Manufacturable Wet Granulation Method Using Porous Calcium Silicate.

PubMed

Fujimoto, Yumi; Hirai, Nobuaki; Takatani-Nakase, Tomoka; Takahashi, Koichi

2016-01-01

The aim of this study was to prepare and evaluate solid dispersion tablets containing a poorly water-soluble drug using porous calcium silicate (PCS) by a wet granulation method. Nifedipine (NIF) was used as the model poorly water-soluble drug. Solid dispersion tablets were prepared with the wet granulation method using ethanol and water by a high-speed mixer granulator. The binder and disintegrant were selected from 7 and 4 candidates, respectively. The dissolution test was conducted using the JP 16 paddle method. The oral absorption of NIF was studied in fasted rats. Xylitol and crospovidone were selected as the binder and disintegrant, respectively. The dissolution rates of NIF from solid dispersion formulations were markedly enhanced compared with NIF powder and physical mixtures. Powder X-ray diffraction (PXRD) confirmed the reduced crystallinity of NIF in the solid dispersion formulations. Fourier transform infrared (FT-IR) showed the physical interaction between NIF and PCS in the solid dispersion formulations. NIF is present in an amorphous state in granules prepared by the wet granulation method using water. The area under the plasma concentration-time curve (AUC) and peak concentration (C(max)) values of NIF after dosing rats with the solid dispersion granules were significantly greater than those after dosing with NIF powder. The solid dispersion formulations of NIF prepared with PCS using the wet granulation method exhibited accelerated dissolution rates and superior oral bioavailability. This method is very simple, and may be applicable to the development of other poorly water-soluble drugs.

Why is it so difficult to classify Renazzo-type (CR) carbonaceous chondrites? - Implications from TEM observations of matrices for the sequences of aqueous alteration

NASA Astrophysics Data System (ADS)

Abreu, Neyda M.

2016-12-01

A number of different classifications have been proposed for the CR chondrites; this study aims at reconciling these different schemes. Mineralogy-based classification has proved particularly challenging for weakly to moderately altered CRs because incipient mineral replacement and elemental mobilization arising from aqueous alteration only affected the most susceptible primary phases, which are generally located in the matrix. Secondary matrix phases are extremely fine-grained (generally sub-micron) and heterogeneously mixed with primary nebular materials. Compositional and isotopic classification parameters are fraught with confounding factors, such as terrestrial weathering, impact processes, and variable abundance of clasts from different regions of the CR parent body or from altogether different planetary bodies. Here, detailed TEM observations from eighteen FIB sections retrieved from the matrices of nine Antarctic CR chondrites (EET 96259, GRA 95229, GRO 95577, GRO 03116, LAP 02342, LAP 04516, LAP 04720, MIL 07525, and MIL 090001) are presented, representing a range of petrologic types. Amorphous Fe-Mg silicates are found to be the dominant phase in all but the most altered CR chondrite matrices, which still retain significant amounts of these amorphous materials. Amorphous Fe-Mg silicates are mixed with phyllosilicates at the nanometer scale. The ratio of amorphous Fe-Mg silicates to phyllosilicates decreases as: (1) the size of phyllosilicates, (2) abundance of magnetite, and (3) replacement of Fe-Ni sulfides increase. Carbonates are only abundant in the most altered CR chondrite, GRO 95577. Nanophase Fe-Ni metal and tochilinite are present small abundances in most CR matrices. Based on the presence, abundance and size of phyllosilicates with respect to amorphous Fe-Mg silicates, the sub-micron features of CR chondrites have been linked to existing classification sequences, and possible reasons for inconsistencies among classification schemes are discussed.

Premixed calcium silicate cement for endodontic applications

PubMed Central

Persson, Cecilia; Engqvist, Håkan

2011-01-01

Calcium silicate-based materials (also called MTA) are increasingly being used in endodontic applications. However, the handling properties of MTA are not optimal when it comes to injectability and cohesion. Premixing the cements using glycerol avoids these issues. However, there is a lack of data on the effect of common cement variables on important properties of premixed cements for endodontic applications. In this study, the effects of liquid-to-powder ratio, amount of radiopacifier and amount of calcium sulfate (added to control the setting time) were screened using a statistical model. In the second part of the study, the liquid-to-powder ratio was optimized for cements containing three different amounts of radiopacifier. Finally, the effect of using glycerol rather than water was evaluated in terms of radiopacity. The setting time was found to increase with the amount of radiopacifier when the liquid-to-powder ratio was fixed. This was likely due to the higher density of the radiopacifier in comparison to the calcium silicate, which gave a higher liquid-to-powder ratio in terms of volume. Using glycerol rather than water to mix the cements led to a decrease in radiopacity of the cement. In conclusion, we were able to produce premixed calcium silicate cements with acceptable properties for use in endodontic applications. PMID:23507729

Premixed calcium silicate cement for endodontic applications: injectability, setting time and radiopacity.

PubMed

Persson, Cecilia; Engqvist, Håkan

2011-01-01

Calcium silicate-based materials (also called MTA) are increasingly being used in endodontic applications. However, the handling properties of MTA are not optimal when it comes to injectability and cohesion. Premixing the cements using glycerol avoids these issues. However, there is a lack of data on the effect of common cement variables on important properties of premixed cements for endodontic applications. In this study, the effects of liquid-to-powder ratio, amount of radiopacifier and amount of calcium sulfate (added to control the setting time) were screened using a statistical model. In the second part of the study, the liquid-to-powder ratio was optimized for cements containing three different amounts of radiopacifier. Finally, the effect of using glycerol rather than water was evaluated in terms of radiopacity. The setting time was found to increase with the amount of radiopacifier when the liquid-to-powder ratio was fixed. This was likely due to the higher density of the radiopacifier in comparison to the calcium silicate, which gave a higher liquid-to-powder ratio in terms of volume. Using glycerol rather than water to mix the cements led to a decrease in radiopacity of the cement. In conclusion, we were able to produce premixed calcium silicate cements with acceptable properties for use in endodontic applications.

Testing Urey's carbonate-silicate cycle using the calcium isotopic composition of sedimentary carbonates

NASA Astrophysics Data System (ADS)

Blättler, Clara L.; Higgins, John A.

2017-12-01

Carbonate minerals constitute a major component of the sedimentary geological record and an archive of a fraction of the carbon and calcium cycled through the Earth's surface reservoirs for over three billion years. For calcium, carbonate minerals constitute the ultimate sink for almost all calcium liberated during continental and submarine weathering of silicate minerals. This study presents >500 stable isotope ratios of calcium in Precambrian carbonate sediments, both limestones and dolomites, in an attempt to characterize the isotope mass balance of the sedimentary carbonate reservoir through time. The mean of the dataset is indistinguishable from estimates of the calcium isotope ratio of bulk silicate Earth, consistent with the Urey cycle being the dominant mechanism exchanging calcium among surface reservoirs. The variability in bulk sediment calcium isotope ratios within each geological unit does not reflect changes in the global calcium cycle, but rather highlights the importance of local mineralogical and/or diagenetic effects in the carbonate record. This dataset demonstrates the potential for calcium isotope ratios to help assess these local effects, such as the former presence of aragonite, even in rocks with a history of neomorphism and recrystallization. Additionally, 29 calcium isotope measurements are presented from ODP (Ocean Drilling Program) Site 801 that contribute to the characterization of altered oceanic crust as an additional sink for calcium, and whose distinct isotopic signature places a limit on the importance of this subduction flux over Earth history.

Calcium silicate insulation structure

DOEpatents

Kollie, Thomas G.; Lauf, Robert J.

1995-01-01

An insulative structure including a powder-filled evacuated casing utilizes a quantity of finely divided synthetic calcium silicate having a relatively high surface area. The resultant structure-provides superior thermal insulating characteristics over a broad temperature range and is particularly well-suited as a panel for a refrigerator or freezer or the insulative barrier for a cooler or a insulated bottle.

Microstructure, Porosity and Mechanical Property Relationships of Calcium-Silicate-Hydrate

DTIC Science & Technology

1991-02-15

feasibility of producing S ,,zeolite-cement composites . calcium silicate hydrate (C-S-H) structure, NAS NMR, C3S, pH, zeolites, aluminosilicate hydrate...3 S pH- Composition Plots......................................... 6 X-ray Diffraction...6 The System CaO-A1203-SiO 2 -H2 0................................. 8 pH- Composition Plots......................................... 8 MASNMR

Amorphous calcium carbonate controls avian eggshell mineralization: A new paradigm for understanding rapid eggshell calcification.

PubMed

Rodríguez-Navarro, Alejandro B; Marie, Pauline; Nys, Yves; Hincke, Maxwell T; Gautron, Joel

2015-06-01

Avian eggshell mineralization is the fastest biogenic calcification process known in nature. How this is achieved while producing a highly crystalline material composed of large calcite columnar single crystals remains largely unknown. Here we report that eggshell mineral originates from the accumulation of flat disk-shaped amorphous calcium carbonate (ACC) particles on specific organic sites on the eggshell membrane, which are rich in proteins and sulfated proteoglycans. These structures known as mammillary cores promote the nucleation and stabilization of a amorphous calcium carbonate with calcitic short range order which predetermine the calcite composition of the mature eggshell. The amorphous nature of the precursor phase was confirmed by the diffuse scattering of X-rays and electrons. The nascent calcitic short-range order of this transient mineral phase was revealed by infrared spectroscopy and HRTEM. The ACC mineral deposited around the mammillary core sites progressively transforms directly into calcite crystals without the occurrence of any intermediate phase. Ionic speciation data suggest that the uterine fluid is equilibrated with amorphous calcium carbonate, throughout the duration of eggshell mineralization process, supporting that this mineral phase is constantly forming at the shell mineralization front. On the other hand, the transient amorphous calcium carbonate mineral deposits, as well as the calcite crystals into which they are converted, form by the ordered aggregation of nanoparticles that support the rapid mineralization of the eggshell. The results of this study alter our current understanding of avian eggshell calcification and provide new insights into the genesis and formation of calcium carbonate biominerals in vertebrates. Copyright © 2015 Elsevier Inc. All rights reserved.

Template-assisted mineral formation via an amorphous liquid phase precursor route

NASA Astrophysics Data System (ADS)

Amos, Fairland F.

The search for alternative routes to synthesize inorganic materials has led to the biomimetic route of producing ceramics. In this method, materials are manufactured at ambient temperatures and in aqueous solutions with soluble additives and insoluble matrix, similar to the biological strategy for the formation of minerals by living organisms. Using this approach, an anionic polypeptide additive was used to induce an amorphous liquid-phase precursor to either calcium carbonate or calcium phosphate. This precursor was then templated on either organic or inorganic substrates. Non-equilibrium morphologies, such as two-dimensional calcium carbonate films, one-dimensional calcium carbonate mesostructures and "molten" calcium phosphate spherulites were produced, which are not typical of the traditional (additive-free) solution grown crystals in the laboratory. In the study of calcium carbonate, the amorphous calcium carbonate mineral formed via the liquid-phase precursor, either underwent a dissolution-recrystallization event or a pseudo-solid-state transformation to produce different morphologies and polymorphs of the mineral. Discrete or aggregate calcite crystals were formed via the dissolution of the amorphous phase to allow the reprecipitation of the stable crystal. Non-equilibrium morphologies, e.g., films, mesotubules and mesowires were templated using organic and inorganic substrates and compartments. These structures were generated via an amorphous solid to crystalline solid transformation. Single crystalline tablets and mesowires of aragonite, which are reported to be found only in nature as skeletal structures of marine organisms, such as mollusk nacre and echinoderm teeth, were successfully synthesized. These biomimetic structures were grown via the polymer-induced liquid-phase precursor route in the presence of magnesium. Only low magnesium-bearing calcite was formed in the absence of the polymer. A similar approach of using a polymeric additive was implemented in calcium phosphate. Spherulitic crystals and films, seemingly formed from a molten state, were produced. These structures served as nucleating surfaces for the radial formation of calcium oxalate minerals. The composite calcium phosphate-calcium oxalate assemblies are similar to the core-shell structures found in certain kidney stones.

Production of High Molecular Weight Organic Compounds on the Surfaces of Amorphous Iron Silicate Catalysts: Implications for Organic Synthesis in the Solar Nebula

NASA Technical Reports Server (NTRS)

Gilmour, I.; Hill, H. G. M.; Pearson, V. K.; Sephton, M. A.; Nuth, J. A., III

2002-01-01

The high molecular weight organic products of Fischer-Tropsch/Haber-Bosch syntheses on the surfaces of Fe-silicate catalysts have been studied by GCMS. Additional information is contained in the original extended abstract.

Physico-chemical characterization of mortars as a tool in studying specific hydraulic components: application to the study of ancient Naxos aqueduct

NASA Astrophysics Data System (ADS)

Maravelaki-Kalaitzaki, P.; Galanos, A.; Doganis, I.; Kallithrakas-Kontos, N.

2011-07-01

Mortars and plasters from the ancient aqueduct on the island of Naxos, Greece, were studied with regard to mineralogical and chemical composition, grain size distribution, raw materials and hydraulic properties, in order to assess their characteristics and design compatible repair mortars. The authentic materials contained lime, crushed-brick, siliceous and calcitic aggregates, in different proportions according to mortar type. Crushed-bricks fired at low temperatures and lightweight volcanic aggregates contained amorphous phases, which upon reaction with lime yielded hydraulic components capable of protecting the construction from the continuous presence of water. Hydraulic calcium silicate/aluminate hydrates, the proportions and the perfect packing of the raw materials, along with the diligent application justify the longevity and durability of the studied samples. The hydraulic properties of samples were pointed out through (a) the well-established CO2/H2O ratio derived from the thermogravimetric analysis and (b) by introducing two powerful indices issued from the chemical analysis, namely CaOhydr and soluble SiO2 hydr. These indices improved the clustering of hydraulic mortars and provided better correlation between mortars, plasters and their binders. By comparing grain size distribution and hydraulicity indices it was possible to distinguish among the construction phases. Based on this study, repair mortars were formulated by hydraulic lime, siliceous sand, calcareous and crushed-brick aggregates, with the optimal water content, ensuring optimum workability and compatible appearance with the authentic ones.

Carbonate formation in non-aqueous environments by solid-gas carbonation of silicates

NASA Astrophysics Data System (ADS)

Day, S. J.; Thompson, S. P.; Evans, A.; Parker, J. E.

2012-02-01

We have produced synthetic analogues of cosmic silicates using the Sol Gel method, producing amorphous silicates of composition Mg(x)Ca(1-x)SiO3. Using synchrotron X-ray powder diffraction on Beamline I11 at the Diamond Light Source, together with a newly-commissioned gas cell, real-time powder diffraction scans have been taken of a range of silicates exposed to CO2 under non-ambient conditions. The SXPD is complemented by other techniques including Raman and Infrared Spectroscopy and SEM imaging.

Imaging of drug loading distributions in individual microspheres of calcium silicate hydrate - an X-ray spectromicroscopy study

NASA Astrophysics Data System (ADS)

Guo, Xiaoxuan; Wang, Zhiqiang; Wu, Jin; Wang, Jian; Zhu, Ying-Jie; Sham, Tsun-Kong

2015-04-01

Imaging is one of the most direct and ideal ways to track drug loading distributions in drug carriers on the molecular level, which will facilitate the optimization of drug carriers and drug loading capacities. Herein, we report the mapping of an individual mesoporous calcium silicate hydrate (CSH) microsphere before and after the loading of ibuprofen (IBU) and the interactions between drug carriers and drug molecules simultaneously by scanning transmission X-ray microscopy (STXM). Nanoscaled X-ray absorption near edge structure (XANES) spectroscopy clearly indicates that IBU is bonded to calcium and silicate sites via carboxylic acid groups. More importantly, STXM has been successfully used to determine the absolute thickness of IBU, revealing its distribution in the CSH microsphere.Imaging is one of the most direct and ideal ways to track drug loading distributions in drug carriers on the molecular level, which will facilitate the optimization of drug carriers and drug loading capacities. Herein, we report the mapping of an individual mesoporous calcium silicate hydrate (CSH) microsphere before and after the loading of ibuprofen (IBU) and the interactions between drug carriers and drug molecules simultaneously by scanning transmission X-ray microscopy (STXM). Nanoscaled X-ray absorption near edge structure (XANES) spectroscopy clearly indicates that IBU is bonded to calcium and silicate sites via carboxylic acid groups. More importantly, STXM has been successfully used to determine the absolute thickness of IBU, revealing its distribution in the CSH microsphere. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr07471h

Present and future of glass-ionomers and calcium-silicate cements as bioactive materials in dentistry: Biophotonics-based interfacial analyses in health and disease

PubMed Central

Watson, Timothy F.; Atmeh, Amre R.; Sajini, Shara; Cook, Richard J.; Festy, Frederic

2014-01-01

Objective Since their introduction, calcium silicate cements have primarily found use as endodontic sealers, due to long setting times. While similar in chemistry, recent variations such as constituent proportions, purities and manufacturing processes mandate a critical understanding of service behavior differences of the new coronal restorative material variants. Of particular relevance to minimally invasive philosophies is the potential for ion supply, from initial hydration to mature set in dental cements. They may be capable of supporting repair and remineralization of dentin left after decay and cavity preparation, following the concepts of ion exchange from glass ionomers. Methods This paper reviews the underlying chemistry and interactions of glass ionomer and calcium silicate cements, with dental tissues, concentrating on dentin–restoration interface reactions. We additionally demonstrate a new optical technique, based around high resolution deep tissue, two-photon fluorescence and lifetime imaging, which allows monitoring of undisturbed cement–dentin interface samples behavior over time. Results The local bioactivity of the calcium-silicate based materials has been shown to produce mineralization within the subjacent dentin substrate, extending deep within the tissues. This suggests that the local ion-rich alkaline environment may be more favorable to mineral repair and re-construction, compared with the acidic environs of comparable glass ionomer based materials. Significance The advantages of this potential re-mineralization phenomenon for minimally invasive management of carious dentin are self-evident. There is a clear need to improve the bioactivity of restorative dental materials and these calcium silicate cement systems offer exciting possibilities in realizing this goal. PMID:24113131

Raman spectroscopic study of ancient South African domestic clay pottery

NASA Astrophysics Data System (ADS)

Legodi, M. A.; de Waal, D.

2007-01-01

The technique of Raman spectroscopy was used to examine the composition of ancient African domestic clay pottery of South African origin. One sample from each of four archaeological sites including Rooiwal, Lydenburg, Makahane and Graskop was studied. Normal dispersive Raman spectroscopy was found to be the most effective analytical technique in this study. XRF, XRD and FT-IR spectroscopy were used as complementary techniques. All representative samples contained common features, which were characterised by kaolin (Al 2Si 2O 5(OH) 5), illite (KAl 4(Si 7AlO 20)(OH) 4), feldspar (K- and NaAlSi 3O 8), quartz (α-SiO 2), hematite (α-Fe 2O 3), montmorillonite (Mg 3(Si,Al) 4(OH) 2·4.5H 2O[Mg] 0.35), and calcium silicate (CaSiO 3). Gypsum (CaSO 4·2H 2O) and calcium carbonates (most likely calcite, CaCO 3) were detected by Raman spectroscopy in Lydenburg, Makahane and Graskop shards. Amorphous carbon (with accompanying phosphates) was observed in the Raman spectra of Lydenburg, Rooiwal and Makahane shards, while rutile (TiO 2) appeared only in Makahane shard. The Raman spectra of Lydenburg and Rooiwal shards further showed the presence of anhydrite (CaSO 4). The results showed that South African potters used a mixture of clays as raw materials. The firing temperature for most samples did not exceed 800 °C, which suggests the use of open fire. The reddish brown and grayish black colours were likely due to hematite and amorphous carbon, respectively.

Characterization of un-hydrated and hydrated BioAggregate™ and MTA Angelus™.

PubMed

Camilleri, J; Sorrentino, F; Damidot, D

2015-04-01

BioAggregate™ is a novel material introduced for use as a root-end filling material. It is tricalcium silicate-based, free of aluminium and uses tantalum oxide as radiopacifier. BioAggregate contains additives to enhance the material performance. The purpose of this research was to characterize the un-hydrated and hydrated forms of BioAggregate using a combination of techniques, verify whether the additives if present affect the properties of the set material and compare these properties to those of MTA Angelus™. Un-hydrated and hydrated BioAggregate and MTA Angelus were assessed. Un-hydrated cement was tested for chemical composition, specific surface area, mineralogy and kinetics of hydration. The set material was investigated for mineralogy, microstructure and bioactivity. Scanning electron microscopy, X-ray energy dispersive spectroscopic analysis, X-ray fluorescence spectroscopy, X-ray diffraction and isothermal calorimetry were employed. The specific surface area was investigated using a gas adsorption method with nitrogen as the probe. BioAggregate was composed of tricalcium silicate, tantalum oxide, calcium phosphate and silicon dioxide and was free of aluminium. On hydration, the tricalcium silicate produced calcium silicate hydrate and calcium hydroxide. The former was deposited around the cement grains, while the latter reacted with the silicon dioxide to form additional calcium silicate hydrate. This resulted in reduction of calcium hydroxide in the aged cement. MTA Angelus reacted in a similar fashion; however, since it contained no additives, the calcium hydroxide was still present in the aged cement. Bioactivity was demonstrated by deposition of hydroxyapatite. BioAggregate exhibited a high specific surface area. Nevertheless, the reactivity determined by isothermal calorimetry appeared to be slow compared to MTA Angelus. The tantalum oxide as opposed to bismuth oxide was inert, and tantalum was not leached in solution. BioAggregate exhibited high calcium ion release early, which was maintained over the 28-day period as opposed to MTA Angelus, which demonstrated low early calcium ion release which increased as the material aged. The mineralogical composition of BioAggregate was different to MTA Angelus. As opposed to MTA Angelus, BioAggregate did not contain aluminium and contained additives such as calcium phosphate and silicon dioxide. As a consequence, BioAggregate reacted more slowly and formation of calcium hydroxide and leaching of calcium ions in solution were not evident as the material aged. The additives in BioAggregate modify the kinetics and the end products of hydration. Although newer generation tricalcium silicate-based materials contain similar constituents to MTA, they do not undergo the same setting reactions, and thus, their clinical performance will not be comparable to that of MTA.

Ultraviolet interstellar linear polarization. I - Applicability of current dust grain models

NASA Technical Reports Server (NTRS)

Wolff, Michael J.; Clayton, Geoffrey C.; Meade, Marilyn R.

1993-01-01

UV spectropolarimetric observations yielding data on the wavelength-dependence of interstellar polarization along eight lines of sight facilitate the evaluation of dust grain models previously used to fit the extinction and polarization in the visible and IR. These models pertain to bare silicate/graphite grains, silicate cores with organic refractory mantles, silicate cores with amorphous carbon mantles, and composite grains. The eight lines-of-sight show three different interstellar polarization dependences.

Preliminary study of raw material for calcium silicate/PVA coating on Ti-6Al-4V alloy

NASA Astrophysics Data System (ADS)

Azam, Farah Atiqah bt Abdul; Shamsudin, Roslinda

2015-09-01

Calcium silicate bioceramic was prepared from the rice husk and limestone resources using the sol gel method. The preparations of CaSiO3 formulation were differ from the previous study due CaO/SiO2 amount with 45:55 ratio. X-Ray Fluorescence analysis was carried out to clarify the amount of SiO2 and CaO content in the limestone and rice husk ash. The high amount of CaO was found in the limestone with the percentages of 97.22%, whereby 89% of SiO2 content of the rice husk ash. Several milling time were studied to obtain the optimized milling ti me and speed in progress to obtain nano size particle. The particle size analysis result confirms that increase in milling time does not certainly reduce the size of particle. The addition of 0.05% polyvinyl alcohol as a binder did not change the phases or composition of calcium silicates after examined by X-Ray diffraction analysis which make it suitable to be used as a binder for calcium silicate coating without changing the chemical structure.

Vibrational investigation of calcium-silicate cements for endodontics in simulated body fluids

NASA Astrophysics Data System (ADS)

Taddei, Paola; Modena, Enrico; Tinti, Anna; Siboni, Francesco; Prati, Carlo; Gandolfi, Maria Giovanna

2011-05-01

Calcium-silicate MTA (Mineral Trioxide Aggregate) cements have been recently developed for oral and endodontic surgery. This study was aimed at investigating commercial (White ProRoot MTA, White and Grey MTA-Angelus) and experimental (wTC-Bi) accelerated calcium-silicate cements with regards to composition, hydration products and bioactivity upon incubation for 1-28 days at 37 °C, in Dulbecco's Phosphate Buffered Saline (DPBS). Deposits on the surface of the cements and the composition changes during incubation were investigated by micro-Raman and ATR/FT-IR spectroscopy, and pH measurements. Vibrational techniques disclosed significant differences in composition among the unhydrated cements, which significantly affected the bioactivity as well as pH, and hydration products of the cements. After one day in DPBS, all the cements were covered by a more or less homogeneous layer of B-type carbonated apatite. The experimental cement maintained a high bioactivity, only slightly lower than the other cements and appears a valid alternative to commercial cements, in view of its adequate setting time properties. The bioactivity represents an essential property to favour bone healing and makes the calcium-silicate cements the gold standard materials for root-apical endodontic surgery.

Evolution of trees and mycorrhizal fungi intensifies silicate mineral weathering

PubMed Central

Quirk, Joe; Beerling, David J.; Banwart, Steve A.; Kakonyi, Gabriella; Romero-Gonzalez, Maria E.; Leake, Jonathan R.

2012-01-01

Forested ecosystems diversified more than 350 Ma to become major engines of continental silicate weathering, regulating the Earth's atmospheric carbon dioxide concentration by driving calcium export into ocean carbonates. Our field experiments with mature trees demonstrate intensification of this weathering engine as tree lineages diversified in concert with their symbiotic mycorrhizal fungi. Preferential hyphal colonization of the calcium silicate-bearing rock, basalt, progressively increased with advancement from arbuscular mycorrhizal (AM) to later, independently evolved ectomycorrhizal (EM) fungi, and from gymnosperm to angiosperm hosts with both fungal groups. This led to ‘trenching’ of silicate mineral surfaces by AM and EM fungi, with EM gymnosperms and angiosperms releasing calcium from basalt at twice the rate of AM gymnosperms. Our findings indicate mycorrhiza-driven weathering may have originated hundreds of millions of years earlier than previously recognized and subsequently intensified with the evolution of trees and mycorrhizas to affect the Earth's long-term CO2 and climate history. PMID:22859556

Multiscale understanding of tricalcium silicate hydration reactions.

PubMed

Cuesta, Ana; Zea-Garcia, Jesus D; Londono-Zuluaga, Diana; De la Torre, Angeles G; Santacruz, Isabel; Vallcorba, Oriol; Dapiaggi, Monica; Sanfélix, Susana G; Aranda, Miguel A G

2018-06-04

Tricalcium silicate, the main constituent of Portland cement, hydrates to produce crystalline calcium hydroxide and calcium-silicate-hydrates (C-S-H) nanocrystalline gel. This hydration reaction is poorly understood at the nanoscale. The understanding of atomic arrangement in nanocrystalline phases is intrinsically complicated and this challenge is exacerbated by the presence of additional crystalline phase(s). Here, we use calorimetry and synchrotron X-ray powder diffraction to quantitatively follow tricalcium silicate hydration process: i) its dissolution, ii) portlandite crystallization and iii) C-S-H gel precipitation. Chiefly, synchrotron pair distribution function (PDF) allows to identify a defective clinotobermorite, Ca 11 Si 9 O 28 (OH) 2 . 8.5H 2 O, as the nanocrystalline component of C-S-H. Furthermore, PDF analysis also indicates that C-S-H gel contains monolayer calcium hydroxide which is stretched as recently predicted by first principles calculations. These outcomes, plus additional laboratory characterization, yielded a multiscale picture for C-S-H nanocomposite gel which explains the observed densities and Ca/Si atomic ratios at the nano- and meso- scales.

Simple technology for recycling phosphate from wastewater to farmland in rural areas.

PubMed

Ohtake, Hisao; Okano, Kenji; Kunisada, Masashi; Takano, Hiroyuki; Toda, Masaya

2018-01-01

A simple technology for phosphate (P i ) recovery has been developed using a bifunctional adsorption-aggregation agent. The bifunctional agent was prepared by soaking calcium silicates in hydrochloric acid solution. Importantly, recyclable calcium silicates were available almost free of charge from the cement industry and also from the steel industry. The acid treatment was essential not only for enhancing the ability of calcium silicates to remove P i from aqueous solution but also for enabling the high settleability of removed P i . On-site experiments using a mobile plant showed that approximately 80% P i could be recovered from anaerobic sludge digestion liquor at a wastewater treatment plant. This technology has the potential to offer a simple, compact service for recycling P i from wastewater to farmland in rural areas.

Laboratory simulation of infrared astrophysical features. Ph.D. Thesis; [emission spectra of comets

NASA Technical Reports Server (NTRS)

Rose, L. A.

1977-01-01

Intermediate resolution emission spectroscopy was used to study a group of 9 terrestrial silicates, 1 synthetic silicate, 6 meteorites and 2 lunar soils; comparisons were made with the intermediate resolution spectra of Comet Kohoutek in order to determine which materials best simulate the 10um astrophysical feature. Mixtures of silicates which would yield spectra matching the spectrum of the comet in the 10um region include: (1) A hydrous layer lattice silicate in combination with a high temperature condensate; (2) an amorphous magnesium silicate in combination with a high temperature condensate and (3) glassy olivine and glassy anorthite in approximately equal proportions.

Laboratory Measurements of Celestial Solids

NASA Technical Reports Server (NTRS)

Sievers, A. J.; Beckwith, S. V. W.

1997-01-01

Our experimental study has focused on laboratory measurements of the low temperature optical properties of a variety of astronomically significant materials in the infrared and mm-wave region of the spectrum. Our far infrared measurements of silicate grains with an open structure have produced a variety of unusual results: (1) the low temperature mass opacity coefficient of small amorphous 2MgO(central dot)SiO2 and MgO(central dot)2SiO2 grains are many times larger than the values previously used for interstellar grain material; (2) all of the amorphous silicate grains studied possess the characteristic temperature dependent signature associated with two level systems in bulk glass; and (3) a smaller but nonzero two level temperature dependence signature is also observed for crystalline particles, its physical origin is unclear. These laboratory measurements yield surprisingly large and variable values for the mm-wave absorption coefficients of small silicate particles similar to interstellar grains, and suggest that the bulk absorptivity of interstellar dust at these long wavelengths will not be well known without such studies. Furthermore, our studies have been useful to better understand the physics of the two level absorption process in amorphous and crystalline grains to gain confidence in the wide applicability of these results.

Effect of Reaction Pathway on the Extent and Mechanism of Uranium(VI) Immobilization with Calcium and Phosphate

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

Mehta, Vrajesh S.; Maillot, Fabien; Wang, Zheming

Phosphate addition to subsurface environments contaminated with uranium can be used as an in situ remediation approach. Batch experiments were conducted to evaluate the dependence of the extent and mechanism of uranium uptake on the pathway for reaction with calcium phosphates. At pH 4.0 and 6.0 uranium uptake occurred via autunite (Ca(UO2)(PO4)3) precipitation irrespective of the starting forms of calcium and phosphate. At pH 7.5, the uptake mechanism depended on the nature of the calcium and phosphate. When dissolved uranium, calcium, and phosphate were added simultaneously, uranium was structurally incorporated into a newly formed amorphous calcium phosphate solid. Adsorption wasmore » the dominant removal mechanism for uranium contacted with pre-formed amorphous calcium phosphate solids,. When U(VI) was added to a suspension containing amorphous calcium phosphate solids as well as dissolved calcium and phosphate, then removal occurred through precipitation (57±4 %) of autunite and adsorption (43±4 %) onto calcium phosphate. The solid phase speciation of the uranium was determined using X-ray absorption spectroscopy and laser induced fluorescence spectroscopy. Dissolved uranium, calcium, and phosphate concentrations with saturation index calculations helped identify removal mechanisms and determine thermodynamically favorable solid phases.« less

Transformation mechanism of amorphous calcium carbonate into calcite in the sea urchin larval spicule.

PubMed

Politi, Yael; Metzler, Rebecca A; Abrecht, Mike; Gilbert, Benjamin; Wilt, Fred H; Sagi, Irit; Addadi, Lia; Weiner, Steve; Gilbert, P U P A; Gilbert, Pupa

2008-11-11

Sea urchin larval spicules transform amorphous calcium carbonate (ACC) into calcite single crystals. The mechanism of transformation is enigmatic: the transforming spicule displays both amorphous and crystalline properties, with no defined crystallization front. Here, we use X-ray photoelectron emission spectromicroscopy with probing size of 40-200 nm. We resolve 3 distinct mineral phases: An initial short-lived, presumably hydrated ACC phase, followed by an intermediate transient form of ACC, and finally the biogenic crystalline calcite phase. The amorphous and crystalline phases are juxtaposed, often appearing in adjacent sites at a scale of tens of nanometers. We propose that the amorphous-crystal transformation propagates in a tortuous path through preexisting 40- to 100-nm amorphous units, via a secondary nucleation mechanism.

Reactive molecular simulation on the calcium silicate hydrates/polyethylene glycol composites

NASA Astrophysics Data System (ADS)

Zhou, Yang; Hou, Dongshuai; Jiang, Jinyang; She, Wei; Yu, Jiao

2017-11-01

Calcium silicate hydrates (C-S-H) may potentially exhibit extraordinary performance when modified by polymers, in which way the properties of cement-based materials can be improved from the genetic level. In this molecular dynamics simulation of the interaction between C-S-H and polyethylene glycol, apart from the H bond network connection in the interface, another chemical adsorption was observed. Calcium of C-S-H broke the Csbnd O bond of PEG and formed a new Casbnd C connection, which created a stronger link between the organic and inorganic phases.

Mechanical Properties and Durability of Advanced Environmental Barrier Coatings in Calcium-Magnesium-Alumino-Silicate Environments

NASA Technical Reports Server (NTRS)

Miladinovich, Daniel S.; Zhu, Dongming

2011-01-01

Environmental barrier coatings are being developed and tested for use with SiC/SiC ceramic matrix composite (CMC) gas turbine engine components. Several oxide and silicate based compositons are being studied for use as top-coat and intermediate layers in a three or more layer environmental barrier coating system. Specifically, the room temperature Vickers-indentation-fracture-toughness testing and high-temperature stability reaction studies with Calcium Magnesium Alumino-Silicate (CMAS or "sand") are being conducted using advanced testing techniques such as high pressure burner rig tests as well as high heat flux laser tests.

Regenerable sorbents for CO.sub.2 capture from moderate and high temperature gas streams

DOEpatents

Siriwardane, Ranjani V [Morgantown, WV

2008-01-01

A process for making a granular sorbent to capture carbon dioxide from gas streams comprising homogeneously mixing an alkali metal oxide, alkali metal hydroxide, alkaline earth metal oxide, alkaline earth metal hydroxide, alkali titanate, alkali zirconate, alkali silicate and combinations thereof with a binder selected from the group consisting of sodium ortho silicate, calcium sulfate dihydrate (CaSO.sub.4.2H.sub.2O), alkali silicates, calcium aluminate, bentonite, inorganic clays and organic clays and combinations thereof and water; drying the mixture and placing the sorbent in a container permeable to a gas stream.

Phase transitions in biogenic amorphous calcium carbonate

NASA Astrophysics Data System (ADS)

Gong, Yutao

Geological calcium carbonate exists in both crystalline phases and amorphous phases. Compared with crystalline calcium carbonate, such as calcite, aragonite and vaterite, the amorphous calcium carbonate (ACC) is unstable. Unlike geological calcium carbonate crystals, crystalline sea urchin spicules (99.9 wt % calcium carbonate and 0.1 wt % proteins) do not present facets. To explain this property, crystal formation via amorphous precursors was proposed in theory. And previous research reported experimental evidence of ACC on the surface of forming sea urchin spicules. By using X-ray absorption near-edge structure (XANES) spectroscopy and photoelectron emission microscopy (PEEM), we studied cross-sections of fresh sea urchin spicules at different stages (36h, 48h and 72h after fertilization) and observed the transition sequence of three mineral phases: hydrated ACC → dehydrated ACC → biogenic calcite. In addition, we unexpectedly found hydrated ACC nanoparticles that are surrounded by biogenic calcite. This observation indicates the dehydration from hydrated ACC to dehydrated ACC is inhibited, resulting in stabilization of hydrated ACC nanoparticles. We thought that the dehydration was inhibited by protein matrix components occluded within the biomineral, and we designed an in vitro assay to test the hypothesis. By utilizing XANES-PEEM, we found that SM50, the most abundant occluded matrix protein in sea urchin spicules, has the function to stabilize hydrated ACC in vitro.

Interpreting the 10 micron Astronomical Silicate Feature

NASA Astrophysics Data System (ADS)

Bowey, Janet E.

1998-11-01

10micron spectra of silicate dust in the diffuse medium towards Cyg OB2 no. 12 and towards field and embedded objects in the Taurus Molecular Cloud (TMC) were obtained with CGS3 at the United Kingdom Infrared Telescope (UKIRT). Cold molecular-cloud silicates are sampled in quiescent lines of sight towards the field stars Taurus-Elias 16 and Elias 13, whilst observations of the embedded young stellar objects HL Tau, Taurus-Elias 7 (Haro6-10) and Elias 18 also include emission from heated dust. To obtain the foreground silicate absorption profiles, featureless continua are estimated using smoothed astronomical and laboratory silicate emissivities. TMC field stars and Cyg OB2 no. 12 are modelled as photospheres reddened by foreground continuum and silicate extinction. Dust emission in the non-photospheric continua of HL Tau and Elias 7 (Haro6-10) is distinguished from foreground silicate absorption using a 10micron disk model, based on the IR-submm model of T Tauri stars by Adams, Lada & Shu (1988), with terms added to represent the foreground continuum and silicate extinction. The absorption profiles of HL Tau and Elias 7 are similar to that of the field star Elias 16. Fitted temperature indices of 0.43 (HL Tau) and 0.33 (Elias 7) agree with Boss' (1996) theoretical models of the 200-300K region, but are lower than those of IR-submm disks (0.5-0.61; Mannings & Emerson 1994); the modelled 10micron emission of HL Tau is optically thin, that of Elias 7 is optically thick. A preliminary arcsecond-resolution determination of the 10micron emissivity near θ1 Ori D in the Trapezium region of Orion and a range of emission temperatures (225-310K) are derived from observations by T. L. Hayward; this Ney-Allen emissivity is 0.6micron narrower than the Trapezium emissivity obtained by Forrest et al. (1975) with a large aperture. Published interstellar grain models, elemental abundances and laboratory studies of Solar System silicates (IDPs, GEMS and meteorites), the 10micron spectra of comets, interstellar silicates, synthetic silicates and terrestrial minerals, and the effects of laboratory processing on the 10micron spectra of crystalline and amorphous silicates are reviewed to provide insight into the mineralogy of interstellar silicate dust. The wavelengths of the peaks of the 10micron silicate profiles decrease between circumstellar, diffuse medium and molecular-cloud environments, indicating (after Gürtler & Henning 1986) that the amorphous pyroxene content of initially olivine-rich interstellar dust increases with time. This is accompanied by an increase in the FWHM of the features which indicates an increase in grain size and/or an increasing fraction of chemically-varied crystalline pyroxene. Fine structure in the Cyg OB2 no. 12, Elias 16, Elias 7, HL Tau profiles indicate that hydrated layer silicates similar to terrestrial serpentines, clays and talc may be a ubiquitous component of interstellar dust. At 10microns the narrow bands of mixed crystalline pyroxenes blend, making their identification difficult. Since no fine structure is observed near 11.2microns, the fraction of crystalline olivine is small. In geology direct olivine-plus-SiO2 to pyroxene reactions occur only at high pressure within the terrestrial mantle. Therefore the fraction of amorphous pyroxene is probably increased by the hydration of Mg-rich olivine to form a serpentine-like hydrated silicate, which is subsequently annealed to form a mixture of amorphous pyroxene and olivine. Terrestrial and laboratory olivine samples are readily converted to serpentine in the presence of water, and (after extended annealing) the first crystalline band to appear is the 11.2micron olivine feature frequently observed in cometary spectra.

Mitigating global warming potentials of methane and nitrous oxide gases from rice paddies under different irrigation regimes.

PubMed

Ali, Muhammad Aslam; Hoque, M Anamul; Kim, Pil Joo

2013-04-01

A field experiment was conducted in Bangladesh Agricultural University Farm to investigate the mitigating effects of soil amendments such as calcium carbide, calcium silicate, phosphogypsum, and biochar with urea fertilizer on global warming potentials (GWPs) of methane (CH4) and nitrous oxide (N2O) gases during rice cultivation under continuous and intermittent irrigations. Among the amendments phosphogypsum and silicate fertilizer, being potential source of electron acceptors, decreased maximum level of seasonal CH4 flux by 25-27 % and 32-38 % in continuous and intermittent irrigations, respectively. Biochar and calcium carbide amendments, acting as nitrification inhibitors, decreased N2O emissions by 36-40 % and 26-30 % under continuous and intermittent irrigations, respectively. The total GWP of CH4 and N2O gases were decreased by 7-27 % and 6-34 % with calcium carbide, phosphogypsum, and silicate fertilizer amendments under continuous and intermittent irrigations, respectively. However, biochar amendments increased overall GWP of CH4 and N2O gases.

Soft X-Ray Irradiation of Silicates: Implications for Dust Evolution in Protoplanetary Disks

NASA Astrophysics Data System (ADS)

Ciaravella, A.; Cecchi-Pestellini, C.; Chen, Y.-J.; Muñoz Caro, G. M.; Huang, C.-H.; Jiménez-Escobar, A.; Venezia, A. M.

2016-09-01

The processing of energetic photons on bare silicate grains was simulated experimentally on silicate films submitted to soft X-rays of energies up to 1.25 keV. The silicate material was prepared by means of a microwave assisted sol-gel technique. Its chemical composition reflects the Mg2SiO4 stoichiometry with residual impurities due to the synthesis method. The experiments were performed using the spherical grating monochromator beamline at the National Synchrotron Radiation Research Center in Taiwan. We found that soft X-ray irradiation induces structural changes that can be interpreted as an amorphization of the processed silicate material. The present results may have relevant implications in the evolution of silicate materials in X-ray-irradiated protoplanetary disks.

Analysis of the color alteration and radiopacity promoted by bismuth oxide in calcium silicate cement.

PubMed

Marciano, Marina Angélica; Estrela, Carlos; Mondelli, Rafael Francisco Lia; Ordinola-Zapata, Ronald; Duarte, Marco Antonio Hungaro

2013-01-01

The aim of the study was to determine if the increase in radiopacity provided by bismuth oxide is related to the color alteration of calcium silicate-based cement. Calcium silicate cement (CSC) was mixed with 0%, 15%, 20%, 30% and 50% of bismuth oxide (BO), determined by weight. Mineral trioxide aggregate (MTA) was the control group. The radiopacity test was performed according to ISO 6876/2001. The color was evaluated using the CIE system. The assessments were performed after 24 hours, 7 and 30 days of setting time, using a spectrophotometer to obtain the ΔE, Δa, Δb and ΔL values. The statistical analyses were performed using the Kruskal-Wallis/Dunn and ANOVA/Tukey tests (p<0.05). The cements in which bismuth oxide was added showed radiopacity corresponding to the ISO recommendations (>3 mm equivalent of Al). The MTA group was statistically similar to the CSC/30% BO group (p>0.05). In regard to color, the increase of bismuth oxide resulted in a decrease in the ΔE value of the calcium silicate cement. The CSC group presented statistically higher ΔE values than the CSC/50% BO group (p<0.05). The comparison between 24 hours and 7 days showed higher ΔE for the MTA group, with statistical differences for the CSC/15% BO and CSC/50% BO groups (p<0.05). After 30 days, CSC showed statistically higher ΔE values than CSC/30% BO and CSC/50% BO (p<0.05). In conclusion, the increase in radiopacity provided by bismuth oxide has no relation to the color alteration of calcium silicate-based cements.

Present and future of glass-ionomers and calcium-silicate cements as bioactive materials in dentistry: biophotonics-based interfacial analyses in health and disease.

PubMed

Watson, Timothy F; Atmeh, Amre R; Sajini, Shara; Cook, Richard J; Festy, Frederic

2014-01-01

Since their introduction, calcium silicate cements have primarily found use as endodontic sealers, due to long setting times. While similar in chemistry, recent variations such as constituent proportions, purities and manufacturing processes mandate a critical understanding of service behavior differences of the new coronal restorative material variants. Of particular relevance to minimally invasive philosophies is the potential for ion supply, from initial hydration to mature set in dental cements. They may be capable of supporting repair and remineralization of dentin left after decay and cavity preparation, following the concepts of ion exchange from glass ionomers. This paper reviews the underlying chemistry and interactions of glass ionomer and calcium silicate cements, with dental tissues, concentrating on dentin-restoration interface reactions. We additionally demonstrate a new optical technique, based around high resolution deep tissue, two-photon fluorescence and lifetime imaging, which allows monitoring of undisturbed cement-dentin interface samples behavior over time. The local bioactivity of the calcium-silicate based materials has been shown to produce mineralization within the subjacent dentin substrate, extending deep within the tissues. This suggests that the local ion-rich alkaline environment may be more favorable to mineral repair and re-construction, compared with the acidic environs of comparable glass ionomer based materials. The advantages of this potential re-mineralization phenomenon for minimally invasive management of carious dentin are self-evident. There is a clear need to improve the bioactivity of restorative dental materials and these calcium silicate cement systems offer exciting possibilities in realizing this goal. Copyright © 2013 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Developmental biology meets materials science: Morphogenesis of biomineralized structures.

PubMed

Wilt, Fred H

2005-04-01

Biomineralization is the process by which metazoa form hard minerals for support, defense, and feeding. The minerals so formed, e.g., teeth, bones, shells, carapaces, and spicules, are of considerable interest to chemists and materials scientists. The cell biology underlying biomineralization is not well understood. The study of the formation of mineralized structures in developing organisms offers opportunities for understanding some intriguing aspects of cell and developmental biology. Five examples of biomineralization are presented: (1) the formation of siliceous spicules and frustules in sponges and diatoms, respectively; (2) the structure of skeletal spicules composed of amorphous calcium carbonate in some tunicates; (3) the secretion of the prism and nacre of some molluscan shells; (4) the development of skeletal spicules of sea urchin embryos; and (5) the formation of enamel of vertebrate teeth. Some speculations on the cellular and molecular mechanisms that support biomineralization, and their evolutionary origins, are discussed.

Insights into Silicate Carbonation Processes in Water-Bearing Supercritical CO2 Fluids

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

Miller, Quin RS; Thompson, Christopher J.; Loring, John S.

2013-07-01

Long-term geologic storage of carbon dioxide (CO2) is considered an integral part to moderating CO2 concentrations in the atmosphere and subsequently minimizing effects of global climate change. Although subsurface injection of CO2 is common place in certain industries, deployment at the scale required for emission reduction is unprecedented and therefore requires a high degree of predictability. Accurately modeling geochemical processes in the subsurface requires experimental derived data for mineral reactions occurring between the CO2, water, and rocks. Most work in this area has focused on aqueous-dominated systems in which dissolved CO2 reacts to form crystalline carbonate minerals. Comparatively little laboratorymore » research has been conducted on reactions occurring between minerals in the host rock and the wet supercritical fluid phase. In this work, we studied the carbonation of wollastonite [CaSiO3] exposed to variably hydrated supercritical CO2 (scCO2) at a range of temperatures (50, 55 and 70 °C) and pressures (90,120 and 160 bar) that simulate conditions in geologic repositories. Mineral transformation reactions were followed by three novel in situ high pressure techniques, including x-ray diffraction that tracked the rate and extents of wollastonite conversion to calcite. Increased dissolved water concentrations in the supercritical CO2 resulted in increased silicate carbonation approaching ~50 wt. %. Development of thin water films on the mineral surface were directly observed with infrared spectroscopy and determined to be critical for facilitating carbonation processes. Even in extreme low water conditions, magic angle spinning nuclear magnetic resonance detected formation of Q3 [Si(OSi)3OH] and Q4 [Si(OSi)4] amorphous silica species. Unlike the thick (<10 μm) passivating silica layers observed in the fully water saturated scCO2 experiments, images obtained from a focused ion beam sectioned sample indicted these coatings were chemically wollastonite but structurally amorphous. In addition, evidence of an intermediate hydrated amorphous calcium carbonate forming under these conditions further emphasize the importance of understanding geochemical processes occurring in water bearing scCO2 fluids.« less

Recalescence during crystallization of stardust: Resolution of the amorphous interstellar medium paradox

NASA Astrophysics Data System (ADS)

Whittington, A. G.; Sehlke, A.; Speck, A. K.

2017-12-01

Dust that coalesces to form planetary systems originates around dying stars, before passing into the interstellar medium (ISM). Historically, observations of broad smooth features in the 10-µm region suggested that dust in circumstellar regions, and in the ISM, was mostly amorphous rather than crystalline. With improved space telescope capabilities, crystalline silicates were discovered in the circumstellar regions around both young and old stars, although they remain undetected in the ISM. Despite intensive study the precise conditions that lead to the formation of crystalline silicates are still unknown, and their absence in the ISM remains problematic. Here we show that recalescence (spontaneous reheating) of rapidly crystallizing dust can explain the formation and apparent disappearance of crystalline silicates in space. We have documented recalescence in rapidly crystallizing Mg-rich silicate melts, with local heating at the crystallization front exceeding 160˚C in some cases. In circumstellar dust shells, amorphous grains with similar compositions condense at temperatures near their glass transition, and if they crystallize, they will recalesce. The higher temperature (T) of newly crystallized dust allows crystalline spectral features to be seen, because flux emitted depends on T4. After cooling to ambient temperature, crystalline spectral features in the ISM are concealed by volumetrically dominant amorphous dust. Our results explain the existence of crystalline silicate pre-solar grains, which are older than the solar system, and have implications for radiative transfer modeling and hydrodynamics of dusty environments, which are sensitive to small variations in optical properties. Our observations of mm-scale temperature differences up to 100˚C in cooling lava suggest that thermal imaging of basaltic lava flows needs to be conducted with mm-scale spatial resolution (see figure; crucible is 5mm diameter). Temperatures recorded with low spatial resolution, which average cooler melt and hotter crystals in a single pixel, will systematically overestimate the temperature of the liquid phase. Only the surface of a lava flow is likely to cool quickly enough for recalescence to occur, but this is precisely the part of the lava that is monitored by thermal imaging.

Transformation mechanism of amorphous calcium carbonate into calcite in the sea urchin larval spicule

PubMed Central

Politi, Yael; Metzler, Rebecca A.; Abrecht, Mike; Gilbert, Benjamin; Wilt, Fred H.; Sagi, Irit; Addadi, Lia; Weiner, Steve; Gilbert, P. U. P. A.

2008-01-01

Sea urchin larval spicules transform amorphous calcium carbonate (ACC) into calcite single crystals. The mechanism of transformation is enigmatic: the transforming spicule displays both amorphous and crystalline properties, with no defined crystallization front. Here, we use X-ray photoelectron emission spectromicroscopy with probing size of 40–200 nm. We resolve 3 distinct mineral phases: An initial short-lived, presumably hydrated ACC phase, followed by an intermediate transient form of ACC, and finally the biogenic crystalline calcite phase. The amorphous and crystalline phases are juxtaposed, often appearing in adjacent sites at a scale of tens of nanometers. We propose that the amorphous-crystal transformation propagates in a tortuous path through preexisting 40- to 100-nm amorphous units, via a secondary nucleation mechanism. PMID:18987314

Discrete dipole approximation models of chrystalline forsterite: Applications to cometary crystalline silicates

NASA Astrophysics Data System (ADS)

Lindsay, Sean Stephen

The shape, size, and composition of crystalline silicates observed in comet comae and external proto-planetary disks are indicative of the formation and evolution of the dust grains during the processes of planetary formation. In this dissertation, I present the 3 -- 40 mum absorption efficiencies( Qabs) of irregularly shaped forsterite crystals computed with the discrete dipole approximation (DDA) code DDSCAT developed by Draine and Flatau and run on the NASA Advanced Supercomputing facility Pleiades. An investigation of grain shapes ranging from spheroidal to irregular indicate that the strong spectral features from forsterite are sensitive to grain shape and are potentially degenerate with the effects of crystal solid state composition (Mg-content). The 10, 11, 18, 23, and 33.5 mum features are found to be the most crystal shape sensitive and should be avoided in determining Mg-content. The distinct spectral features for the three shape classes are connected with crystal formation environment using a condensation experiment by (Kobatake et al., 2008). The condensation experiment demonstrates that condensed forsterite crystal shapes are dependent on the condensation environmental temperature. I generate DDSCAT target analog shapes to the condensed crystal shapes. These analog shapes are represented by the three shape classes: 1) equant, 2) a, c-columns, and 3) b-shortened platelets. Each of these shape classes exhibit distinct spectral features that can be used to interpret grain shape characteristics from 8 --- 40 mum spectroscopy of astronomical objects containing crystalline silicates. Synthetic spectral energy distributions (SEDs) of the coma of Hale-Bopp at rh = 2.8 AU are generated by thermally modeling the flux contributions of 5 mineral species present in comets. The synthetic SEDs are constrained using a chi2- minimization technique. The mineral species are amorphous carbon, amorphous pyroxene, amorphous olivine, crystalline enstatite, and crystalline forsterite. Using the DDSCAT computed absorption efficiencies for a large variety of forsterite crystal shapes, which are computed for 66 grain sizes between 0.1 -- 5.0 mum, the flux contribution of irregularly shaped forsterite is computed. The forsterite flux contribution is then summed with the amorphous and crystalline enstatite contributions to generate the total synthetic SED. The DDSCAT forsterite grain shape synthetic SEDs reveal that the crystalline silicates in the coma of Hale-Bopp are irregular in shape with two distinct shape characteristics related to specific formation mechanisms: 1) equant grains with sharp ( ≲ 90°) angles between the faces, edges, and vertices that formed as high temperature condensates in the inner 1 -- 3 AU radial region of the Solar System's protoplanetary disk; and 2) c-shortened platelet shapes that likely formed from collisional processing of the crystals. The 8 -- 40 mum silicate spectral features of Hale-Bopp's coma are compared to the silicate spectral features of the comae of 17P/Holmes during 2007 outburst and 9P/Tempel 1 during the Deep Impact experiment to show that the silicate features with crystalline resonances are remarkably similar. The similarity in silicate spectral features suggests that the grain populations in the comae of these comets are similar in shape, size, and compositon. However, Hale-Bopp is a nearly isotropic comet (NIC) that dynamically came from the Oort cloud, and 17P and 9P are ecliptic comets (ECs) that dynamically came from the Scattered Disk. The different dynamical source regions yet similar silicate (amorphous and crystalline) grain populations suggest that ECs and NICs innately have similar grains and that the typically weaker silicate features of ECs are an effect of the surface grains becoming compacted with numerous perihelion passages. Hence, the differences in silicate between ECs and NICs are the result of grain structure and not grain composition. (Abstract shortened by UMI.)

Adsorption of selenium by amorphous iron oxyhydroxide and manganese dioxide

USGS Publications Warehouse

Balistrieri, L.S.; Chao, T.T.

1990-01-01

This work compares and models the adsorption of selenium and other anions on a neutral to alkaline surface (amorphous iron oxyhydroxide) and an acidic surface (manganese dioxide). Selenium adsorption on these oxides is examined as a function of pH, particle concentration, oxidation state, and competing anion concentration in order to assess how these factors might influence the mobility of selenium in the environment. The data indicate that 1. 1) amorphous iron oxyhydroxide has a greater affinity for selenium than manganese dioxide, 2. 2) selenite [Se(IV)] adsorption increases with decreasing pH and increasing particle concentration and is stronger than selenate [Se(VI)] adsorption on both oxides, and 3. 3) selenate does not adsorb on manganese dioxide. The relative affinity of selenate and selenite for the oxides and the lack of adsorption of selenate on a strongly acidic surface suggests that selenate forms outer-sphere complexes while selenite forms inner-sphere complexes with the surfaces. The data also indicate that the competition sequence of other anions with respect to selenite adsorption at pH 7.0 is phosphate > silicate > molybdate > fluoride > sulfate on amorphous iron oxyhydroxide and molybdate ??? phosphate > silicate > fluoride > sulfate on manganese dioxide. The adsorption of phosphate, molybdate, and silicate on these oxides as a function of pH indicates that the competition sequences reflect the relative affinities of these anions for the surfaces. The Triple Layer surface complexation model is used to provide a quantitative description of these observations and to assess the importance of surface site heterogeneity on anion adsorption. The modeling results suggest that selenite forms binuclear, innersphere complexes with amorphous iron oxyhydroxide and monodentate, inner-sphere complexes with manganese dioxide and that selenate forms outer-sphere, monodentate complexes with amorphous iron oxyhydroxide. The heterogeneity of the oxide surface sites is reflected in decreasing equilibrium constants for selenite with increasing adsorption density and both experimental observations and modeling results suggest that manganese dioxide has fewer sites of higher energy for selenite adsorption than amorphous iron oxyhydroxide. Modeling and interpreting the adsorption of phosphate, molybdate, and silicate on the oxides are made difficult by the lack of constraint in choosing surface species and the fact that equally good fits can be obtained with different surface species. Finally, predictions of anion competition using the model results from single adsorbate systems are not very successful because the model does not account for surface site heterogeneity. Selenite adsorption data from a multi-adsorbate system could be fit if the equilibrium constant for selenite is decreased with increasing anion adsorption density. ?? 1990.

Application of soil block without burning process and calcium silicate panels as building wall in mountainous area

NASA Astrophysics Data System (ADS)

Noerwasito, Vincentius Totok; Nasution, Tanti Satriana Rosary

2017-11-01

Utilization of local building materials in a residential location in mountainous area is very important, considering local material as a low-energy building material because of low transport energy. The local building materials used in this study are walls made from soil blocks. The material was made by the surrounding community from compacted soil without burning process. To maximize the potential of soil block to the outdoor temperature in the mountains, it is necessary to add non-local building materials as an insulator from the influence of the outside air. The insulator was calcium silicate panel. The location of the research is Trawas sub-district, Mojokerto regency, which is a mountainous area. The research problem is on applying the composition of local materials and calcium silicate panels that it will be able to meet the requirements as a wall building material and finding to what extent the impact of the wall against indoor temperature. The result from this research was the application of soil block walls insulated by calcium silicate panels in a building model. Besides, because of the utilization of those materials, the building has a specific difference between indoor and outdoor temperature. Thus, this model can be applied in mountainous areas in Indonesia.

Conversion of melt-derived microfibrous borate (13-93B3) and silicate (45S5) bioactive glass in a simulated body fluid.

PubMed

Liu, Xin; Rahaman, Mohamed N; Day, Delbert E

2013-03-01

Microfibrous bioactive glasses are showing a considerable capacity to heal soft tissue wounds, but little information is available on the mechanism of healing. In the present study, the conversion of microfibrous borate bioactive glass (diameter = 0.2-5 μm) with the composition designated 13-93B3 (5.5 Na2O, 11.1 K2O, 4.6 MgO, 18.5 CaO, 3.7 P2O5, 56.6 B2O3 wt%) was evaluated in vitro as a function of immersion time in a simulated body fluid (SBF) at 37 °C using structural and chemical techniques. Silicate 45S5glass microfibers (45 SiO2, 24.5 Na2O, 24.5 CaO, 6 P2O5 wt%) were also studied for comparison. Microfibrous 13-93B3 glass degraded almost completely and converted to a calcium phosphate material within 7-14 days in SBF, whereas >85 % of the silica remained in the 45S5 microfibers, forming a silica gel phase. An amorphous calcium phosphate (ACP) product that formed on the 13-93B3 microfibers crystallized at a slower rate to hydroxyapatite (HA) when compared to the ACP that formed on the 45S5 fibers. For immersion times >3 days, the 13-93B3 fibers released a higher concentration of Ca into the SBF than the 45S5 fibers. The fast and more complete degradation, slow crystallization of the ACP product, and higher concentration of dissolved Ca in SBF could contribute to the capacity of the microfibrous borate 13-93B3 glass to heal soft tissue wounds.

Trapping Planetary Noble Gases During the Fischer-Tropsch-Type Synthesis of Organic Materials

NASA Technical Reports Server (NTRS)

Nuth, Joseph A.; Johnson, N. M.; Meshik, A.

2010-01-01

When hydrogen, nitrogen and CO arc exposed to amorphous iron silicate surfaces at temperatures between 500 - 900K, a carbonaceous coating forms via Fischer-Tropsch type reactions!, Under normal circumstances such a catalytic coating would impede or stop further reaction. However, we find that this coating is a better catalyst than the amorphous iron silicates that initiate these rcactions:u . The formation of a self-perpetuating catalytic coating on grain surfaces could explain the rich deposits of macromolecular carbon found in primitive meteorites and would imply that protostellar nebulae should be rich in organic materiaL Many more experiments are needed to understand this chemical system and its application to protostellar nebulae.

Incorporation of bitumen and calcium silicate in cement and lime stabilized soil blocks

NASA Astrophysics Data System (ADS)

Kwan, W. H.; Cheah, C. B.; Ramli, M.; Al-Sakkaf, Y. K.

2017-04-01

Providing affordable housing is the most critical problem in many of the developing countries. Using earth materials in building construction is one of the feasible methods to address this issue and it can be a way towards sustainable construction as well. However, the published information on the stabilized soil blocks is limited. Therefore, the present study is conducted to examine the characterization of the soils and engineering properties of the stabilized soil blocks. Four types of stabilizer were used in the study, namely; cement, slaked lime, bitumen emulsion and calcium silicate. Cement and slaked lime were added at different percentages in the range of 5% to 15%, with interval of 2.5%. The percentage was determined based on weight of soil. Meanwhile, bitumen emulsion and calcium silicate were incorporated at various percentages together with 10% of cement. Dosage of bitumen emulsion is in the range of 2% to 10% at interval of 2% while calcium silicate was incorporated at 0.50%, 0.75%, 1.00%, 1.25%, 1.50% and 2.00%. Results show that cement is the most viable stabilizer for the soil block among all stabilizers in this study. The bulk density, optimum moisture content and compressive strengths were increased with the increasing cement content. The most suitable cement content was 10% added at moisture content of 12%. Lime, bitumen and calcium contents were recommended at 5.0%, 6.0% and 1.25%, respectively.

Corrosion resistant thermal barrier coating. [protecting gas turbines and other engine parts

NASA Technical Reports Server (NTRS)

Levine, S. R.; Miller, R. A.; Hodge, P. E. (Inventor)

1981-01-01

A thermal barrier coating system for protecting metal surfaces at high temperature in normally corrosive environments is described. The thermal barrier coating system includes a metal alloy bond coating, the alloy containing nickel, cobalt, iron, or a combination of these metals. The system further includes a corrosion resistant thermal barrier oxide coating containing at least one alkaline earth silicate. The preferred oxides are calcium silicate, barium silicate, magnesium silicate, or combinations of these silicates.

A Comparative Chemical Study of Calcium Silicate-Containing and Epoxy Resin-Based Root Canal Sealers.

PubMed

Reszka, Przemysław; Nowicka, Alicja; Lipski, Mariusz; Dura, Włodzimierz; Droździk, Agnieszka; Woźniak, Krzysztof

2016-01-01

Objective. The present study assessed the chemical elements in two novel calcium silicate-containing root canal sealers, BioRoot RCS and Well-Root ST, compared to a calcium silicate-containing root canal sealer that has been on the market for several years, MTA Fillapex, and epoxy resin-based sealer AHPlus. Material and Methods. The sealers were mixed and manipulated according to the manufacturers' instructions. Twelve cylindrical molds (inner diameter 4 mm; height 3 mm) were placed on a glass petri dish and packed with the materials. The dish was transferred to an incubator. After 72 h the molds were examined by scanning electron microscopy and energy dispersive X-ray microanalysis. Results. BioRoot RCS and Well-Root ST had high peaks of calcium, zirconium, oxygen, carbon, silicon, and chlorine. Well-Root ST also had sodium, magnesium, aluminum, and titanium peaks. MTA Fillapex and AHPlus had carbon, oxygen, calcium, titanium, and bismuth peaks. A silicon peak was also observed for MTA Fillapex, and zirconium and tungsten peaks for AHPlus. Conclusion. BioRoot RSC had the highest degree of purity. The clinical implication of metals contained in the other sealers needs to be investigated.

A Comparative Chemical Study of Calcium Silicate-Containing and Epoxy Resin-Based Root Canal Sealers

PubMed Central

Reszka, Przemysław; Dura, Włodzimierz; Droździk, Agnieszka; Woźniak, Krzysztof

2016-01-01

Objective. The present study assessed the chemical elements in two novel calcium silicate-containing root canal sealers, BioRoot RCS and Well-Root ST, compared to a calcium silicate-containing root canal sealer that has been on the market for several years, MTA Fillapex, and epoxy resin-based sealer AHPlus. Material and Methods. The sealers were mixed and manipulated according to the manufacturers' instructions. Twelve cylindrical molds (inner diameter 4 mm; height 3 mm) were placed on a glass petri dish and packed with the materials. The dish was transferred to an incubator. After 72 h the molds were examined by scanning electron microscopy and energy dispersive X-ray microanalysis. Results. BioRoot RCS and Well-Root ST had high peaks of calcium, zirconium, oxygen, carbon, silicon, and chlorine. Well-Root ST also had sodium, magnesium, aluminum, and titanium peaks. MTA Fillapex and AHPlus had carbon, oxygen, calcium, titanium, and bismuth peaks. A silicon peak was also observed for MTA Fillapex, and zirconium and tungsten peaks for AHPlus. Conclusion. BioRoot RSC had the highest degree of purity. The clinical implication of metals contained in the other sealers needs to be investigated. PMID:28097154

Doped Calcium Silicate Ceramics: A New Class of Candidates for Synthetic Bone Substitutes

PubMed Central

No, Young Jung; Li, Jiao Jiao; Zreiqat, Hala

2017-01-01

Doped calcium silicate ceramics (DCSCs) have recently gained immense interest as a new class of candidates for the treatment of bone defects. Although calcium phosphates and bioactive glasses have remained the mainstream of ceramic bone substitutes, their clinical use is limited by suboptimal mechanical properties. DCSCs are a class of calcium silicate ceramics which are developed through the ionic substitution of calcium ions, the incorporation of metal oxides into the base binary xCaO–ySiO2 system, or a combination of both. Due to their unique compositions and ability to release bioactive ions, DCSCs exhibit enhanced mechanical and biological properties. Such characteristics offer significant advantages over existing ceramic bone substitutes, and underline the future potential of adopting DCSCs for clinical use in bone reconstruction to produce improved outcomes. This review will discuss the effects of different dopant elements and oxides on the characteristics of DCSCs for applications in bone repair, including mechanical properties, degradation and ion release characteristics, radiopacity, and biological activity (in vitro and in vivo). Recent advances in the development of DCSCs for broader clinical applications will also be discussed, including DCSC composites, coated DCSC scaffolds and DCSC-coated metal implants. PMID:28772513

Calcium silicate-based sealers: Assessment of physicochemical properties, porosity and hydration.

PubMed

Marciano, Marina Angélica; Duarte, Marco Antonio Hungaro; Camilleri, Josette

2016-02-01

Investigation of hydration, chemical, physical properties and porosity of experimental calcium silicate-based sealers. Experimental calcium silicate-based sealers with calcium tungstate and zirconium oxide radio-opacifiers were prepared by mixing 1g of powder to 0.3 mL of 80% distilled water and 20% propylene glycol. MTA and MTA Fillapex were used as controls. The raw materials and set sealers were characterized using a combination of scanning electron microscopy, energy dispersive spectroscopy and X-ray diffraction. Physical properties were analyzed according to ANSI/ADA. The pH and calcium ion release were assessed after 3, 24, 72 and 168 h. The porosity was assessed using mercury intrusion porosimetry. The analysis of hydration of prototype sealers revealed calcium hydroxide as a by-product resulting in alkaline pH and detection of calcium ion release, with high values in initial periods. The radiopacity was similar to MTA for the sealers containing high amounts of radio-opacifiers (p>0.05). Flowability was higher and film thickness was lower for resinous MTA Fillapex sealer (p<0.05). The test sealers showed water sorption and porosity similar to MTA (p>0.05). The prototype sealers presented adequate hydration, elevated pH and calcium ion release. Regarding physical properties, elevated proportions of radio-opacifiers were necessary to accomplish adequate radiopacity, enhance flowability and reduce film thickness. All the tested sealers presented water sorption and porosity similar to MTA. Copyright © 2015 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Ion release and mechanical properties of calcium silicate and calcium hydroxide materials used for pulp capping.

PubMed

Natale, L C; Rodrigues, M C; Xavier, T A; Simões, A; de Souza, D N; Braga, R R

2015-01-01

To compare the ion release and mechanical properties of a calcium hydroxide (Dycal) and two calcium silicate (MTA Angelus and Biodentine) cements. Calcium and hydroxyl ion release in water from 24-h set cements were calculated from titration with HCl (n = 3). Calcium release after 7, 14, 21 and 28 days at pH 5.5 and 7.0 was measured using ICP-OES (n = 6). Flexural strength (FS) and modulus (E) were tested after 48-h storage, and compressive strength (CS) was tested after 48 h and 7 days (n = 10). Ion release and mechanical data were subjected to anova/Tukey and Kruskal-Wallis/Mann-Whitney tests, respectively (α = 0.05). Titration curves revealed that Dycal released significantly fewer ions in solution than calcium silicates (P < 0.001). Calcium release remained constant at pH 7.0, whilst at pH 5.5, it dropped significantly by 24% after 21 days (P < 0.05). At pH 5.5, MTA Angelus released significantly more calcium than Dycal (P < 0.01), whilst Biodentine had superior ion release than Dycal at pH 7.0 (P < 0.01). Biodentine had superior flexural strength, flexural modulus and compressive strength than the other cements, whilst MTA Angelus had higher modulus than Dycal (P < 0.001). Immediate calcium and hydroxyl ion release in solution was significantly lower for Dycal. In general, all materials released constant calcium levels over 28 days, but release from Dycal was significantly lower than Biodentine and MTA Angelus depending on pH conditions. Biodentine had substantially higher strength and modulus than MTA Angelus and Dycal, both of which demonstrated low stress-bearing capabilities. © 2014 International Endodontic Journal. Published by John Wiley & Sons Ltd.

SOFT X-RAY IRRADIATION OF SILICATES: IMPLICATIONS FOR DUST EVOLUTION IN PROTOPLANETARY DISKS

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

Ciaravella, A.; Cecchi-Pestellini, C.; Jiménez-Escobar, A.

2016-09-01

The processing of energetic photons on bare silicate grains was simulated experimentally on silicate films submitted to soft X-rays of energies up to 1.25 keV. The silicate material was prepared by means of a microwave assisted sol–gel technique. Its chemical composition reflects the Mg{sub 2}SiO{sub 4} stoichiometry with residual impurities due to the synthesis method. The experiments were performed using the spherical grating monochromator beamline at the National Synchrotron Radiation Research Center in Taiwan. We found that soft X-ray irradiation induces structural changes that can be interpreted as an amorphization of the processed silicate material. The present results may havemore » relevant implications in the evolution of silicate materials in X-ray-irradiated protoplanetary disks.« less

Phase transitions in biogenic amorphous calcium carbonate.

PubMed

Gong, Yutao U T; Killian, Christopher E; Olson, Ian C; Appathurai, Narayana P; Amasino, Audra L; Martin, Michael C; Holt, Liam J; Wilt, Fred H; Gilbert, P U P A

2012-04-17

Crystalline biominerals do not resemble faceted crystals. Current explanations for this property involve formation via amorphous phases. Using X-ray absorption near-edge structure (XANES) spectroscopy and photoelectron emission microscopy (PEEM), here we examine forming spicules in embryos of Strongylocentrotus purpuratus sea urchins, and observe a sequence of three mineral phases: hydrated amorphous calcium carbonate (ACC · H(2)O) → dehydrated amorphous calcium carbonate (ACC) → calcite. Unexpectedly, we find ACC · H(2)O-rich nanoparticles that persist after the surrounding mineral has dehydrated and crystallized. Protein matrix components occluded within the mineral must inhibit ACC · H(2)O dehydration. We devised an in vitro, also using XANES-PEEM, assay to identify spicule proteins that may play a role in stabilizing various mineral phases, and found that the most abundant occluded matrix protein in the sea urchin spicules, SM50, stabilizes ACC · H(2)O in vitro.

Phase transitions in biogenic amorphous calcium carbonate

PubMed Central

Gong, Yutao U. T.; Killian, Christopher E.; Olson, Ian C.; Appathurai, Narayana P.; Amasino, Audra L.; Martin, Michael C.; Holt, Liam J.; Wilt, Fred H.; Gilbert, P. U. P. A.

2012-01-01

Crystalline biominerals do not resemble faceted crystals. Current explanations for this property involve formation via amorphous phases. Using X-ray absorption near-edge structure (XANES) spectroscopy and photoelectron emission microscopy (PEEM), here we examine forming spicules in embryos of Strongylocentrotus purpuratus sea urchins, and observe a sequence of three mineral phases: hydrated amorphous calcium carbonate (ACC·H2O) → dehydrated amorphous calcium carbonate (ACC) → calcite. Unexpectedly, we find ACC·H2O-rich nanoparticles that persist after the surrounding mineral has dehydrated and crystallized. Protein matrix components occluded within the mineral must inhibit ACC·H2O dehydration. We devised an in vitro, also using XANES-PEEM, assay to identify spicule proteins that may play a role in stabilizing various mineral phases, and found that the most abundant occluded matrix protein in the sea urchin spicules, SM50, stabilizes ACC·H2O in vitro. PMID:22492931

Glycolytic intermediates induce amorphous calcium carbonate formation in crustaceans.

PubMed

Sato, Ai; Nagasaka, Seiji; Furihata, Kazuo; Nagata, Shinji; Arai, Isao; Saruwatari, Kazuko; Kogure, Toshihiro; Sakuda, Shohei; Nagasawa, Hiromichi

2011-04-01

It has been thought that phosphorus in biominerals made of amorphous calcium carbonate (ACC) might be related to ACC formation, but no such phosphorus-containing compounds have ever been identified. Crustaceans use ACC biominerals in exoskeleton and gastroliths so that they will have easy access to calcium carbonate inside the body before and after molting. We have identified phosphoenolpyruvate and 3-phosphoglycerate, intermediates of the glycolytic pathway, in exoskeleton and gastroliths and found them important for stabilizing ACC.

Synthesis, characterization and modelling of zinc and silicate co-substituted hydroxyapatite

PubMed Central

Friederichs, Robert J.; Chappell, Helen F.; Shepherd, David V.; Best, Serena M.

2015-01-01

Experimental chemistry and atomic modelling studies were performed here to investigate a novel ionic co-substitution in hydroxyapatite (HA). Zinc, silicate co-substituted HA (ZnSiHA) remained phase pure after heating to 1100°C with Zn and Si amounts of 0.6 wt% and 1.2 wt%, respectively. Unique lattice expansions in ZnSiHA, silicate Fourier transform infrared peaks and changes to the hydroxyl IR stretching region suggested Zn and silicate co-substitution in ZnSiHA. Zn and silicate insertion into HA was modelled using density functional theory (DFT). Different scenarios were considered where Zn substituted for different calcium sites or at a 2b site along the c-axis, which was suspected in singly substituted ZnHA. The most energetically favourable site in ZnSiHA was Zn positioned at a previously unreported interstitial site just off the c-axis near a silicate tetrahedron sitting on a phosphate site. A combination of experimental chemistry and DFT modelling provided insight into these complex co-substituted calcium phosphates that could find biomedical application as a synthetic bone mineral substitute. PMID:26040597

Niobium pentoxide as radiopacifying agent of calcium silicate-based material: evaluation of physicochemical and biological properties.

PubMed

Silva, Guilherme F; Tanomaru-Filho, Mário; Bernardi, Maria I B; Guerreiro-Tanomaru, Juliane M; Cerri, Paulo S

2015-11-01

The physicochemical properties and the tissue reaction promoted by microparticulated or nanoparticulated niobium pentoxide (Nb2O5) added to calcium silicate-based cement (CS), compared to MTA-Angelus™, were evaluated. Materials were submitted to the tests of radiopacity, setting time, pH, and calcium ion release. Polyethylene tubes filled with the materials were implanted into rats subcutaneously. After 7, 15, 30, and 60 days, the specimens were fixed and embedded in paraffin. Hematoxylin & eosin (H&E)-stained sections were used to compute the number of inflammatory cells (IC). Interleukin-6 (IL-6) detection was performed, and the number of immunolabeled cells was obtained; von Kossa method was also carried out. Data were subjected to ANOVA and Tukey test (p ≤ 0.05). Nb2O5micro and Nb2O5nano provided to the CS radiopacity values (3.52 and 3.75 mm Al, respectively) superior to the minimum recommended. Groups containing Nb2O5 presented initial setting time significantly superior than mineral trioxide aggregate (MTA). All materials presented an alkaline pH and released calcium ions. The number of IC and IL-6 immunolabeled cells in the CS + Nb2O5 groups was significantly reduced in comparison to MTA in all periods. von Kossa-positive structures were observed adjacent to implanted materials in all periods. The addition of Nb2O5 to the CS resulted in a material biocompatible and with adequate characteristics regarding radiopacity and final setting time and provides an alkaline pH to the environment. Furthermore, the particle size did not significantly affect the physicochemical and biological properties of the calcium silicate-based cement. Niobium pentoxide can be used as radiopacifier for the development of calcium silicate-based materials.

Mid-infrared observations of sungrazing comet C/2012 S1 (ISON) with the Subaru Telescope

NASA Astrophysics Data System (ADS)

Ootsubo, T.; Usui, F.; Takita, S.; Watanabe, J.; Yanamandra-Fisher, P.; Honda, M.; Kawakita, H.; Furusho, R.

2014-07-01

Comets are the frozen reservoirs of the early solar nebula and are made of ice and dust. The determination of the properties for cometary dust provides us insight into both the early-solar-nebula environment and the formation process of the planetary system. A silicate feature is often observed in comet spectra in the mid-infrared region and may be used for probing the early history of the solar system. In most cases, the feature shows the existence of crystalline silicate (for example, 11.3 microns) together with amorphous silicate [1,2]. Since the crystallization of silicates from amorphous ones generally requires high-temperature annealing above 800 K (e.g., [3,4]), it is believed that the crystalline silicate grains produced at the inner part of the disk were transported to the outer cold regions where the comet nuclei formed. Comet C/2012 S1 (ISON) is a long-period Oort Cloud comet, discovered in September 2012. In particular, comet ISON is a sungrazing comet, which was predicted to pass close by the Sun and the Earth and becoming a bright object. Mid-infrared observations of this new comet and investigation of the 10-micron silicate feature help us understand the formation of crystalline silicate grains in the early solar nebula. We conducted observations of comet ISON in the mid-infrared wavelength region with the Cooled Mid-Infrared Camera and Spectrometer (COMICS) on the Subaru Telescope on Mauna Kea, Hawaii [5,6,7]. The observation of comet ISON was carried out on 2013 October 19 and 21 UT. Since the weather conditions were not so good when we observed, we carried out N-band imaging observations (8.8 and 12.4 microns) and N-band low-resolution spectroscopy. The spectrum of comet ISON can be fit with the 260--265-K blackbody spectrum when we use the regions of 7.8--8.2 and 12.4--13.0 microns as the continuum. The spectrum has only a weak silicate excess feature, which may be able to attribute to small amorphous olivine grains. We could not detect a clear crystalline silicate feature in the spectrum of our observations. We will compare the spectrum with other Oort Cloud comets, such as comets C/2011 L4 (PanSTARRS) and C/2013 R1 (Lovejoy), and discuss the dust properties and the birthplace of comet ISON.

Targeted Control of Permeability Using Carbonate Dissolution/Precipitation Reactions

NASA Astrophysics Data System (ADS)

Clarens, A. F.; Tao, Z.; Plattenberger, D.

2016-12-01

Targeted mineral precipitation reactions are a promising approach for controlling fluid flow in the deep subsurface. Here we studied the potential to use calcium and magnesium bearing silicates as cation donors that would react with aqueous phase CO2 under reservoir conditions to form solid carbonate precipitates. Preliminary experiments in high pressure and temperature columns suggest that these reactions can effectively lower the permeability of a porous media. Wollastonite (CaSiO3) was used as the model silicate, injected as solid particles into the pore space of a packed column, which was then subsequently flooded with CO2(aq). The reactions occur spontaneously, leveraging the favorable kinetics that occur at the high temperature and pressure conditions characteristic of the deep subsurface, to form solid phase calcium carbonate (CaCO3) and amorphous silica (SiO2) within the pore space. Both x-ray tomography imaging of reacted columns and electron microscopy imaging of thin sections were used to characterize where dissolution/precipitation occurred within the porous media. The spatial distribution of the products was closely tied to the flow rate and the duration of the experiment. The SiO2 product precipitated in close spatial proximity to the CaSiO3 reactant. The CaCO3 product, which is sensitive to the low pH and high pCO2 brine, precipitated out of solution further down the column as Ca2+ ions moved with the brine. The permeability of the columns decreased by several orders of magnitude after injecting the CaSiO3 particles. Following carbonation, the permeability decreased even further as precipitates filled flow paths within the pore network. A pore network model was developed to help understand the interplay between precipitation kinetics and flow in altering the permeability of the porous media. The effect of particle concentration and size, pore size, reaction time, and pCO2, are explored on pore/fracture aperture and reaction extent. To provide better control of these dynamics and ultimately devise a mechanism to deliver carbonation seed particles into leakage pathways, we are exploring the potential to functionalize the silicate particles using temperature sensitive polymer coatings.

In vitro synthesis and stabilization of amorphous calcium carbonate (ACC) nanoparticles within liposomes

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

Tester, Chantel C.; Brock, Ryan E.; Wu, Ching-Hsuan

2012-02-07

We show that amorphous calcium carbonate (ACC) can be synthesized in phospholipid bilayer vesicles (liposomes). Liposome-encapsulated ACC nanoparticles are stable against aggregation, do not crystallize for at least 20 h, and are ideally suited to investigate the influence of lipid chemistry, particle size, and soluble additives on ACC in situ.

Evaluation of European District Heating Systems for Application to Army Installations in the United States

DTIC Science & Technology

2006-07-01

pipes in hooded channels, and the steel insulated pipes are insulated with mineral wool . In the thermo- concrete laying system the insulation...depends on the type foam insulation used. • Class “A” steel carrier pipe with a mineral wool , foam glass, fiber glass, or calcium silicate insulation...with a mineral wool , foam glass, fiber glass, or calcium silicate insulation covered by a steel con- duit, which has a polyurethane foam insulation

Development of the foremost light-curable calcium-silicate MTA cement as root-end in oral surgery. Chemical-physical properties, bioactivity and biological behavior.

PubMed

Gandolfi, Maria Giovanna; Taddei, Paola; Siboni, Francesco; Modena, Enrico; Ciapetti, Gabriela; Prati, Carlo

2011-07-01

An innovative light-curable calcium-silicate cement containing a HEMA-TEGDMA-based resin (lc-MTA) was designed to obtain a bioactive fast setting root-end filling and root repair material. lc-MTA was tested for setting time, solubility, water absorption, calcium release, alkalinizing activity (pH of soaking water), bioactivity (apatite-forming ability) and cell growth-proliferation. The apatite-forming ability was investigated by micro-Raman, ATR-FTIR and ESEM/EDX after immersion at 37°C for 1-28 days in DPBS or DMEM+FBS. The marginal adaptation of cement in root-end cavities of extracted teeth was assessed by ESEM/EDX, and the viability of Saos-2 cell on cements was evaluated. lc-MTA demonstrated a rapid setting time (2min), low solubility, high calcium release (150-200ppm) and alkalinizing power (pH 10-12). lc-MTA proved the formation of bone-like apatite spherulites just after 1 day. Apatite precipitates completely filled the interface porosities and created a perfect marginal adaptation. lc-MTA allowed Saos-2 cell viability and growth and no compromising toxicity was exerted. HEMA-TEGDMA creates a polymeric network able to stabilize the outer surface of the cement and a hydrophilic matrix permeable enough to allow water absorption. SiO(-)/Si-OH groups from the mineral particles induce heterogeneous nucleation of apatite by sorption of calcium and phosphate ions. Oxygen-containing groups from poly-HEMA-TEGDMA provide additional apatite nucleating sites through the formation of calcium chelates. The strong novelty was that the combination of a hydraulic calcium-silicate powder and a poly-HEMA-TEGDMA hydrophilic resin creates the conditions (calcium release and functional groups able to chelate Ca ions) for a bioactive fast setting light-curable material for clinical applications in dental and maxillofacial surgery. The first and unique/exclusive light-curable calcium-silicate MTA cement for endodontics and root-end application was created, with a potential strong impact on surgical procedures. Copyright © 2011 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Production of Organic Grain Coatings by Surface-Mediated Reactions and the Consequences of This Process for Meteoritic Constituents

NASA Technical Reports Server (NTRS)

Nuth, Joseph A., III; Johnson, Natasha M.

2011-01-01

When hydrogen, nitrogen and CO are exposed to amorphous iron silicate surfaces at temperatures between 500 - 900K, a carbonaceous coating forms via Fischer-Tropsch type reactions. Under normal circumstances such a catalytic coating would impede or stop further reaction. However, we find that this coating is a better catalyst than the amorphous iron silicates that initiate these reactions. The formation of a self-perpetuating catalytic coating on grain surfaces could explain the rich deposits of macromolecular carbon found in primitive meteorites and would imply that protostellar nebulae should be rich in organic material. Many more experiments are needed to understand this chemical system and its application to protostellar nebulae.

Influence of substrate mineralogy on bacterial mineralization of calcium carbonate: implications for stone conservation.

PubMed

Rodriguez-Navarro, Carlos; Jroundi, Fadwa; Schiro, Mara; Ruiz-Agudo, Encarnación; González-Muñoz, María Teresa

2012-06-01

The influence of mineral substrate composition and structure on bacterial calcium carbonate productivity and polymorph selection was studied. Bacterial calcium carbonate precipitation occurred on calcitic (Iceland spar single crystals, marble, and porous limestone) and silicate (glass coverslips, porous sintered glass, and quartz sandstone) substrates following culturing in liquid medium (M-3P) inoculated with different types of bacteria (Myxococcus xanthus, Brevundimonas diminuta, and a carbonatogenic bacterial community isolated from porous calcarenite stone in a historical building) and direct application of sterile M-3P medium to limestone and sandstone with their own bacterial communities. Field emission scanning electron microscopy (FESEM), atomic force microscopy (AFM), powder X-ray diffraction (XRD), and 2-dimensional XRD (2D-XRD) analyses revealed that abundant highly oriented calcite crystals formed homoepitaxially on the calcitic substrates, irrespective of the bacterial type. Conversely, scattered spheroidal vaterite entombing bacterial cells formed on the silicate substrates. These results show that carbonate phase selection is not strain specific and that under equal culture conditions, the substrate type is the overruling factor for calcium carbonate polymorph selection. Furthermore, carbonate productivity is strongly dependent on the mineralogy of the substrate. Calcitic substrates offer a higher affinity for bacterial attachment than silicate substrates, thereby fostering bacterial growth and metabolic activity, resulting in higher production of calcium carbonate cement. Bacterial calcite grows coherently over the calcitic substrate and is therefore more chemically and mechanically stable than metastable vaterite, which formed incoherently on the silicate substrates. The implications of these results for technological applications of bacterial carbonatogenesis, including building stone conservation, are discussed.

Influence of Substrate Mineralogy on Bacterial Mineralization of Calcium Carbonate: Implications for Stone Conservation

PubMed Central

Jroundi, Fadwa; Schiro, Mara; Ruiz-Agudo, Encarnación; González-Muñoz, María Teresa

2012-01-01

The influence of mineral substrate composition and structure on bacterial calcium carbonate productivity and polymorph selection was studied. Bacterial calcium carbonate precipitation occurred on calcitic (Iceland spar single crystals, marble, and porous limestone) and silicate (glass coverslips, porous sintered glass, and quartz sandstone) substrates following culturing in liquid medium (M-3P) inoculated with different types of bacteria (Myxococcus xanthus, Brevundimonas diminuta, and a carbonatogenic bacterial community isolated from porous calcarenite stone in a historical building) and direct application of sterile M-3P medium to limestone and sandstone with their own bacterial communities. Field emission scanning electron microscopy (FESEM), atomic force microscopy (AFM), powder X-ray diffraction (XRD), and 2-dimensional XRD (2D-XRD) analyses revealed that abundant highly oriented calcite crystals formed homoepitaxially on the calcitic substrates, irrespective of the bacterial type. Conversely, scattered spheroidal vaterite entombing bacterial cells formed on the silicate substrates. These results show that carbonate phase selection is not strain specific and that under equal culture conditions, the substrate type is the overruling factor for calcium carbonate polymorph selection. Furthermore, carbonate productivity is strongly dependent on the mineralogy of the substrate. Calcitic substrates offer a higher affinity for bacterial attachment than silicate substrates, thereby fostering bacterial growth and metabolic activity, resulting in higher production of calcium carbonate cement. Bacterial calcite grows coherently over the calcitic substrate and is therefore more chemically and mechanically stable than metastable vaterite, which formed incoherently on the silicate substrates. The implications of these results for technological applications of bacterial carbonatogenesis, including building stone conservation, are discussed. PMID:22447589

Reduction of calcium flux from the extracellular region and endoplasmic reticulum by amorphous nano-silica particles owing to carboxy group addition on their surface.

PubMed

Onodera, Akira; Yayama, Katsutoshi; Morosawa, Hideto; Ishii, Yukina; Tsutsumi, Yasuo; Kawai, Yuichi

2017-03-01

Several studies have reported that amorphous nano-silica particles (nano-SPs) modulate calcium flux, although the mechanism remains incompletely understood. We thus analyzed the relationship between calcium flux and particle surface properties and determined the calcium flux route. Treatment of Balb/c 3T3 fibroblasts with nano-SPs with a diameter of 70 nm (nSP70) increased cytosolic calcium concentration, but that with SPs with a diameter of 300 or 1000 nm did not. Surface modification of nSP70 with a carboxy group also did not modulate calcium flux. Pretreatment with a general calcium entry blocker almost completely suppressed calcium flux by nSP70. Preconditioning by emptying the endoplasmic reticulum (ER) calcium stores slightly suppressed calcium flux by nSP70. These results indicate that nSP70 mainly modulates calcium flux across plasma membrane calcium channels, with subsequent activation of the ER calcium pump, and that the potential of calcium flux by nano-SPs is determined by the particle surface charge.

Properties of a novel polysiloxane-guttapercha calcium silicate-bioglass-containing root canal sealer.

PubMed

Gandolfi, M G; Siboni, F; Prati, C

2016-05-01

Root canal filling sealers based on polymethyl hydrogensiloxane or polymethyl hydrogensiloxane-guttapercha--introduced to improve the quality of conventional guttapercha-based and resin-based systems--showed advantages in handiness and clinical application. The aim of the study was to evaluate the chemical-physical properties of a novel polysiloxane-guttapercha calcium silicate-containing root canal sealer (GuttaFlow bioseal). GuttaFlow bioseal was examined and compared with GuttaFlow2, RoekoSeal and MTA Fillapex sealers. Setting times, open and impervious porosity and apparent porosity, water sorption, weight loss, calcium release, and alkalinizing activity were evaluated. ESEM-EDX-Raman analyses of fresh materials and after soaking in simulated body fluid were also performed. Marked differences were obtained among the materials. GuttaFlow bioseal showed low solubility and porosity, high water sorption, moderate calcium release and good alkalinizing activity. MTA Fillapex showed the highest calcium release, alkalinizing activity and solubility, RoekoSeal the lowest calcium release, no alkalinizing activity, very low solubility and water sorption. Only GuttaFlow bioseal showed apatite forming ability. GuttaFlow bioseal showed alkalinizing activity together with negligible solubility and slight calcium release. Therefore, the notable nucleation of apatite and apatite precursors can be related to the co-operation of CaSi particles (SiOH groups) with polysiloxane (SiOSi groups). The incorporation of a calcium silicate component into polydimethyl polymethylhydrogensiloxane guttapercha sealers may represent an attractive strategy to obtain a bioactive biointeractive flowable guttapercha sealer for moist/bleeding apices with bone defects in endodontic therapy. Copyright © 2016 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Hydrothermal Synthesis of Dicalcium Silicate Based Cement

NASA Astrophysics Data System (ADS)

Dutta, N.; Chatterjee, A.

2017-06-01

It is imperative to develop low energy alternative binders considering the large amounts of energy consumed as well as carbon dioxide emissions involved in the manufacturing of ordinary Portland cement. This study is on the synthesis of a dicalcium silicate based binder using a low temperature hydrothermal route.The process consists of synthesizing an intermediate product consisting of a calcium silicate hydrate phase with a Ca:Si ratio of 2:1 and further thermal treatment to produce the β-Ca2SiO4 (C2S) phase.Effect of various synthesis parameters like water to solid ratio, dwell time and temperature on the formation of the desired calcium silicate hydrate phase is reported along with effect of heating conditions for formation of the β-C2S phase. Around 77.45% of β-C2S phase was synthesized by thermal treatment of the intermediate phase at 820°C.

Microwave hydrothermal transformation of amorphous calcium carbonate nanospheres and application in protein adsorption.

PubMed

Qi, Chao; Zhu, Ying-Jie; Chen, Feng

2014-03-26

Calcium carbonate and calcium phosphate are the main components of biominerals. Among all of the forms of biominerals, amorphous calcium carbonate (ACC) and amorphous calcium phosphate (ACP) are the most important forms because they play a pivotal role in the process of biomineralization and are the precursors to the crystalline polymorphs. In this work, we first synthesized ACC in vitro using adenosine 5'-triphosphate disodium salt (ATP) as the stabilizer and investigated the transformation of the ACC under microwave hydrothermal conditions, and ACC/ACP composite nanospheres and carbonated hydroxyapatite (CHA) nanospheres were successfully prepared. In this novel strategy, ATP has two main functions: it serves as the stabilizer for ACC and the phosphorus source for ACP and CHA. Most importantly, the morphology and the size of the ACC precursor can be well-preserved after microwave heating, so it provides a new method for the preparation of calcium phosphate nanostructured materials using phosphorus-containing biomolecule-stabilized ACC as the precursor. Furthermore, the as-prepared ACC/ACP composite nanospheres have excellent biocompatibility and high protein adsorption capacity, indicating that they are promising for applications in biomedical fields such as drug delivery and protein adsorption.

Magnesium-aspartate-based crystallization switch inspired from shell molt of crustacean

PubMed Central

Tao, Jinhui; Zhou, Dongming; Zhang, Zhisen; Xu, Xurong; Tang, Ruikang

2009-01-01

Many animals such as crustacean periodically undergo cyclic molt of the exoskeleton. During this process, amorphous calcium mineral phases are biologically stabilized by magnesium and are reserved for the subsequent rapid formation of new shell tissue. However, it is a mystery how living organisms can regulate the transition of the precursor phases precisely. We reveal that the shell mineralization from the magnesium stabilized precursors is associated with the presence of Asp-rich proteins. It is suggested that a cooperative effect of magnesium and Asp-rich compound can result into a crystallization switch in biomineralization. Our in vitro experiments confirm that magnesium increases the lifetime of amorphous calcium carbonate and calcium phosphate in solution so that the crystallization can be temporarily switched off. Although Asp monomer alone inhibits the crystallization of pure amorphous calcium minerals, it actually reduces the stability of the magnesium-stabilized precursors to switch on the transformation from the amorphous to crystallized phases. These modification effects on crystallization kinetics can be understood by an Asp-enhanced magnesium desolvation model. The interesting magnesium-Asp-based switch is a biologically inspired lesson from nature, which can be developed into an advanced strategy to control material fabrications. PMID:20007788

Magnesium-aspartate-based crystallization switch inspired from shell molt of crustacean.

PubMed

Tao, Jinhui; Zhou, Dongming; Zhang, Zhisen; Xu, Xurong; Tang, Ruikang

2009-12-29

Many animals such as crustacean periodically undergo cyclic molt of the exoskeleton. During this process, amorphous calcium mineral phases are biologically stabilized by magnesium and are reserved for the subsequent rapid formation of new shell tissue. However, it is a mystery how living organisms can regulate the transition of the precursor phases precisely. We reveal that the shell mineralization from the magnesium stabilized precursors is associated with the presence of Asp-rich proteins. It is suggested that a cooperative effect of magnesium and Asp-rich compound can result into a crystallization switch in biomineralization. Our in vitro experiments confirm that magnesium increases the lifetime of amorphous calcium carbonate and calcium phosphate in solution so that the crystallization can be temporarily switched off. Although Asp monomer alone inhibits the crystallization of pure amorphous calcium minerals, it actually reduces the stability of the magnesium-stabilized precursors to switch on the transformation from the amorphous to crystallized phases. These modification effects on crystallization kinetics can be understood by an Asp-enhanced magnesium desolvation model. The interesting magnesium-Asp-based switch is a biologically inspired lesson from nature, which can be developed into an advanced strategy to control material fabrications.

Preparation of reactive beta-dicalcium silicate

DOEpatents

Shen, M.S.; Chen, J.M.; Yang, R.T.

1980-02-28

This invention relates to the preparation of fine particles of reactive beta-dicalcium silicate by means of a solid state process which comprises firing a mixture of calcium sulfate, silica, and a reducing additive selected from the group consisting of calcium sulfide, carbon, carbon monoxide, methane, and hydrogen, at a temperature of about 850 to 1000/sup 0/C. A carrier gas such as nitrogen or carbon dioxide may also be added, if desired. A high concentration of sulfur dioxide is a by-product of this process.

Preparation of reactive beta-dicalcium silicate

DOEpatents

Shen, Ming-Shing; Chen, James M.; Yang, Ralph T.

1982-01-01

This invention relates to the preparation of fine particles of reactive beta-dicalcium silicate by means of a solid state process which comprises firing a mixture of calcium sulfate, silica and a reducing additive selected from the group consisting of calcium sulfide, carbon, carbon monoxide, methane and hydrogen, at a temperature of about 850.degree.-1000.degree. C. A carrier gas such as nitrogen or carbon dioxide may also be added, if desired. A high concentration of sulfur dioxide is a by-product of this process.

Struvite crystallization versus amorphous magnesium and calcium phosphate precipitation during the treatment of a saline industrial wastewater.

PubMed

Crutchik, D; Garrido, J M

2011-01-01

Struvite crystallization (MgNH(4)PO(4)·6H(2)O, MAP) could be an alternative for the sustainable and economical recovery of phosphorus from concentrated wastewater streams. Struvite precipitation is recommended for those wastewaters which have high orthophosphate concentration. However the presence of a cheap magnesium source is required in order to make the process feasible. For those wastewater treatment plants (WWTP) located near the seashore magnesium could be economically obtained using seawater. However seawater contains calcium ions that could interfere in the process, by promoting the precipitation of amorphous magnesium and calcium phosphates. Precipitates composition was affected by the NH(4)(+)/PO(4)(3-) molar ratio used. Struvite or magnesium and calcium phosphates were obtained when NH(4)(+)/PO(4)(3-) was fixed at 4.7 or 1.0, respectively. This study demonstrates that by manipulating the NH(4)(+)/PO(4)(3-) it is possible to obtain pure struvite crystals, instead of precipitates of amorphous magnesium and calcium phosphates. This was easily performed by using either raw or secondary treated wastewater with different ammonium concentrations.

Intrinsic Nano-Ductility of Glasses: The Critical Role of Composition

NASA Astrophysics Data System (ADS)

Wang, Bu; Yu, Yingtian; Lee, Young; Bauchy, Mathieu

2015-02-01

Understanding, predicting and eventually improving the resistance to fracture for silicate materials is of primary importance to design tougher new glasses suitable for advanced applications. However, the fracture mechanism at the atomic level in amorphous silicate materials is still a topic of debate. In particular, there are some controversies about the existence of ductility at the nanoscale during crack propagation. Here, we present simulations of fracture of three archetypical silicate glasses, using molecular dynamics. The simulations clearly show that, depending on their composition, silicate glasses can exhibit different degrees of ductility at the nanoscale. Additionally, we show that the methodology used in the present work can provide realistic predictions of fracture energy and toughness.

Mineralogical changes of a well cement in various H2S-CO2(-brine) fluids at high pressure and temperature.

PubMed

Jacquemet, Nicolas; Pironon, Jacques; Saint-Marc, Jérémie

2008-01-01

The reactivity of a crushed well cement in contact with (1) a brine with dissolved H2S-CO2; (2) a dry H2S-CO2 supercritical phase; (3) a two-phase fluid associating a brine with dissolved H2S-CO2 and a H2S-CO2 supercritical phase was investigated in batch experiments at 500 bar and 120, 200 degrees C. All of the experiments showed that following 15-60 days cement carbonation occurred. The H2S reactivity with cement is limited since it only transformed the ferrites (minor phases) by sulfidation. It appeared that the primary parameter controlling the degree of carbonation (i.e., the rate of calcium carbonates precipitation and CSH (Calcium Silicate Hydrates) decalcification) is the physical state of the fluid phase contacting the minerals. The carbonation degree is complete when the minerals contact at least the dry H2S-CO2 supercritical phase and partial when they contactthe brine with dissolved H2S-CO2. Aragonite (calcium carbonate polymorph) precipitated specifically within the dry H2S-CO2 supercritical phase. CSH cristallinity is improved by partial carbonation while CSH are amorphized by complete carbonation. However, the features evidenced in this study cannot be directly related to effective features of cement as a monolith. Further studies involving cement as a monolith are necessary to ascertain textural, petrophysical, and mechanical evolution of cement.

In vitro characterisation of a sol-gel derived in situ silica-coated silicate and carbonate co-doped hydroxyapatite nanopowder for bone grafting.

PubMed

Latifi, Seyed Mohsen; Fathi, Mohammadhossein; Sharifnabi, Ali; Varshosaz, Jaleh

2017-06-01

Design and synthesis of materials with better properties and performance are essential requirements in the field of biomaterials science that would directly improve patient quality of life. For this purpose, in situ silica-coated silicate and carbonate co-doped hydroxyapatite (Sc/S.C.HA) nanopowder was synthesized via the sol-gel method. Characterisation of the prepared nanopowder was carried out by XRD, FTIR, TEM, SEM, EDX, ICP, zeta potential, acid dissolution test, and cell culture test. The substitution of the silicate and carbonate ions into hydroxyapatite structure was confirmed by FTIR analysis. XRD analysis showed that silica is an amorphous phase, which played a role in covering the surface of the S.C.HA nanoparticles as confirmed by acid dissolution test. Low thickness and low integrity of the amorphous silica surface layer facilitated ions release from S.C.HA nanoparticles into physiological saline solution. Zeta potential of the prepared nanopowder suspended in physiological saline solution was -27.3±0.2mV at pH7.4. This negatively charged surface, due to the presence of amorphous silica layer upon the S.C.HA nanoparticles, not only had an accelerating effect on in vitro biomineralization of apatite, but also had a positive effect on cell attachment. Copyright © 2017 Elsevier B.V. All rights reserved.

Synthesis, characterization and modelling of zinc and silicate co-substituted hydroxyapatite.

PubMed

Friederichs, Robert J; Chappell, Helen F; Shepherd, David V; Best, Serena M

2015-07-06

Experimental chemistry and atomic modelling studies were performed here to investigate a novel ionic co-substitution in hydroxyapatite (HA). Zinc, silicate co-substituted HA (ZnSiHA) remained phase pure after heating to 1100 °C with Zn and Si amounts of 0.6 wt% and 1.2 wt%, respectively. Unique lattice expansions in ZnSiHA, silicate Fourier transform infrared peaks and changes to the hydroxyl IR stretching region suggested Zn and silicate co-substitution in ZnSiHA. Zn and silicate insertion into HA was modelled using density functional theory (DFT). Different scenarios were considered where Zn substituted for different calcium sites or at a 2b site along the c-axis, which was suspected in singly substituted ZnHA. The most energetically favourable site in ZnSiHA was Zn positioned at a previously unreported interstitial site just off the c-axis near a silicate tetrahedron sitting on a phosphate site. A combination of experimental chemistry and DFT modelling provided insight into these complex co-substituted calcium phosphates that could find biomedical application as a synthetic bone mineral substitute. © 2015 The Author(s) Published by the Royal Society. All rights reserved.

The nature of cometary dust as determined from infrared observations

NASA Technical Reports Server (NTRS)

Swamy, K. S. Krishna; Sandford, Scott A.; Allamandola, Louis J.; Witteborn, Fred C.; Bregman, Jesse D.

1989-01-01

The infrared measurements of comets, the compositional information available from interplanetary dust particles (IDPs), and the recent results of flybys to Comet Halley can help in restricting the nature and composition of cometary dust models (c.f., Proceedings of the 20th ESLAB Symposium on Exploration of Halley's Comet, 1986). Researchers tried to incorporate some of these results into a coherent model to account for the observed cometary infrared emission. The presence of 10 and 3.4 micron features in Comet Halley (c.f. Bregman et al. 1987; Wickramasinghe and Allen 1986) indicated the presence of at least two components in the grain material, namely silicates and some form of amorphous carbon. These two components could reside in separate grains or may be parts of composite particles. Both these cases have been considered (see Krishna Swamy el a. 1988a, 1988b). In the absence of refractive index data for cometary analogs, the authors used the optical constants of olivine-rich lunar material 12009.48 (Perry et al. 1972) for the infrared region and that of alpha:C-H film for amorphous carbon (angus et al. 1986). For the visible region, a value of m = 1.38-0.39i was used for the silicates, and values published by Arakawa et al. (1985) were used for the amorphous carbon. These materials should give a representative behavior of the expected results. The model results were compared to observational data. The strength of the 3.4 micron and 10 micron features relative to the adjacent continuum, as well as the slope of the continuum between 2500 and 1250 cm(exp -1) (4 to 8 microns), were used as criteria for comparison. Model calculations with alpha approx. equals -3.5, and also the size distribution function inferred for Comet Halley, with a mass fraction (X) of silicate to amorphous carbon grains of about 40 to 1 can fit the data. A good match is obtained for the infrared spectra of Comets Halley and West from a 40 to 1 mixture of silicate and amorphous carbon grains with a a(exp -3.5) size distribution function. The results are consistent with compositional constraints provided by interplanetary dust particles (IPDs) and Halley flyby data. The variation of grain temperature with heliocentric distance appears to account for the major changes observed in cometary spectra.

Dentin-cement Interfacial Interaction

PubMed Central

Atmeh, A.R.; Chong, E.Z.; Richard, G.; Festy, F.; Watson, T.F.

2012-01-01

The interfacial properties of a new calcium-silicate-based coronal restorative material (Biodentine™) and a glass-ionomer cement (GIC) with dentin have been studied by confocal laser scanning microscopy (CLSM), scanning electron microscopy (SEM), micro-Raman spectroscopy, and two-photon auto-fluorescence and second-harmonic-generation (SHG) imaging. Results indicate the formation of tag-like structures alongside an interfacial layer called the “mineral infiltration zone”, where the alkaline caustic effect of the calcium silicate cement’s hydration products degrades the collagenous component of the interfacial dentin. This degradation leads to the formation of a porous structure which facilitates the permeation of high concentrations of Ca2+, OH-, and CO32- ions, leading to increased mineralization in this region. Comparison of the dentin-restorative interfaces shows that there is a dentin-mineral infiltration with the Biodentine, whereas polyacrylic and tartaric acids and their salts characterize the penetration of the GIC. A new type of interfacial interaction, “the mineral infiltration zone”, is suggested for these calcium-silicate-based cements. PMID:22436906

Process for production desulfurized of synthesis gas

DOEpatents

Wolfenbarger, James K.; Najjar, Mitri S.

1993-01-01

A process for the partial oxidation of a sulfur- and silicate-containing carbonaceous fuel to produce a synthesis gas with reduced sulfur content which comprises partially oxidizing said fuel at a temperature in the range of 1900.degree.-2600.degree. F. in the presence of a temperature moderator, an oxygen-containing gas and a sulfur capture additive which comprises a calcium-containing compound portion, a sodium-containing compound portion, and a fluoride-containing compound portion to produce a synthesis gas comprising H.sub.2 and CO with a reduced sulfur content and a molten slag which comprises (1) a sulfur-containing sodium-calcium-fluoride silicate phase; and (2) a sodium-calcium sulfide phase.

Silicon based substrate with calcium aluminosilicate/thermal barrier layer

NASA Technical Reports Server (NTRS)

Eaton, Jr., Harry Edwin (Inventor); Allen, William Patrick (Inventor); Miller, Robert Alden (Inventor); Jacobson, Nathan S. (Inventor); Smialek, James L. (Inventor); Opila, Elizabeth J. (Inventor); Lee, Kang N. (Inventor); Nagaraj, Bangalore A. (Inventor); Wang, Hongyu (Inventor); Meschter, Peter Joel (Inventor)

2001-01-01

A barrier layer for a silicon containing substrate which inhibits the formation of gaseous species of silicon when exposed to a high temperature aqueous environment comprises a calcium alumino silicate.

Brain aluminium accumulation and oxidative stress in the presence of calcium silicate dental cements.

PubMed

Demirkaya, K; Demirdöğen, B Can; Torun, Z Öncel; Erdem, O; Çırak, E; Tunca, Y M

2017-10-01

Mineral trioxide aggregate (MTA) is a calcium silicate dental cement used for various applications in dentistry. This study was undertaken to test whether the presence of three commercial brands of calcium silicate dental cements in the dental extraction socket of rats would affect the brain aluminium (Al) levels and oxidative stress parameters. Right upper incisor was extracted and polyethylene tubes filled with MTA Angelus, MTA Fillapex or Theracal LC, or left empty for the control group, were inserted into the extraction socket. Rats were killed 7, 30 or 60 days after operation. Brain tissues were obtained before killing. Al levels were measured by atomic absorption spectrometry. Thiobarbituric acid reactive substances (TBARS) levels, catalase (CAT), superoxide dismutase (SOD) and glutathione peroxidase (GPx) activities were determined using spectrophotometry. A transient peak was observed in brain Al level of MTA Angelus group on day 7, while MTA Fillapex and Theracal LC groups reached highest brain Al level on day 60. Brain TBARS level, CAT, SOD and GPx activities transiently increased on day 7 and then returned to almost normal levels. This in vivo study for the first time indicated that initial washout may have occurred in MTA Angelus, while element leaching after the setting is complete may have taken place for MTA Fillapex and Theracal LC. Moreover, oxidative stress was induced and antioxidant enzymes were transiently upregulated. Further studies to search for oxidative neuronal damage should be done to completely understand the possible toxic effects of calcium silicate cements on the brain.

Rapid hydrothermal flow synthesis and characterisation of carbonate- and silicate-substituted calcium phosphates

PubMed Central

Knowles, Jonathan C; Rehman, Ihtesham; Darr, Jawwad A

2013-01-01

A range of crystalline and nano-sized carbonate- and silicate-substituted hydroxyapatite has been successfully produced by using continuous hydrothermal flow synthesis technology. Ion-substituted calcium phosphates are better candidates for bone replacement applications (due to improved bioactivity) as compared to phase-pure hydroxyapatite. Urea was used as a carbonate source for synthesising phase pure carbonated hydroxyapatite (CO3-HA) with ≈5 wt% substituted carbonate content (sample 7.5CO3-HA) and it was found that a further increase in urea concentration in solution resulted in biphasic mixtures of carbonate-substituted hydroxyapatite and calcium carbonate. Transmission electron microscopy images revealed that the particle size of hydroxyapatite decreased with increasing urea concentration. Energy-dispersive X-ray spectroscopy result revealed a calcium deficient apatite with Ca:P molar ratio of 1.45 (±0.04) in sample 7.5CO3-HA. For silicate-substituted hydroxyapatite (SiO4-HA) silicon acetate was used as a silicate ion source. It was observed that a substitution threshold of ∼1.1 wt% exists for synthesis of SiO4-HA in the continuous hydrothermal flow synthesis system, which could be due to the decreasing yields with progressive increase in silicon acetate concentration. All the as-precipitated powders (without any additional heat treatments) were analysed using techniques including Transmission electron microscopy, X-ray powder diffraction, Differential scanning calorimetry, Thermogravimetric analysis, Raman spectroscopy and Fourier transform infrared spectroscopy. PMID:22983020

Preliminary study on removing Cs⁺/Sr²⁺ by activated porous calcium silicate-A by-product from high-alumina fly ash recycling industry.

PubMed

Chu, Yingying; Wang, Rong; Chen, Mengjun

2015-01-01

¹³⁷Cs⁺/⁹⁰Sr²⁺-containing radioactive wastewater is one of the most important problems that the world has been facing with. A by-product, activated porous calcium silicate, is generated at high levels by the pre-desiliconizing and soda-lime-sintering processes for producing Al₂O₃from high-alumina fly ash. In order to examine if this by-product could be used as an absorbent for removal of ¹³⁷Cs⁺/⁹⁰Sr²⁺ from radioactive wastewater, various parameters, such as pH, adsorbent dose, contact time, and initial concentration, were discussed. Results indicated that the equilibrium reached in about 2 hr. Activated porous calcium silicate was highly pH sensitive and able to remove Cs(+)/Sr²⁺ in a near-neutral environment. The adsorption equilibrium was best described by Freundlich isotherm equations, and the adsorption of Cs⁺/Sr²⁺ was a physical process. The adsorption kinetic data could be better fitted by the pseudo-second-order model, and the adsorption was controlled by multidiffusion. Current study showed that activated porous calcium silicate has a good adsorption of Cs⁺/Sr²⁺ for their removal. However, other characteristics, such as selectivity because of coexisting cations, elution and regeneration, thermal stability, and acid resistance, should be discussed carefully before using it in an actual field.

Sea urchin spine calcite forms via a transient amorphous calcium carbonate phase.

PubMed

Politi, Yael; Arad, Talmon; Klein, Eugenia; Weiner, Steve; Addadi, Lia

2004-11-12

The skeletons of adult echinoderms comprise large single crystals of calcite with smooth convoluted fenestrated morphologies, raising many questions about how they form. By using water etching, infrared spectroscopy, electron diffraction, and environmental scanning electron microscopy, we show that sea urchin spine regeneration proceeds via the initial deposition of amorphous calcium carbonate. Because most echinoderms produce the same type of skeletal material, they probably all use this same mechanism. Deposition of transient amorphous phases as a strategy for producing single crystals with complex morphology may have interesting implications for the development of sophisticated materials.

Silicon based substrate with calcium aluminosilicate environmental/thermal barrier layer

NASA Technical Reports Server (NTRS)

Eaton, Jr., Harry Edwin (Inventor); Allen, William Patrick (Inventor); Miller, Robert Alden (Inventor); Jacobson, Nathan S. (Inventor); Smialek, James L. (Inventor); Opila, Elizabeth J. (Inventor); Lee, Kang N. (Inventor); Nagaraj, Bangalore A. (Inventor); Wang, Hongyu (Inventor); Meschter, Peter Joel (Inventor)

2001-01-01

A barrier layer for a silicon containing substrate which inhibits the formation of gaseous species of silicon when exposed to a high temperature aqueous environment comprises a calcium alumino silicate.

Effect of Casein Phosphopeptide-Amorphous Calcium Phosphate and Three Calcium Phosphate on Enamel Microhardness.

PubMed

Haghgou, En Hr; Haghgoo, Roza; Roholahi, Mohamad R; Ghorbani, Zahra

2017-07-01

This study aims to investigate the effect of casein phos-phopeptide-amorphous calcium phosphate and three calcium phosphate (CPP-ACP and TCP) on increasing the microhardness of human enamel after induction of erosion. A total of 26 healthy human-impacted third molar teeth were chosen, and their hardness measured using a microhardness testing machine. The samples were immersed in Coca Cola (pH = 4.7) for 8 minutes. Then, micro-hardness was measured again, and these samples were randomly divided into four groups (two control groups and two experimental groups). (1) Negative control group: Artificial saliva was used for 10 minutes, (2) positive control group: Fluoride gel was used for 10 minutes, (3) β-TCP group: TCP was used for 10 minutes, (4) CCP-ACP group: CCP-ACP was used for 10 minutes. The final microhardness of those samples was measured, and the changes in microhardness of teeth within group and between groups were analyzed using the paired and analysis of variance tests respectively. Results were considered statistically significant at a level of p < 0.05. No significant difference was observed in microhard-ness between CPP-ACP group and TCP group (p = 0.368) during the time microhardness significantly dropped after soaking in soda. Casein phosphopeptide-amorphous calcium phosphate and TCP increased the microhardness of teeth. The increase in hardness in the TCP group was higher than in the CPP-ACP group, but this difference was not significant (p = 0.36). Casein phosphopeptide-amorphous calcium phosphate and TCP can affect the remineralization of erosive lesions.

An in vitro comparison of casein phosphopeptide-amorphous calcium phosphate paste, casein phosphopeptide-amorphous calcium phosphate paste with fluoride and casein phosphopeptide-amorphous calcium phosphate varnish on the inhibition of demineralization and promotion of remineralization of enamel.

PubMed

Thakkar, Prachi Jayesh; Badakar, Chandrashekhar M; Hugar, Shivayogi M; Hallikerimath, Seema; Patel, Punit M; Shah, Parin

2017-01-01

This study aims to determine and compare the extent of inhibition of demineralization and promotion of remineralization of permanent molar enamel with and without application of three remineralizing agents. Forty extracted permanent molars were randomly divided into two groups 1 and 2, longitudinally sectioned into four and divided into subgroups A, B, C, and D. The sections were coated with nail varnish leaving a window of 3 mm × 3 mm. All sections of Group 1 were treated with their respective subgroup-specific agent: Casein phosphopeptide-amorphous calcium phosphate (CPP-ACP) paste for subgroup A, CPP-amorphous calcium phosphate fluoride (ACPF) paste for subgroup B, CPP-ACPF varnish for subgroup C and subgroup D served as a control. The sections were then subjected to demineralization for 12 days following which lesional depth was measured under the stereomicroscope. All the sections of Group 2 were subjected to demineralization for 12 days, examined for lesional depth, then treated with their respective subgroup specific agents and immersed in artificial saliva for 7 days. The sections were then examined again under the stereomicroscope to measure the lesional depth. CPP-ACPF varnish caused significant inhibition of demineralization. All three agents showed significant remineralization of previously demineralized lesions. However, CPP-ACPF varnish showed the greatest remineralization, followed by CPP-ACPF paste and then CPP-ACP paste. This study shows that CPP-ACPF varnish is effective in preventing demineralization as well as promoting remineralization of enamel. Thus, it can be used as an effective preventive measure for pediatric patients where compliance with the use of tooth mousse may be questionable.

Formulation and characterization of a compacted multiparticulate system for modified release of water-soluble drugs--part 1--acetaminophen.

PubMed

Cantor, Stuart L; Hoag, Stephen W; Augsburger, Larry L

2009-03-01

The aim of this study was to characterize and evaluate a modified release, multiparticulate tablet formulation consisting of placebo beads and drug-loaded beads. Acetaminophen (APAP) bead formulations containing ethylcellulose (EC) from 40-60% and placebo beads containing 30% calcium silicate and prepared using 0-20% alcohol were developed using extrusion-spheronization and studied using a central composite experimental design. Particle size and true density of beads were measured. Segregation testing was performed using the novel ASTM D6940-04 method on a 50:50 blend of uncoated APAP beads (60%EC) : calcium silicate placebo beads (10% alcohol). Tablets were prepared using an instrumented Stokes-B2 rotary tablet press and evaluated for crushing strength and dissolution rate. Compared with drug beads (60%EC), placebo beads (10% alcohol) were smaller but had higher true densities: 864.8 mum and 1.27 g/cm(3), and 787.1 mum and 1.73 g/cm(3), respectively. Segregation testing revealed that there was approximately a 20% difference in drug content (as measured by the coefficient of variation) between initial and final blend samples. Although calcium silicate-based placebo beads were shown to be ineffective cushioning agents in blends with Surelease(R)-coated APAP beads, they were found to be very compactibile when used alone and gave tablet crushing strength values between 14 and 17 kP. The EC in the APAP bead matrix minimally suppressed the drug release from uncoated beads (t(100%) = 2 h). However, while tablets containing placebo beads reformulated with glycerol monostearate (GMS) showed a slower release rate (t(60%)= 5 h) compared with calcium silicate-based placebos, some coating damage ( approximately 30%) still occurred on compression as release was faster than coated APAP beads alone. While tablets containing coated drug beads can be produced with practical crushing strengths (>8 kP) and low compression pressures (10-35 MPa), dissolution studies revealed that calcium silicate-based placebos are ineffective as cushioning agents. Blend segregation was likely observed due to the particle size and the density differences between APAP beads and calcium silicate-based placebo beads; placebo bead percolation can perhaps be minimized by increasing their size during the extrusion-spheronization process. The GMS- based placebos offer greater promise as cushioning agents for compacted, coated drug beads; however, this requires an optimized compression pressure range and drug bead : placebo bead ratio (i.e., 50:50).

Constraints on cosmic silicates

NASA Astrophysics Data System (ADS)

Ossenkopf, V.; Henning, Th.; Mathis, J. S.

1992-08-01

Observational determinations of opacities of circumstellar silicates, relative to the peak value near 10 microns, are used to estimate the optical constants n and k, the real and imaginary parts of the index of refraction. Circumstellar dust is modified by processing within the interstellar medium. This leads to higher band strengths and a somewhat larger ratio of the opacities at the 18 and 10-micron peaks, compared with circumstellar silicates. By using an effective-medium theory, we calculate the effects of small spherical inclusions of various materials (various oxides, sulfides, carbides, amorphous carbon, and metallic iron) upon silicate opacities. Some of these can increase the absorption coefficient k in the 2-8 micron region appreciably, as is needed to reconcile laboratory silicate opacities with observations of both the interstellar medium and envelopes around late-type stars. We give tables of two sets of optical constants for warm oxygen-deficient and cool oxygen-rich silicates, representative for circumstellar and interstellar silicates. The required opacity in the 2-8 micron region is provided by iron and magnetite.

Predictive Mechanical Characterization of Macro-Molecular Material Chemistry Structures of Cement Paste at Nano Scale - Two-phase Macro-Molecular Structures of Calcium Silicate Hydrate, Tri-Calcium Silicate, Di-Calcium Silicate and Calcium Hydroxide

NASA Astrophysics Data System (ADS)

Padilla Espinosa, Ingrid Marcela

Concrete is a hierarchical composite material with a random structure over a wide range of length scales. At submicron length scale the main component of concrete is cement paste, formed by the reaction of Portland cement clinkers and water. Cement paste acts as a binding matrix for the other components and is responsible for the strength of concrete. Cement paste microstructure contains voids, hydrated and unhydrated cement phases. The main crystalline phases of unhydrated cement are tri-calcium silicate (C3S) and di-calcium silicate (C2S), and of hydrated cement are calcium silicate hydrate (CSH) and calcium hydroxide (CH). Although efforts have been made to comprehend the chemical and physical nature of cement paste, studies at molecular level have primarily been focused on individual components. Present research focuses on the development of a method to model, at molecular level, and analysis of the two-phase combination of hydrated and unhydrated phases of cement paste as macromolecular systems. Computational molecular modeling could help in understanding the influence of the phase interactions on the material properties, and mechanical performance of cement paste. Present work also strives to create a framework for molecular level models suitable for potential better comparisons with low length scale experimental methods, in which the sizes of the samples involve the mixture of different hydrated and unhydrated crystalline phases of cement paste. Two approaches based on two-phase cement paste macromolecular structures, one involving admixed molecular phases, and the second involving cluster of two molecular phases are investigated. The mechanical properties of two-phase macromolecular systems of cement paste consisting of key hydrated phase CSH and unhydrated phases C3S or C2S, as well as CSH with the second hydrated phase CH were calculated. It was found that these cement paste two-phase macromolecular systems predicted an isotropic material behavior. Also, these systems exhibited a high bulk modulus, compared to the elastic modulus. These results are an indication and concur with the high compression strength of cement paste seen at engineering length scale. In addition, the bulk modulus of two-phase systems consisting of hydrated CSH and unhydrated C3S or C2S was found to increase with higher levels of unhydrated components. The interaction energies of two-phase cement paste molecular structures studied in the present work were calculated, showing that a higher interaction is attained when the two phases are admixed as small components instead of cluster of phases. Finally, the mechanical behavior under shear deformation was predicted by using a quasi-static deformation method and analyzed for a representative two-phase (CSH and C2S) macromolecular structure of cement paste.

3D Observation of GEMS by Electron Tomography

NASA Technical Reports Server (NTRS)

Matsuno, Junya; Miyake, Akira; Tsuchiyama, Akira; Nakamura-Messenger, Keiko; Messenger, Scott

2014-01-01

Amorphous silicates in chondritic porous interplanetary dust particles (CP-IDPs) coming from comets are dominated by glass with embedded metal and sulfides (GEMS). GEMS grains are submicron-sized rounded objects (typically 100-500) nm in diameter) with anaometer-sized (10-50 nm) Fe-Ni metal and sulfide grains embedded in an amorphous silicate matrix. Several formation processes for GEMS grains have been proposed so far, but these models are still being debated [2-5]. Bradley et al. proposed that GEMS grains are interstellar silicate dust that survived various metamorphism or alteration processes in the protoplanetary disk and that they are amorphiation products of crystalline silicates in the interstellar medium by sputter-deposition of cosmic ray irradiation, similar to space weathering [2,4]. This consideration is based on the observation of nano-sized crystals (approximately 10 nm) called relict grains in GEMS grains and their shapes are pseudomorphs to the host GEMS grains. On the other hand, Keller and Messenger proposed that most GEMS formed in the protoplanetary disk as condensates from high temperature gas [3,5]. This model is based on the fact that most GEMS grains have solar isotopic compositions and have extremely heterogeneous and non-solar elemental compositions. Keller and Messenger (2011) also reported that amorphous silicates in GEMS grains are surrounded by sulfide grains, which formed as sulfidization of metallic iron grains located on the GEMS surface. The previous studies were performed with 2D observation by using transmission electron microscopy (TEM) or scanning TEM (STEM). In order to understand the structure of GEMS grains described above more clearly, we observed 3D structure of GEMS grains by electron tomography using a TEM/STEM (JEM-2100F, JEOL) at Kyoto University. Electron tomography gives not only 3D structures but also gives higher spatial resolution (approximately a few nm) than that in conventional 2D image, which is restricted by sample thickness ) approx. or greater than 50 nm). Three cluster IDPs (L2036AA5 cluster4, L2009L8 cluster 13 and W726A2) were used for the observations. ID W726A2 was collected without silicon oil, which is ordinary used to collect IDPs, so this sample has no possibility of contaminations caused by silicon oil or solvent to rinse it [6]. The samples were embedded in epoxy risin and sliced into ultrathin sections (50-300 nm) using an ultramicotome. The sections were observed by BF-TEM and HAADF-STEM (high angle annular dark field-scanning TEM) modes. Images were obtained by rotating the sample tilt angle over a range of +/- 65 deg in 1 deg steps. The obtained images were reconstructed to slice images. Mineral phases in the slice images were estimated by comparing with a 2D elemental map obtained by an EDS (energy dispersive X-ray spectroscopy) system equipped in the TEM/STEM. Careful examination of the slice images confirmed that iron grains are embedded in the amorphous silicate matrix of the GEMS grains, but sulfide grains were mainly present on the surface of the amorphous silicate. These results are consistent with the model that GEMS grains formed as condensates [3,5], although more data are needed to conclude the origin of GEMS grains. The present study is the first successful example adapting the electron tomography to the IDPs. This type of analysis will be important for planetary material sciences in the future.

Confined Water in Layered Silicates: The Origin of Anomalous Thermal Expansion Behavior in Calcium-Silicate-Hydrates

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

Krishnan, N. M. Anoop; Wang, Bu; Falzone, Gabriel

Water, under conditions of nanoscale confinement, exhibits anomalous dynamics, and enhanced thermal deformations, which may be further enhanced when such water is in contact with hydrophilic surfaces. Such heightened thermal deformations of water could control the volume stability of hydrated materials containing nanoconfined structural water. Understanding and predicting the thermal deformation coefficient (TDC, often referred to as the CTE, coefficient of thermal expansion), which represents volume changes induced in materials under conditions of changing temperature, is of critical importance for hydrated solids including: hydrogels, biological tissues, and calcium silicate hydrates, as changes in their volume can result in stress development,more » and cracking. By pioneering atomistic simulations, we examine the physical origin of thermal expansion in calcium-silicate-hydrates (C–S–H), the binding agent in concrete that is formed by the reaction of cement with water. We report that the TDC of C–S–H shows a sudden increase when the CaO/SiO 2 (molar ratio; abbreviated as Ca/Si) exceeds 1.5. This anomalous behavior arises from a notable increase in the confinement of water contained in the C–S–H’s nanostructure. We identify that confinement is dictated by the topology of the C–S–H’s atomic network. Altogether, the results suggest that thermal deformations of hydrated silicates can be altered by inducing compositional changes, which in turn alter the atomic topology and the resultant volume stability of the solids.« less

Confined Water in Layered Silicates: The Origin of Anomalous Thermal Expansion Behavior in Calcium-Silicate-Hydrates.

PubMed

Krishnan, N M Anoop; Wang, Bu; Falzone, Gabriel; Le Pape, Yann; Neithalath, Narayanan; Pilon, Laurent; Bauchy, Mathieu; Sant, Gaurav

2016-12-28

Water, under conditions of nanoscale confinement, exhibits anomalous dynamics, and enhanced thermal deformations, which may be further enhanced when such water is in contact with hydrophilic surfaces. Such heightened thermal deformations of water could control the volume stability of hydrated materials containing nanoconfined structural water. Understanding and predicting the thermal deformation coefficient (TDC, often referred to as the CTE, coefficient of thermal expansion), which represents volume changes induced in materials under conditions of changing temperature, is of critical importance for hydrated solids including: hydrogels, biological tissues, and calcium silicate hydrates, as changes in their volume can result in stress development, and cracking. By pioneering atomistic simulations, we examine the physical origin of thermal expansion in calcium-silicate-hydrates (C-S-H), the binding agent in concrete that is formed by the reaction of cement with water. We report that the TDC of C-S-H shows a sudden increase when the CaO/SiO 2 (molar ratio; abbreviated as Ca/Si) exceeds 1.5. This anomalous behavior arises from a notable increase in the confinement of water contained in the C-S-H's nanostructure. We identify that confinement is dictated by the topology of the C-S-H's atomic network. Taken together, the results suggest that thermal deformations of hydrated silicates can be altered by inducing compositional changes, which in turn alter the atomic topology and the resultant volume stability of the solids.

CaCl 2 -Accelerated Hydration of Tricalcium Silicate: A STXM Study Combined with 29 Si MAS NMR

DOE PAGES

Li, Qinfei; Ge, Yong; Geng, Guoqing; ...

2015-01-01

Tmore » he effect of calcium chloride (CaCl 2 ) on tricalcium silicate (C 3 S) hydration was investigated by scanning transmission X-ray microscopy (SXM) with Near Edge X-ray Absorption Fine Structure (NEXAFS) spectra and 29 Si MAS NMR. SXM is demonstrated to be a powerful tool for studying the chemical composition of a cement-based hydration system. he Ca L 3,2 -edge NEXAFS spectra obtained by examining C 3 S hydration in the presence of CaCl 2 showed that this accelerator does not change the coordination of calcium in the calcium silicate hydrate (C-S-H), which is the primary hydration product. O K-edge NEXAFS is also very useful in distinguishing the chemical components in hydrated C 3 S. Based on the Ca L 3,2 -edge spectra and chemical component mapping, we concluded that CaCl 2 prefers to coexist with unhydrated C 3 S instead of C-S-H. In Si K-edge NEXAFS analysis, CaCl 2 increases the degree of silicate polymerization of C-S-H in agreement with the 29 Si CP/MAS NMR results, which show that the presence of CaCl 2 in hydrated C 3 S considerably accelerates the formation of middle groups ( Q 2 ) and branch sites ( Q 3 ) in the silicate chains of C-S-H gel at 1-day hydration.« less

Confined Water in Layered Silicates: The Origin of Anomalous Thermal Expansion Behavior in Calcium-Silicate-Hydrates

DOE PAGES

Krishnan, N. M. Anoop; Wang, Bu; Falzone, Gabriel; ...

2016-12-06

Water, under conditions of nanoscale confinement, exhibits anomalous dynamics, and enhanced thermal deformations, which may be further enhanced when such water is in contact with hydrophilic surfaces. Such heightened thermal deformations of water could control the volume stability of hydrated materials containing nanoconfined structural water. Understanding and predicting the thermal deformation coefficient (TDC, often referred to as the CTE, coefficient of thermal expansion), which represents volume changes induced in materials under conditions of changing temperature, is of critical importance for hydrated solids including: hydrogels, biological tissues, and calcium silicate hydrates, as changes in their volume can result in stress development,more » and cracking. By pioneering atomistic simulations, we examine the physical origin of thermal expansion in calcium-silicate-hydrates (C–S–H), the binding agent in concrete that is formed by the reaction of cement with water. We report that the TDC of C–S–H shows a sudden increase when the CaO/SiO 2 (molar ratio; abbreviated as Ca/Si) exceeds 1.5. This anomalous behavior arises from a notable increase in the confinement of water contained in the C–S–H’s nanostructure. We identify that confinement is dictated by the topology of the C–S–H’s atomic network. Altogether, the results suggest that thermal deformations of hydrated silicates can be altered by inducing compositional changes, which in turn alter the atomic topology and the resultant volume stability of the solids.« less

Modeling Nanomechanical Behavior of Calcium-Silicate-Hydrate

DTIC Science & Technology

2012-08-01

applicability to hardened pastes of tricalcium silicate, Portland cement, and blends of Portland cement with blast-furnace slag , metakaolin, or silica...Hydrated Nanocomposites: Concrete, Bone, and Shale. J. Am. Ceram . Soc., 90(9): 2677-2692. Wu, Jianzhong. and John M. Prausnitz. 2002. Generalizations for

CURRENT STATUS OF ADVACATE PROCESS FOR FLUE GAS DESULFURIZATION

EPA Science Inventory

The following report discusses current bench- and pilot-plant advances in preparation of ADVAnced siliCATE (ADVACATE) calcium silicate sorbentsfor flue gas desulfurization. It also discusses current bench- and pilot-plant advances in sorbent preparation. Fly ash was ground in a l...

Addition of a Fluoride-containing Radiopacifier Improves Micromechanical and Biological Characteristics of Modified Calcium Silicate Cements.

PubMed

Antonijevic, Djordje; Jeschke, Anke; Colovic, Bozana; Milovanovic, Petar; Jevremovic, Danimir; Kisic, Danilo; vom Scheidt, Annika; Hahn, Michael; Amling, Michael; Jokanovic, Vukoman; Busse, Björn; Djuric, Marija

2015-12-01

Calcium silicate cements (CSCs) with the addition of nanohydroxyapatite and calcium carbonate play a critical role in dental applications. To further improve their properties, particularly radiopacity and biointeractivity, the fluoride-containing radiopacifier ytterbium trifluoride (YbF3) was added to their composition, and biological and mechanical characteristics were evaluated. YbF3 was added to 3 different CSCs: cement I (CSC + calcium carbonate), cement II (CSC + nanohydroxyapatite), and Portland cement. Material characterization encompassed measurements of pH, calcium, ytterbium, and fluoride ion release; radiopacity; setting time; porosity; microindentation properties; wettability; and Fourier transform infrared spectroscopic, x-ray diffraction, and scanning electron microscopic analyses. Osteoblast- and osteoclast-like cells were grown on the materials' surface to evaluate their adherence. The addition of calcium carbonate, nanohydroxyapatite, and 30 wt% of YbF3 improved radiopacity and the setting time of experimental cements. The pH values did not differ among the groups. The greatest ytterbium and fluoride releases occurred in the Portland cement + YbF3 group. Combined x-ray diffraction and Fourier transform infrared spectroscopic analysis showed the presence of calcium hydroxide and calcium silicate hydrates. In addition, the presence of calcium ytterbium fluoride and ytterbium oxide proved that YbF3 reacted with cement compounds. Wettability of cement I + YbF3 was superior to other formulations, but its porosity and microindentation properties were weaker than in the Portland cement + YbF3 mixture. Cement II + YbF3 presented micromechanical indentation and porosity characteristics similar to the Portland-based cement formulation. Osteoclast- and osteoblast-like cells adhered to the cements' surfaces without alteration of the cell structural integrity. YbF3-containing CSCs with nanostructured hydroxyapatite and calcium carbonate are well suited for dental application. Copyright © 2015 American Association of Endodontists. Published by Elsevier Inc. All rights reserved.

A novel sol-gel-derived calcium silicate cement with short setting time for application in endodontic repair of perforations

PubMed Central

Lee, Bor-Shiunn; Lin, Hong-Ping; Chan, Jerry Chun-Chung; Wang, Wei-Chuan; Hung, Ping-Hsuan; Tsai, Yu-Hsin; Lee, Yuan-Ling

2018-01-01

Mineral trioxide aggregate (MTA) is the most frequently used repair material in endodontics, but the long setting time and reduced mechanical strength in acidic environments are major shortcomings. In this study, a novel sol-gel-derived calcium silicate cement (sCSC) was developed using an initial Ca/Si molar ratio of 3, with the most effective mixing orders of reactants and optimal HNO3 catalyst volumes. A Fourier transform infrared spectrometer, scanning electron microscope with energy-dispersive X-ray spectroscopy, and X-ray powder diffractometer were used for material characterization. The setting time, compressive strength, and microhardness of sCSC after hydration in neutral and pH 5 environments were compared with that of MTA. Results showed that sCSC demonstrated porous microstructures with a setting time of ~30 min, and the major components of sCSC were tricalcium silicate, dicalcium silicate, and calcium oxide. The optimal formula of sCSC was sn200, which exhibited significantly higher compressive strength and microhardness than MTA, irrespective of neutral or pH 5 environments. In addition, both sn200 and MTA demonstrated good biocompatibility because cell viability was similar to that of the control. These findings suggest that sn200 merits further clinical study for potential application in endodontic repair of perforations. PMID:29386894

A novel sol-gel-derived calcium silicate cement with short setting time for application in endodontic repair of perforations.

PubMed

Lee, Bor-Shiunn; Lin, Hong-Ping; Chan, Jerry Chun-Chung; Wang, Wei-Chuan; Hung, Ping-Hsuan; Tsai, Yu-Hsin; Lee, Yuan-Ling

2018-01-01

Mineral trioxide aggregate (MTA) is the most frequently used repair material in endodontics, but the long setting time and reduced mechanical strength in acidic environments are major shortcomings. In this study, a novel sol-gel-derived calcium silicate cement (sCSC) was developed using an initial Ca/Si molar ratio of 3, with the most effective mixing orders of reactants and optimal HNO 3 catalyst volumes. A Fourier transform infrared spectrometer, scanning electron microscope with energy-dispersive X-ray spectroscopy, and X-ray powder diffractometer were used for material characterization. The setting time, compressive strength, and microhardness of sCSC after hydration in neutral and pH 5 environments were compared with that of MTA. Results showed that sCSC demonstrated porous microstructures with a setting time of ~30 min, and the major components of sCSC were tricalcium silicate, dicalcium silicate, and calcium oxide. The optimal formula of sCSC was sn200, which exhibited significantly higher compressive strength and microhardness than MTA, irrespective of neutral or pH 5 environments. In addition, both sn200 and MTA demonstrated good biocompatibility because cell viability was similar to that of the control. These findings suggest that sn200 merits further clinical study for potential application in endodontic repair of perforations.

Effect of tetracalcium phosphate/monetite toothpaste on dentin remineralization and tubule occlusion in vitro.

PubMed

Medvecky, L; Stulajterova, R; Giretova, M; Mincik, J; Vojtko, M; Balko, J; Briancin, J

2018-03-01

To investigate the tubule occlusion and remineralization potential of a novel toothpaste with active tetracalcium phosphate/monetite mixtures under de/remineralization cycling. Dentin de/remineralization cycling protocol consisted of demineralization in 1% citric acid at pH 4.6 with following remineralization with toothpastes and soaking in artificial saliva. Effectiveness of toothpastes to promote remineralization was evaluated by measurement of microhardness recovery, analysis of surface roughness, thickness of coating and scanning electron microscopy. The novel tetracalcium phosphate/monetite dentifrice had comparable remineralization potential as commercial calcium silicate/phosphate (SENSODYNE ® ) and magnesium aluminum silicate (Colgate ® ) toothpastes and significantly higher than control saliva (p<0.02). Surface roughness was significantly lower after treatment with prepared and SENSODYNE ® dentifirice (p<0.05). The coatings on dentin surfaces was significantly thicker after applying toothpastes as compared to negative control (p<0.001). The new fluoride toothpaste formulation with bioactive tetracalcium phosphate/monetite calcium phosphate mixture effectively occluded dentin tubules and showed good dentin remineralization potential under de/remineralization cycling. It could replace professional powder preparation based on this mixture. It was demonstrated that prepared dentifrice had comparable properties with commercial fluoride calcium silicate/phosphate or magnesium aluminum silicate dentifrices. Copyright © 2017 The Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Stable prenucleation mineral clusters are liquid-like ionic polymers

PubMed Central

Demichelis, Raffaella; Raiteri, Paolo; Gale, Julian D.; Quigley, David; Gebauer, Denis

2011-01-01

Calcium carbonate is an abundant substance that can be created in several mineral forms by the reaction of dissolved carbon dioxide in water with calcium ions. Through biomineralization, organisms can harness and control this process to form various functional materials that can act as anything from shells through to lenses. The early stages of calcium carbonate formation have recently attracted attention as stable prenucleation clusters have been observed, contrary to classical models. Here we show, using computer simulations combined with the analysis of experimental data, that these mineral clusters are made of an ionic polymer, composed of alternating calcium and carbonate ions, with a dynamic topology consisting of chains, branches and rings. The existence of a disordered, flexible and strongly hydrated precursor provides a basis for explaining the formation of other liquid-like amorphous states of calcium carbonate, in addition to the non-classical behaviour during growth of amorphous calcium carbonate. PMID:22186886

Effects of Incorporating High-Volume Fly Ash into Tricalcium Silicate on the Degree of Silicate Polymerization and Aluminum Substitution for Silicon in Calcium Silicate Hydrate

DOE PAGES

Bae, Sungchul; Taylor, Rae; Kilcoyne, David; ...

2017-02-04

This study assesses the quantitative effects of incorporating high-volume fly ash (HVFA) into tricalcium silicate (C 3S) paste on the hydration, degree of silicate polymerization, and Al substitution for Si in calcium silicate hydrate (C–S–H). Thermogravimetric analysis and isothermal conduction calorimetry showed that, although the induction period of C 3S hydration was significantly extended, the degree of hydration of C 3S after the deceleration period increased due to HVFA incorporation. Synchrotron-sourced soft X-ray spectromicroscopy further showed that most of the C 3S in the C 3S-HVFA paste was fully hydrated after 28 days of hydration, while that in the puremore » C 3S paste was not. The chemical shifts of the Si K edge peaks in the near-edge X-ray fine structure of C–S–H in the C 3S-HVFA paste directly indicate that Al substitutes for Si in C–S–H and that the additional silicate provided by the HVFA induces an enhanced degree of silicate polymerization. This new spectromicroscopic approach, supplemented with 27Al and 29Si magic-angle spinning nuclear magnetic resonance spectroscopy and transmission electron microscopy, turned out to be a powerful characterization tool for studying a local atomic binding structure of C–S–H in C 3S-HVFA system and presented results consistent with previous literature.« less

Effects of Incorporating High-Volume Fly Ash into Tricalcium Silicate on the Degree of Silicate Polymerization and Aluminum Substitution for Silicon in Calcium Silicate Hydrate

PubMed Central

Bae, Sungchul; Taylor, Rae; Kilcoyne, David; Moon, Juhyuk; Monteiro, Paulo J. M.

2017-01-01

This study assesses the quantitative effects of incorporating high-volume fly ash (HVFA) into tricalcium silicate (C3S) paste on the hydration, degree of silicate polymerization, and Al substitution for Si in calcium silicate hydrate (C–S–H). Thermogravimetric analysis and isothermal conduction calorimetry showed that, although the induction period of C3S hydration was significantly extended, the degree of hydration of C3S after the deceleration period increased due to HVFA incorporation. Synchrotron-sourced soft X-ray spectromicroscopy further showed that most of the C3S in the C3S-HVFA paste was fully hydrated after 28 days of hydration, while that in the pure C3S paste was not. The chemical shifts of the Si K edge peaks in the near-edge X-ray fine structure of C–S–H in the C3S-HVFA paste directly indicate that Al substitutes for Si in C–S–H and that the additional silicate provided by the HVFA induces an enhanced degree of silicate polymerization. This new spectromicroscopic approach, supplemented with 27Al and 29Si magic-angle spinning nuclear magnetic resonance spectroscopy and transmission electron microscopy, turned out to be a powerful characterization tool for studying a local atomic binding structure of C–S–H in C3S-HVFA system and presented results consistent with previous literature. PMID:28772490

Effects of Incorporating High-Volume Fly Ash into Tricalcium Silicate on the Degree of Silicate Polymerization and Aluminum Substitution for Silicon in Calcium Silicate Hydrate

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

Bae, Sungchul; Taylor, Rae; Kilcoyne, David

This study assesses the quantitative effects of incorporating high-volume fly ash (HVFA) into tricalcium silicate (C 3S) paste on the hydration, degree of silicate polymerization, and Al substitution for Si in calcium silicate hydrate (C–S–H). Thermogravimetric analysis and isothermal conduction calorimetry showed that, although the induction period of C 3S hydration was significantly extended, the degree of hydration of C 3S after the deceleration period increased due to HVFA incorporation. Synchrotron-sourced soft X-ray spectromicroscopy further showed that most of the C 3S in the C 3S-HVFA paste was fully hydrated after 28 days of hydration, while that in the puremore » C 3S paste was not. The chemical shifts of the Si K edge peaks in the near-edge X-ray fine structure of C–S–H in the C 3S-HVFA paste directly indicate that Al substitutes for Si in C–S–H and that the additional silicate provided by the HVFA induces an enhanced degree of silicate polymerization. This new spectromicroscopic approach, supplemented with 27Al and 29Si magic-angle spinning nuclear magnetic resonance spectroscopy and transmission electron microscopy, turned out to be a powerful characterization tool for studying a local atomic binding structure of C–S–H in C 3S-HVFA system and presented results consistent with previous literature.« less

Mineralogical composition of boiler fouling and slagging deposits and their relation to fly ashes: the case of Kardia power plant.

PubMed

Kostakis, George

2011-01-30

Slagging and fouling deposits from a pulverized lignite fired steam generating unit of the Kardia power plant (West Macedonia, Greece) were mineralogically investigated. The structure and cohesion of these deposits varied, usually depending on the level height of the boiler unit where they were formed. Some of the deposits had complex phase composition. The dominant components of the deposits of the burner zone and of the lower and intermediate boiler zones were the amorphous, anhydrite and hematite, while those of the highest levels contained amorphous, and anhydrite. Furthermore, in deposits formed in various other boiler areas gehlenite, anorthite, diopside, quartz, Ca(2)SiO(4), brownmillerite and other crystalline phases were also identified, usually in low amounts or in traces. The major part of the phases constituting the deposits were formed in the boiler, since only a minor part derived from the unreacted minerals present in lignite. Anhydrite was generated from the reaction of SO(2) with CaO formed mainly by the calcination of calcite as well as from dehydration of gypsum contained in lignite, while hematite was produced mainly from the oxidation of pyrite. The calcium-containing silicates formed in the boiler were mainly the products of reactions between CaO and minerals contained in the lignite. Copyright © 2010 Elsevier B.V. All rights reserved.

The Effect of Specific Surface Area of Chitin-Metal Silicate Coprocessed Excipient on the Chemical Decomposition of Cefotaxime Sodium.

PubMed

Al-Nimry, Suhair S; Alkhamis, Khouloud A; Alzarieni, Kawthar Z

2017-02-01

Chitin-metal silicates are multifunctional excipients used in tablets. Previously, a correlation between the surface acidity of chitin-calcium and chitin-magnesium silicate and the chemical decomposition of cefotaxime sodium was found but not with chitin-aluminum silicate. This lack of correlation could be due to the catalytic effect of silica alumina or the difference in surface area of the excipients. The objective of this study was to investigate the effect of the specific surface area of the excipient on the chemical decomposition of cefotaxime sodium in the solid state. Chitin was purified and coprocessed with different metal silicates to prepare the excipients. The specific surface area was determined using gas adsorption. The chemical decomposition was studied at constant temperature and relative humidity. Also, the degradation in solution was studied. A correlation was found between the degradation rate constant and the surface area of chitin-aluminum and chitin-calcium silicate but not with chitin-magnesium silicate. This was due to the small average pore diameter of this excipient. Also, the degradation in solution was slower than in solid state. In conclusion, the stability of cefotaxime sodium was dependent on the surface area of the excipient in contact with the drug. Copyright © 2017 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

Disappearance of 19P/Borrelly's Silicate Feature in 2001 Apparition Is Attributed to Increase in Grain Size

NASA Technical Reports Server (NTRS)

Wooden, D. H.; Woodward, C. E.; Harker, D. E.

2002-01-01

We report on observations and analysis of HIFOGS 10 microns spectrophotometry of short period comet 19P/Borrelly on 2003 October 13, 15 UT at the NASA IRTF. 19P/Borrelly is one of two short period comets, comet 4PIFaye being the other, to have a silicate feature detected. During Borrelly s perihelion passage in 1994 December, a silicate feature was present with a flux-to-continuum ratio of 0.25. Two apparitions later in 2003 October, the silicate feature is absent. Thermal emission modeling using amorphous olivine and amorphous carbon shows that a slight increase in grain size accounts for the disappearance of the silicate feature. Analysis of 19P/Borrelly suggests grain size, and not the absence of olivine minerals, may be responsible for the absence of silicate features in most short period comets. 19P/Borrelly is one of the more active short period comets. However, short period comets as a family are less active than long period comets. Short period comets probably originated in the Kuiper Belt and suffered collisions while in residence in the outer solar system. Upon evolution into orbits that take them through the inner solar system, the surfaces of short period comets are exposed to sunlight through their many perihelion passages. This is in contrast to long period comets which probably originated near Jupiter and were expelled to the Oort cloud where they have existed and been exposed to cosmic ray processing. By studying the grain properties in short period comets and comparing to long period comets, we compare the effects on the grain populations of different parent body evolution histories. Upcoming opportunities to study short and long period comets will be advertised.

Interstellar silicate dust in the z = 0.685 absorber toward TXS 0218+357

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

Aller, Monique C.; Kulkarni, Varsha P.; Liger, Nicholas

2014-04-10

We report the detection of interstellar silicate dust in the z {sub abs} = 0.685 absorber along the sightline toward the gravitationally lensed blazar TXS 0218+357. Using Spitzer Space Telescope Infrared Spectrograph data, we detect the 10 μm silicate absorption feature with a detection significance of 10.7σ. We fit laboratory-derived silicate dust profile templates obtained from the literature to the observed 10 μm absorption feature and find that the best single-mineral fit is obtained using an amorphous olivine template with a measured peak optical depth of τ{sub 10} = 0.49 ± 0.02, which rises to τ{sub 10} ∼ 0.67 ±more » 0.04 if the covering factor is taken into account. We also detected the 18 μm silicate absorption feature in our data with a >3σ significance. Due to the proximity of the 18 μm absorption feature to the edge of our covered spectral range, and associated uncertainty about the shape of the quasar continuum normalization near 18 μm, we do not independently fit this feature. We find, however, that the shape and depth of the 18 μm silicate absorption are well matched to the amorphous olivine template prediction, given the optical depth inferred for the 10 μm feature. The measured 10 μm peak optical depth in this absorber is significantly higher than those found in previously studied quasar absorption systems. However, the reddening, 21 cm absorption, and velocity spread of Mg II are not outliers relative to other studied absorption systems. This high optical depth may be evidence for variations in dust grain properties in the interstellar medium between this and the previously studied high redshift galaxies.« less

Calcium silicate hydrates: Solid and liquid phase composition

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

Lothenbach, Barbara, E-mail: Barbara.lothenbach@empa.ch; Nonat, André

This paper presents a review on the relationship between the composition, the structure and the solution in which calcium silicate hydrate (C–S–H) is equilibrated. The silica chain length in C–S–H increases with the silicon concentration and the calcium content in the interlayer space with the calcium concentrations. Sodium and potassium are taken up in the interlayer space, preferentially at low calcium concentrations and thus by low Ca/Si C–S–H. Aluminium uptake in C–S–H increases strongly at higher aluminium concentrations in the solution. At low Ca/Si, aluminium substitutes silica in the bridging position, at Ca/Si > 1 aluminium is bound in TAH.more » Recently developed thermodynamic models are closely related to the structure of C–S–H and tobermorite, and able to model not only the solubility and the chemical composition of the C–S–H, but also to predict the mean silica chain length and the uptake of aluminium.« less

Metastable Eutectic Equilibrium in Natural Environments: Recent Developments and Research Opportunities

NASA Technical Reports Server (NTRS)

Rietmeijer, Fans J. M.; Nuth, Joseph A., II; Jablonska, Mariola; Karner, James M.

2000-01-01

Chemical ordering at metastable eutectics was recognized in non-equilibrium gas-to- solid condensation experiments to constrain 'silicate' dust formation in O-rich circumstellar environments. The predictable metastable eutectic behavior successfully predicted the observed ferromagnesiosilica, compositions of circumstellar dust, presolar and solar nebula grains in the matrix of the collected aggregate IDPs. Many of the experimentally determined metastable eutectic solids match the fundamental building blocks of common rock-forming layer silicates: this could have implications for the origin of Life. The physical conditions conducive to metastable eutectic behavior, i.e. high temperature and (ultra)fast quenching, lead to unique amorphous, typically nano- to micrometer-sized, materials. The new paradigm of metastable eutectic behavior opens the door to new and exciting research opportunities in uncovering the many implications of these unique amorphous and typically nano- to micrometer-sized, metastable eutectic materials.

The mineralogy of newly formed dust in active galactic nuclei

NASA Astrophysics Data System (ADS)

Srinivasan, Sundar; Kemper, F.; Zhou, Yeyan; Hao, Lei; Gallagher, Sarah C.; Shangguan, Jinyi; Ho, Luis C.; Xie, Yanxia; Scicluna, Peter; Foucaud, Sebastien; Peng, Rita H. T.

2017-12-01

The tori around active galactic nuclei (AGN) are potential formation sites for large amounts of dust, and they may help resolve the so-called dust budget crisis at high redshift. We investigate the dust composition in 53 of the 87 Palomar Green (PG) quasars showing the 9.7 μm silicate feature in emission. By simultaneously fitting the mid-infrared spectroscopic features and the underlying continuum, we estimate the mass fraction in various amorphous and crystalline dust species. We find that the dust consists predominantly of alumina and amorphous silicates, with a small fraction in crystalline form. The mean crystallinity is 8 ±6%, with more than half of the crystallinities greater than 5%, well above the upper limit determined for the Galaxy. Higher values of crystallinity are found for higher oxide fractions and for more luminous sources.

Tooth Discoloration Induced by Different Calcium Silicate-based Cements: A Systematic Review of In Vitro Studies.

PubMed

Możyńska, Joanna; Metlerski, Marcin; Lipski, Mariusz; Nowicka, Alicja

2017-10-01

On the basis of many clinical observations, some calcium silicate-based cements have a high potential for staining tooth tissue. This feature greatly limits the use of those cements, particularly for anterior teeth. This review aimed to provide a systematic evaluation of published in vitro studies to determine the effect of different calcium silicate-based cements on dental tissue discoloration. This literature review was developed according to the Preferred Reporting Items for Systematic Reviews and Meta-Analyses statement. The literature search was based on all publications without a year limit. The last search was performed on October 22, 2016. An electronic search was performed on MEDLINE (PubMed), Cochrane, and Scopus. The articles were selected to address the following research question: Which materials based on calcium silicate-based cements have hard tissue staining potential? The necessary information was extracted by 2 authors independently using a standardized form. The search resulted in 390 titles from all databases. Twenty-three studies met the inclusion criteria. Most of the studies exhibited a moderate risk of bias. The results indicated that some materials showed a strong potential for staining, including gray and white MTA Angelus (Londrina, PR, Brazil), gray and white ProRoot MTA (Dentsply, Tulsa, OK), and Ortho MTA (BioMTA, Seoul, Korea). Individual study results showed that Biodentine (Septodont, Saint Maur des Fosses, France), Retro MTA (BioMTA), Portland cement, EndoSequence Root Repair Material (Brasseler USA, Savannah, GA), Odontocem (Australian Dental Manufacturing, Brisbane, Australia), MM-MTA (Micro Mega, Besancon Cedex, France), and MTA Ledermix (Riemser Pharma GmbH, Greiswald-Insel Riems, Germany) were materials with the smallest staining potential. This review clearly showed that some calcium silicate-based cements have a high potential for staining hard tissue. On the other hand, some showed only a small change in color, which was nearly invisible to the human eye (ΔE <3.3). However, more long-term clinical studies are needed. Copyright © 2017 American Association of Endodontists. Published by Elsevier Inc. All rights reserved.

Kinetics of apatite formation on a calcium-silicate cement for root-end filling during ageing in physiological-like phosphate solutions.

PubMed

Gandolfi, Maria Giovanna; Taddei, Paola; Tinti, Anna; De Stefano Dorigo, Elettra; Rossi, Piermaria Luigi; Prati, Carlo

2010-12-01

The bioactivity of calcium silicate mineral trioxide aggregate (MTA) cements has been attributed to their ability to produce apatite in presence of phosphate-containing fluids. This study evaluated surface morphology and chemical transformations of an experimental accelerated calcium-silicate cement as a function of soaking time in different phosphate-containing solutions. Cement discs were immersed in Dulbecco's phosphate-buffered saline (DPBS) or Hank's balanced salt solution (HBSS) for different times (1-180 days) and analysed by scanning electron microscopy connected with an energy dispersive X-ray analysis (SEM-EDX) and micro-Raman spectroscopy. SEM-EDX revealed Ca and P peaks after 14 days in DPBS. A thin Ca- and P-rich crystalline coating layer was detected after 60 days. A thicker multilayered coating was observed after 180 days. Micro-Raman disclosed the 965-cm(-1) phosphate band at 7 days only on samples stored in DPBS and later the 590- and 435-cm(-1) phosphate bands. After 60-180 days, a layer approximately 200-900 μm thick formed displaying the bands of carbonated apatite (at 1,077, 965, 590, 435 cm(-1)) and calcite (at 1,088, 713, 280 cm(-1)). On HBSS-soaked, only calcite bands were observed until 90 days, and just after 180 days, a thin apatite-calcite layer appeared. Micro-Raman and SEM-EDX demonstrated the mineralization induction capacity of calcium-silicate cements (MTAs and Portland cements) with the formation of apatite after 7 days in DPBS. Longer time is necessary to observe bioactivity when cements are immersed in HBSS.

Cytotoxicity and Bioactivity of Calcium Silicate Cements Combined with Niobium Oxide in Different Cell Lines.

PubMed

Mestieri, Leticia Boldrin; Gomes-Cornélio, Ana Lívia; Rodrigues, Elisandra Márcia; Faria, Gisele; Guerreiro-Tanomaru, Juliane Maria; Tanomaru-Filho, Mário

2017-01-01

The aim of this study was to evaluate the cytotoxicity and bioactivity of calcium silicate-based cements combined with niobium oxide (Nb2O5) micro and nanoparticles, comparing the response in different cell lines. This evaluation used four cell lines: two primary cultures (human dental pulp cells - hDPCs and human dental follicle cells - hDFCs) and two immortalized cultures (human osteoblast-like cells - Saos-2 and mouse periodontal ligament cells - mPDL). The tested materials were: White Portland Cement (PC), mineral trioxide aggregate (MTA), white Portland cement combined with microparticles (PC/Nb2O5µ) or nanoparticles (PC/Nb2O5n) of niobium oxide (Nb2O5). Cytotoxicity was evaluated by the methylthiazolyldiphenyl-tetrazolium bromide (MTT) and trypan blue exclusion assays and bioactivity by alkaline phosphatase (ALP) enzyme activity. Results were analyzed by ANOVA and Tukey test (a=0.05). PC/Nb2O5n presented similar or higher cell viability than PC/Nb2O5µ in all cell lines. Moreover, the materials presented similar or higher cell viability than MTA. Saos-2 exhibited high ALP activity, highlighting PC/Nb2O5µ material at 7 days of exposure. In conclusion, calcium silicate cements combined with micro and nanoparticles of Nb2O5 presented cytocompatibility and bioactivity, demonstrating the potential of Nb2O5 as an alternative radiopacifier agent for these cements. The different cell lines had similar response to cytotoxicity evaluation of calcium silicate cements. However, bioactivity was more accurately detected in human osteoblast-like cell line, Saos-2.

Multi-Functions of Carbonated Calcium Deficient Hydroxyapatite (CDHA)

NASA Astrophysics Data System (ADS)

Zhou, Huan

Natural bone is a complex composite mainly constituted of inorganic minerals and organic collagen molecules. Calcium phosphate (CaP) based materials have been proposed as the predominant bone substitute for bone tissue engineering applications due to their chemical similarity to bone mineral. Amorphous carbonated calcium deficient hydroxyapatite (CDHA) is an important compound among CaP materials because of the amorphous crystallite structure. The presence of extra ions in its lattice structure not only influences cell attachment and proliferation of osteoblasts, but also helps in bone metabolism. Biomimetic coating approach is the most widely used approach to produce CDHA coatings to implant. It is a process using simulated body fluid (SBF) to deposit bone-like CDHA coating to various material surfaces. The CDHA formation mechanism, SBF compositions and reacting conditions of biomimetic coating have already been sufficiently studied and compared in the past 20 years. It is an attempt in this thesis to explore new applications of SBF in biomedical research, focusing on different biomaterial applications: 1) based on the low temperature reaction condition of SBF, bisphosphonate incorporated CDHA coatings were deposited onto Ti6Al4V surface for the treatment of osteoporosis; 2) amorphous calcium phosphate nanospheres with extra elements in the lattice structure were prepared by a novel microwave assisted approach, providing a new potential of CaP materials production; 3) CDHA particles formed in SBF can be used as great fillers with biopolymers for preparing biocomposites for biomedical applications; 4) based on the high activity of CDHA amorphous structure and the stabilization ability of ethanol, yttrium and europium doped calcium phosphates were prepared using CDHA as a sacrificing template. In the end, future work based on these observations in the thesis is addressed, including areas of drug delivery, biocomposite fabrication and preparation of functionalized calcium phosphate materials.

Drying-induced atomic structural rearrangements in sodium-based calcium-alumino-silicate-hydrate gel and the mitigating effects of ZrO 2 nanoparticles

DOE PAGES

Yang, Kengran; Özçelik, V. Ongun; Garg, Nishant; ...

2018-01-01

Drying-induced nanoscopic alterations to the local atomic structure of silicate-activated slag and the mitigated effects of nano-ZrO2 are elucidated using in situ X-ray pair distribution function analysis.

Drying-induced atomic structural rearrangements in sodium-based calcium-alumino-silicate-hydrate gel and the mitigating effects of ZrO 2 nanoparticles

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

Yang, Kengran; Özçelik, V. Ongun; Garg, Nishant

Drying-induced nanoscopic alterations to the local atomic structure of silicate-activated slag and the mitigated effects of nano-ZrO2 are elucidated using in situ X-ray pair distribution function analysis.

Mechanical and physical properties of calcium silicate/alumina composite for biomedical engineering applications.

PubMed

Shirazi, F S; Mehrali, M; Oshkour, A A; Metselaar, H S C; Kadri, N A; Abu Osman, N A

2014-02-01

The focus of this study is to investigate the effect of Al2O3 on α-calcium silicate (α-CaSiO3) ceramic. α-CaSiO3 was synthesized from CaO and SiO2 using mechanochemical method followed by calcinations at 1000°C. α-CaSiO3 and alumina were grinded using ball mill to create mixtures, containing 0-50w% of Al2O3 loadings. The powders were uniaxially pressed and followed by cold isostatic pressing (CIP) in order to achieve greater uniformity of compaction and to increase the shape capability. Afterward, the compaction was sintered in a resistive element furnace at both 1150°C and 1250°C with a 5h holding time. It was found that alumina reacted with α-CaSiO3 and formed alumina-rich calcium aluminates after sintering. An addition of 15wt% of Al2O3 powder at 1250°C were found to improve the hardness and fracture toughness of the calcium silicate. It was also observed that the average grain sizes of α-CaSiO3 /Al2O3 composite were maintained 500-700nm after sintering process. © 2013 Published by Elsevier Ltd.

Calcium carbonate precipitation by heterotrophic bacteria isolated from biofilms formed on deteriorated ignimbrite stones: influence of calcium on EPS production and biofilm formation by these isolates.

PubMed

López-Moreno, Angélica; Sepúlveda-Sánchez, José David; Mercedes Alonso Guzmán, Elia Mercedes; Le Borgne, Sylvie

2014-01-01

Heterotrophic CaCO3-precipitating bacteria were isolated from biofilms on deteriorated ignimbrites, siliceous acidic rocks, from Morelia Cathedral (Mexico) and identified as Enterobacter cancerogenus (22e), Bacillus sp. (32a) and Bacillus subtilis (52g). In solid medium, 22e and 32a precipitated calcite and vaterite while 52g produced calcite. Urease activity was detected in these isolates and CaCO3 precipitation increased in the presence of urea in the liquid medium. In the presence of calcium, EPS production decreased in 22e and 32a and increased in 52g. Under laboratory conditions, ignimbrite colonization by these isolates only occurred in the presence of calcium and no CaCO3 was precipitated. Calcium may therefore be important for biofilm formation on stones. The importance of the type of stone, here a siliceous stone, on biological colonization is emphasized. This calcium effect has not been reported on calcareous materials. The importance of the effect of calcium on EPS production and biofilm formation is discussed in relation to other applications of CaCO3 precipitation by bacteria.

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

Azam, Farah 'Atiqah bt Abdul; Shamsudin, Roslinda, E-mail: linda@ukm.edu.my

Calcium silicate bioceramic was prepared from the rice husk and limestone resources using the sol gel method. The preparations of CaSiO{sub 3} formulation were differ from the previous study due CaO/SiO{sub 2} amount with 45:55 ratio. X-Ray Fluorescence analysis was carried out to clarify the amount of SiO{sub 2} and CaO content in the limestone and rice husk ash. The high amount of CaO was found in the limestone with the percentages of 97.22%, whereby 89% of SiO{sub 2} content of the rice husk ash. Several milling time were studied to obtain the optimized milling ti me and speed inmore » progress to obtain nano size particle. The particle size analysis result confirms that increase in milling time does not certainly reduce the size of particle. The addition of 0.05% polyvinyl alcohol as a binder did not change the phases or composition of calcium silicates after examined by X-Ray diffraction analysis which make it suitable to be used as a binder for calcium silicate coating without changing the chemical structure.« less

Amorphous Calcium Carbonate Precipitation by Cellular Biomineralization in Mantle Cell Cultures of Pinctada fucata

PubMed Central

Xiang, Liang; Kong, Wei; Su, Jingtan; Liang, Jian; Zhang, Guiyou; Xie, Liping; Zhang, Rongqing

2014-01-01

The growth of molluscan shell crystals is generally thought to be initiated from the extrapallial fluid by matrix proteins, however, the cellular mechanisms of shell formation pathway remain unknown. Here, we first report amorphous calcium carbonate (ACC) precipitation by cellular biomineralization in primary mantle cell cultures of Pinctada fucata. Through real-time PCR and western blot analyses, we demonstrate that mantle cells retain the ability to synthesize and secrete ACCBP, Pif80 and nacrein in vitro. In addition, the cells also maintained high levels of alkaline phosphatase and carbonic anhydrase activity, enzymes responsible for shell formation. On the basis of polarized light microscopy and scanning electron microscopy, we observed intracellular crystals production by mantle cells in vitro. Fourier transform infrared spectroscopy and X-ray diffraction analyses revealed the crystals to be ACC, and de novo biomineralization was confirmed by following the incorporation of Sr into calcium carbonate. Our results demonstrate the ability of mantle cells to perform fundamental biomineralization processes via amorphous calcium carbonate, and these cells may be directly involved in pearl oyster shell formation. PMID:25405357

Mid-infrared spectra of cometary dust: the evasion of its silicate mineralogy

NASA Astrophysics Data System (ADS)

Kimura, H.; Chigai, T.; Yamamoto, T.

2008-04-01

Infrared spectra of dust in cometary comae provide a way to identify its silicate constituents, and this is crucial for correctly understanding the condition under which our planetary system is formed. Recent studies assign a newly detected peak at a wavelength of 9.3 μm to pyroxenes and regard them as the most abundant silicate minerals in comets. Here we dispense with this pyroxene hypothesis to numerically reproduce the infrared features of cometary dust in the framework of our interstellar dust models. Presolar interstellar dust in a comet is modeled as fluffy aggregates consisting of submicrometer-sized organic grains with an amorphous-silicate core that undergoes nonthermal crystallization in a coma. We assert that forsterite (Mg2SiO4) is the carrier of all the observed features, including the 9.3 μm peak and that the major phase of iron is sulfides rather than iron-rich silicates.

Ion-Doped Silicate Bioceramic Coating of Ti-Based Implant

PubMed Central

Mohammadi, Hossein; Sepantafar, Mohammadmajid

2016-01-01

Titanium and its alloy are known as important load-bearing biomaterials. The major drawbacks of these metals are fibrous formation and low corrosion rate after implantation. The surface modification of biomedical implants through various methods such as plasma spray improves their osseointegration and clinical lifetime. Different materials have been already used as coatings on biomedical implant, including calcium phosphates and bioglass. However, these materials have been reported to have limited clinical success. The excellent bioactivity of calcium silicate (Ca-Si) has been also regarded as coating material. However, their high degradation rate and low mechanical strength limit their further coating application. Trace element modification of (Ca-Si) bioceramics is a promising method, which improves their mechanical strength and chemical stability. In this review, the potential of trace element-modified silicate coatings on better bone formation of titanium implant is investigated. PMID:26979401

Techno - economic and leachability effect of Ca2SiO4 interlocking composite brick

NASA Astrophysics Data System (ADS)

Namboonruang, Weerapol; Yongam-nuai, Prayoon; Suphadon, Nutthanun

2017-07-01

This work studied the possibility to produce the new novel calcium silicate ceramic kiln ash composite brick (CSCACB) which was the combination of the local Ratchaburi soil and calcium silicate kiln ash (CSCA) wasted from the ceramic industry. The chemical and physical properties of the composite brick were investigated. Also, the mechanical properties such as the compressive strength, flexural strength and as well as the leachability property were determined. By summary, this invented materials has enough quality to produce as local commercial products considered by the strength properties, environmental effect, price and appropriated implementation.

The Surface Properties of Teeth Treated with Resin Infiltration or Amorphous Calcium Phosphate

DTIC Science & Technology

2012-05-04

properties of color stability and surface roughness of demineralized enamel treated with resin infiltration (ICON) or with casein phosphopeptide...amorphous calcium phosphate (MI Paste, CPP-ACP). Methods: Fifty human enamel blocks (4 x 4 mm2) were prepared. Each block was treated with 1M HCl (pH...and 5 (see Figure 2). Conclusion: The results of this study do not provide conclusive evidence that the standard of care for enamel

The determination of calcium in phosphate, carbonate, and silicate rocks by flame photometer

USGS Publications Warehouse

Kramer, Henry

1956-01-01

A method has been developed for the determination of calcium in phosphate, carbonate, and silicate rocks using the Beckman flame photometer, with photomultiplier attachement. The sample is dissolved in hydrofluoric, nitric, and perchloric acids, the hydrofluoric and nitric acids are expelled, a radiation buffer consisting of aluminum, magnesium, iron, sodium, potassium, phosphoric acid, and nitric acid is added, and the solution is atomized in an oxy-hydrogen flame with an instrument setting of 554 mµ. Measurements are made by comparison against calcium standards, prepared in the same manner, in the 0 to 50 ppm range. The suppression of calcium emission by aluminum and phosphate was overcome by the addition of a large excess of magnesium. This addition almost completely restores the standard curve obtained from a solution of calcium nitrate. Interference was noted when the iron concentration in the aspirated solution (including the iron from the buffer) exceeded 100 ppm iron. Other common rock-forming elements did not interfere. The results obtained by this procedure are within ± 2 percent of the calcium oxide values obtained by other methods in the range 1 to 95 percent calcium oxide. In the 0 to 1 percent calcium oxide range the method compares favorably with standard methods.

Amorphous manganese-calcium oxides as a possible evolutionary origin for the CaMn₄ cluster in photosystem II.

PubMed

Najafpour, Mohammad Mahdi

2011-06-01

In this paper a few calcium-manganese oxides and calcium-manganese minerals are studied as catalysts for water oxidation. The natural mineral marokite is also studied as a catalyst for water oxidation for the first time. Marokite is made up of edge-sharing Mn(3+) in a distorted octahedral environment and eight-coordinate Ca(2+) centered polyhedral layers. The structure is similar to recent models of the oxygen evolving complex in photosystem II. Thus, the oxygen evolving complex in photosystem II does not have an unusual structure and could be synthesized hydrothermally. Also in this paper, oxygen evolution is studied with marokite (CaMn₂O₄), pyrolusite (MnO₂) and compared with hollandite (Ba(0.2)Ca(0.15)K(0.3)Mn(6.9)Al(0.2)Si(0.3)O(16)), hausmannite (Mn₃O₄), Mn₂O₃.H₂O, Ca Mn₃O₆.H₂O, CaMn₄O₈.H₂O, CaMn₂O₄.H₂O and synthetic marokite (CaMn₂O₄). I propose that the origin of the oxygen evolving complex in photosystem II resulted from absorption of calcium and manganese ions that were precipitated together in the archean oceans by protocyanobacteria because of changing pH from ~5 to ~8-10. As reported in this paper, amorphous calcium-manganese oxides with different ratios of manganese and calcium are effective catalysts for water oxidation. The bond types and lengths of the calcium and manganese ions in the calcium-manganese oxides are directly comparable to those in the OEC. This primitive structure of these amorphous calcium-manganese compounds could be changed and modified by environmental groups (amino acids) to form the oxygen evolving complex in photosystem II.

TRANSIENT AMORPHOUS CALCIUM PHOSPHATE IN FORMING ENAMEL

PubMed Central

Beniash, Elia; Metzler, Rebecca A.; Lam, Raymond S.K.; Gilbert, P.U.P.A.

2009-01-01

Enamel, the hardest tissue in the body, begins as a three-dimensional network of nanometer size mineral particles, suspended in a protein gel. This mineral network serves as a template for mature enamel formation. To further understand the mechanisms of enamel formation we characterized the forming enamel mineral at an early secretory stage using x-ray absorption near-edge structure (XANES) spectromicroscopy, transmission electron microscopy (TEM), FTIR microspectroscopy and polarized light microscopy. We show that the newly formed enamel mineral is amorphous calcium phosphate (ACP), which eventually transforms into apatitic crystals. Interestingly, the size, shape and spatial organization of these amorphous mineral particles and older crystals are essentially the same, indicating that the mineral morphology and organization in enamel is determined prior to its crystallization. Mineralization via transient amorphous phases has been previously reported in chiton teeth, mollusk shells, echinoderm spicules and spines, and recent reports strongly suggest the presence transient amorphous mineral in forming vertebrate bones. The present finding of transient ACP in murine tooth enamel suggests that this strategy might be universal. PMID:19217943

Amorphous and crystalline calcium carbonate distribution in the tergite cuticle of moulting Porcellio scaber (Isopoda, Crustacea).

PubMed

Neues, Frank; Hild, Sabine; Epple, Matthias; Marti, Othmar; Ziegler, Andreas

2011-07-01

The main mineral components of the isopod cuticle consists of crystalline magnesium calcite and amorphous calcium carbonate. During moulting isopods moult first the posterior and then the anterior half of the body. In terrestrial species calcium carbonate is subject to resorption, storage and recycling in order to retain significant fractions of the mineral during the moulting cycle. We used synchrotron X-ray powder diffraction, elemental analysis and Raman spectroscopy to quantify the ACC/calcite ratio, the mineral phase distribution and the composition within the anterior and posterior tergite cuticle during eight different stages of the moulting cycle of Porcellio scaber. The results show that most of the amorphous calcium carbonate (ACC) is resorbed from the cuticle, whereas calcite remains in the old cuticle and is shed during moulting. During premoult resorption of ACC from the posterior cuticle is accompanied by an increase within the anterior tergites, and mineralization of the new posterior cuticle by resorption of mineral from the anterior cuticle. This suggests that one reason for using ACC in cuticle mineralization is to facilitate resorption and recycling of cuticular calcium carbonate. Furthermore we show that ACC precedes the formation of calcite in distal layers of the tergite cuticle. Copyright © 2011 Elsevier Inc. All rights reserved.

Experimental exploration of the hydrodynamic effect polishing machinability for different types of material

NASA Astrophysics Data System (ADS)

Peng, W. Q.; Li, Y.; Wang, Z.; Li, S. Y.

2018-01-01

Hydrodynamic effect polishing (HEP), in which the material removal relies on the chemisorption between nanoparticles and the workpiece surface in elastic mode, can realize automatic level smooth surface without surface/subsurface damage. The machinability of different types of optical material (such as monocrystalline silicon and crystalline quartz, amorphous silicate glass, Zerodur and so on) were investigated experimentally. The workpiece surfaces before and after being polished by HEP was observed by atomic force microscopy. The experimental results show the surface roughness of monocrystalline silicon and quartz, amorphous silicate glass have decreased from Rms 0.737nm to Rms 0.175nm, Rms 0.490nm to Rms 0.187nm, Rms 0.469nm to Rms 0.157nm respectively, and meanwhile all the defects and bumpy structures have been removed clearly. However the surface roughness has increased from Rms 0.213nm to Rms 0.321nm with the obvious increment of micro unevenness. By comparison, we can conclude that excellent performance is shown when HEP is applied on the optical material structure with a single monocrystalline or amorphous component. However the ultrasmooth surface cannot be obtained when HEP was applied on the combinational materials such as Zerodur glass. The micro unevenness increases gradually along with polishing process due to the different material removal of the monocrystalline and amorphous component.

Molding mineral within microporous hydrogels by a polymer-induced liquid-precursor (PILP) process.

PubMed

Cheng, Xingguo; Gower, Laurie B

2006-01-01

Natural biominerals often have exquisite morphologies, where the cells exercise a high degree of crystallographic control through secretion of biological macromolecules and regulation of ion transport. One important example is the sea urchin spine. It has recently been shown to be formed through deposition of a transient amorphous calcium carbonate (ACC) precursor phase that later transforms to single-crystalline calcite, ultimately forming an elaborate three-dimensional microporous calcium carbonate structure with interconnected pores. Macromolecules associated with the mineral phase are thought to play a key role in regulating this transformation. The work described here mimics this type of morphological control by "molding" an amorphous calcium carbonate precursor within a porous poly(2-hydroxyethyl methacrylate) (PHEMA) hydrogel that has been prepared as a negative replica from the void space of an urchin spine. Using an acidic biomimetic polymer as a process-directing agent, we show that polyaspartic acid induces amorphous calcium carbonate (ACC) nanoparticles, which have fluidic character and therefore are able to infiltrate the PHEMA hydrogel replica and coalesce into the convoluted morphology that replicates the original microporous structure of the sea urchin spine. By "molding" calcium carbonate into a complex morphology at room temperature, using a precursor process that is induced by a biomimetic acidic macromolecule, the PILP process is a useful in vitro model for examining different aspects of the amorphous-to-crystalline transformation process that is apparently used by a variety of biomineralizing organisms. For example, although we were able to replicate the overall morphology of the spine, it had polycrystalline texture; further studies with this system will focus on controlling the nucleation event, which may help to elucidate how such a convoluted structure can be prepared with single-crystalline texture via an amorphous precursor. Through a better understanding of the mechanisms used by organisms to regulate crystal properties, such biomimetic processes can lead to the synthesis of materials with superior electronic, mechanical, and optical properties.

Metastable Eutectic Equilibrium in Natural Environments: Recent Development and Research Opportunities

NASA Technical Reports Server (NTRS)

Rietmeijer, Frans J. M.; Nuth, Joseph A., III; Jablonska, Mariola; Karner, James M.

2000-01-01

Chemical ordering at metastable eutectics was recognized in non-equilibrium gas-to- solid condensation experiments to constrain 'silicate' dust formation in O-rich circumstellar environments. The predictable metastable eutectic behavior successfully predicted the observed ferromagnesiosilica compositions of circumstellar dust presolar and solar nebula grains in the matrix of the collected aggregate IDPs (Interplanetary Dust Particles). Many of the experimentally determined metastable eutectic solids match the fundamental building blocks of common rock-forming layer silicates: this could have implications for the origin of Life. The physical conditions conducive to metastable eutectic behavior, i.e. high temperature and (ultra) fast quenching, lead to unique amorphous, typically nano- to micrometer-sized, materials. The new paradigm of metastable eutectic behavior opens the door to new and exciting research opportunities in uncovering the many implications of these unique amorphous, and typically nano-to micrometer-sized, metastable eutectic materials.

Laboratory Annealing Experiments Of Refractory Silicate Grain Analogs Using Differential Scanning Calorimetry

NASA Technical Reports Server (NTRS)

Kimura, Yuki; Nuth, Joseph A., III; Tsukamota, Katsuo; Kaito, Chihiro

2010-01-01

Exothermic reactions during the annealing of laboratory synthesized amorphous magnesium-bearing silicate particles used as grain analogs of cosmic dust were detected by differential scanning calorimetry (DSC) in air. With infrared spectroscopy and transmission electron microscopy, we show that cosmic dust could possibly undergo fusion to larger particles, with oxidation of magnesium silicide and crystallization of forsterite as exothermic reactions in the early solar system. The reactions begin at approximately 425, approximately 625, and approximately 1000 K, respectively, and the reaction energies (enthalpies) are at least 727, 4151, and 160.22 J per gram, respectively. During the crystallization of forsterite particles, the spectral evolution of the 10 micrometer feature from amorphous to crystalline was observed to begin at lower temperature than the crystallization temperature of 1003 K. During spectral evolution at lower temperature, nucleation and/or the formation of nanocrystallites of forsterite at the surface of the grain analogs was observed.

Pseudowollastonite Carbonation Could Enable New Frontiers in Carbon Storage

NASA Astrophysics Data System (ADS)

Plattenberger, D.; Tao, Z.; Ling, F. T.; Peters, C. A.; Clarens, A. F.

2017-12-01

One of the primary challenges of CO2 mineral trapping is that precipitation reactions are reversible. A wide range of solid magnesium, iron, or calcium carbonates (such as magnesite, MgCO3) can be synthesized by reacting mineral silicates (such as olivine, Mg2SiO4) with CO2 to produce mineral carbonates. However, if CO2 remains present at high concentrations, as would be the case in many subsurface environments, the carbonate minerals could re-dissolve, making the precipitated carbonates impermanent forms of storage. In this work, we study pseudowollastonite (CaSiO3), a crystalline form of calcium silicate that is common in slags, cement, and calcium-rich volcanic formations, for its potential to produce other secondary mineral phases that may be resistant to dissolution under low pH conditions. These secondary mineral precipitation phases have morphologies and X-ray diffraction patterns that resemble both calcium silicate hydrate gels as well as crystalline calcium silicate carbonate hydrates. The combination of these phases forms a complex system that may resist acid attack while providing strength and limiting flow in the subsurface environment. High pressure and temperature column experiments carried out in our lab show that pseudowollastonite carbonation effectively lowers permeability in columns of sintered glass beads. Many of the pore throats are clogged by precipitates, as seen using micro X-ray tomography of intact columns and electron microscopy of thin sections. The spatial distribution of the products suggests that calcite forms toward the inlet of the columns where the pCO2 is highest. This forms a barrier that reduces, but does not eliminate, the availability of CO2 deeper in the porous media where the secondary phases precipitate. The existence of the calcite zone drives the reduction in permeability and the depth of this zone is self-limiting, which could have important implications for limiting leakage and unwanted migration of CO2 in some instances.

Physicochemical properties of calcium silicate-based formulations MTA Repair HP and MTA Vitalcem.

PubMed

Guimarães, Bruno Martini; Prati, Carlo; Duarte, Marco Antonio Hungaro; Bramante, Clovis Monteiro; Gandolfi, Maria Giovanna

2018-04-05

This study aimed to analyze the following physicochemical properties: radiopacity, final setting time, calcium release, pH change, solubility, water sorption, porosity, surface morphology, and apatite-forming ability of two calcium silicate-based materials. We tested MTA Repair HP and MTA Vitalcem in comparison with conventional MTA, analyzing radiopacity and final setting time. Water absorption, interconnected pores and apparent porosity were measured after 24-h immersion in deionized water at 37°C. Calcium and pH were tested up to 28 d in deionized water. We analyzed data using two-way ANOVA with Student-Newman-Keuls tests (p<0.05). We performed morphological and chemical analyses of the material surfaces using ESEM/EDX after 28 d in HBSS. MTA Repair HP showed similar radiopacity to that of conventional MTA. All materials showed a marked alkalinizing activity within 3 h, which continued for 28 d. MTA Repair HP showed the highest calcium release at 28 d (p<0.05). MTA Vitalcem showed statistically higher water sorption and solubility values (p<0.05). All materials showed the ability to nucleate calcium phosphate on their surface after 28 d in HBSS. MTA Repair HP and MTA Vitalcem had extended alkalinizing activity and calcium release that favored calcium phosphate nucleation. The presence of the plasticizer in MTA HP might increase its solubility and porosity. The radiopacifier calcium tungstate can be used to replace bismuth oxide.

Effect of Exposed Surface Area, Volume and Environmental pH on the Calcium Ion Release of Three Commercially Available Tricalcium Silicate Based Dental Cements.

PubMed

Rajasekharan, Sivaprakash; Vercruysse, Chris; Martens, Luc; Verbeeck, Ronald

2018-01-13

Tricalcium silicate cements (TSC) are used in dental traumatology and endodontics for their bioactivity which is mostly attributed to formation of calcium hydroxide during TSC hydration and its subsequent release of calcium and hydroxide ions. The aim of this study was to determine the effect of volume (Vol), exposed surface area (ESA) and pH of surrounding medium on calcium ion release. Three commercially available hydraulic alkaline dental cements were mixed and condensed into cylindrical tubes of varying length and diameter ( n = 6/group). For the effect of ESA and Vol, tubes were immersed in 10 mL of deionized water. To analyze the effect of environmental pH, the tubes were randomly immersed in 10 mL of buffer solutions with varying pH (10.4, 7.4 or 4.4). The solutions were collected and renewed at various time intervals. pH and/or calcium ion release was measured using a pH glass electrode and atomic absorption spectrophotometer respectively. The change of pH, short-term calcium ion release and rate at which calcium ion release reaches maximum were dependent on ESA ( p < 0.05) while maximum calcium ion release was dependent on Vol of TSC ( p < 0.05). Maximum calcium ion release was significantly higher in acidic solution followed by neutral and alkaline solution ( p < 0.05).

Effect of Exposed Surface Area, Volume and Environmental pH on the Calcium Ion Release of Three Commercially Available Tricalcium Silicate Based Dental Cements

PubMed Central

Rajasekharan, Sivaprakash; Vercruysse, Chris; Martens, Luc; Verbeeck, Ronald

2018-01-01

Tricalcium silicate cements (TSC) are used in dental traumatology and endodontics for their bioactivity which is mostly attributed to formation of calcium hydroxide during TSC hydration and its subsequent release of calcium and hydroxide ions. The aim of this study was to determine the effect of volume (Vol), exposed surface area (ESA) and pH of surrounding medium on calcium ion release. Three commercially available hydraulic alkaline dental cements were mixed and condensed into cylindrical tubes of varying length and diameter (n = 6/group). For the effect of ESA and Vol, tubes were immersed in 10 mL of deionized water. To analyze the effect of environmental pH, the tubes were randomly immersed in 10 mL of buffer solutions with varying pH (10.4, 7.4 or 4.4). The solutions were collected and renewed at various time intervals. pH and/or calcium ion release was measured using a pH glass electrode and atomic absorption spectrophotometer respectively. The change of pH, short-term calcium ion release and rate at which calcium ion release reaches maximum were dependent on ESA (p < 0.05) while maximum calcium ion release was dependent on Vol of TSC (p < 0.05). Maximum calcium ion release was significantly higher in acidic solution followed by neutral and alkaline solution (p < 0.05). PMID:29342837

Downstream processing of reverse osmosis brine: Characterisation of potential scaling compounds.

PubMed

Zaman, Masuduz; Birkett, Greg; Pratt, Christopher; Stuart, Bruce; Pratt, Steven

2015-09-01

Reverse osmosis (RO) brine produced at a full-scale coal seam gas (CSG) water treatment facility was characterized with spectroscopic and other analytical techniques. A number of potential scalants including silica, calcium, magnesium, sulphates and carbonates, all of which were present in dissolved and non-dissolved forms, were characterized. The presence of spherical particles with a size range of 10-1000 nm and aggregates of 1-10 microns was confirmed by transmission electron microscopy (TEM). Those particulates contained the following metals in decreasing order: K, Si, Sr, Ca, B, Ba, Mg, P, and S. Characterization showed that nearly one-third of the total silicon in the brine was present in the particulates. Further, analysis of the RO brine suggested supersaturation and precipitation of metal carbonates and sulphates during the RO process should take place and could be responsible for subsequently capturing silica in the solid phase. However, the precipitation of crystalline carbonates and sulphates are complex. X-ray diffraction analysis did not confirm the presence of common calcium carbonates or sulphates but instead showed the presence of a suite of complex minerals, to which amorphous silica and/or silica rich compounds could have adhered. A filtration study showed that majority of the siliceous particles were less than 220 nm in size, but could still be potentially captured using a low molecular weight ultrafiltration membrane. Copyright © 2015 Elsevier Ltd. All rights reserved.

Evaluation of the radiopacity of calcium silicate cements containing different radiopacifiers.

PubMed

Camilleri, J; Gandolfi, M G

2010-01-01

To identify the suitable ratio of alternative radiopacifiers to impart the necessary radiopacity to calcium silicate cements (CSC) and assess the purity of the radiopacifying agents. Alternative radiopacifying materials for incorporation into CSC included barium sulphate, titanium oxide, zinc oxide, gold powder and silver/tin alloy. The chemical composition of the alternative radipacifying materials and bismuth oxide, which is used in mineral trioxide aggregate (MTA), was determined using energy dispersive X-ray analysis. In addition, using an aluminium step-wedge and densitometer, the radiopacity of each material was evaluated as recommended by international standards. The optical density was compared with the relevant thickness of aluminium (Al). A commercial MTA and CSC were used as controls. Statistical analysis comparing the radiodensity of the different cements to MTA was performed using anova with P = 0.05 and post hoc Tukey test. All percentage replacements of bismuth oxide, gold and silver-tin alloy powder, and the 25% and 30% replacements with barium sulphate and zinc oxide had radiopacities greater than 3 mm thickness of aluminium (Al) recommended by ISO 6876 (2002). The 25% replacement of cement with gold powder and 20% replacement of cement with silver/tin alloy powder exhibited radiopacity values of 8.04 mm Al and 7.52 mm Al, respectively, similar to MTA (P > 0.05). The cement replaced with 20% bismuth oxide showed a radiopacity of 6.83 mm Al, lower than MTA (P = 0.003). Silver/tin alloy and gold powder imparted the necessary radiopacity to a calcium silicate-based cement. Barium sulphate was also a suitable radiopacifier together with a lower concentration of silver/tin alloy and gold powder that achieved the radiodensity recommended by ISO 6876. Further research is required to investigate the broader properties of the calcium silicate-based cement with the different radiopacifiers.

Capillarity creates single-crystal calcite nanowires from amorphous calcium carbonate.

PubMed

Kim, Yi-Yeoun; Hetherington, Nicola B J; Noel, Elizabeth H; Kröger, Roland; Charnock, John M; Christenson, Hugo K; Meldrum, Fiona C

2011-12-23

Single-crystal calcite nanowires are formed by crystallization of morphologically equivalent amorphous calcium carbonate (ACC) particles within the pores of track etch membranes. The polyaspartic acid stabilized ACC is drawn into the membrane pores by capillary action, and the single-crystal nature of the nanowires is attributed to the limited contact of the intramembrane ACC particle with the bulk solution. The reaction environment then supports transformation to a single-crystal product. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Amorphous calcium carbonate transforms into calcite during sea urchin larval spicule growth

PubMed Central

Beniash, E.; Aizenberg, J.; Addadi, L.; Weiner, S.

1997-01-01

Sea urchin larvae form an endoskeleton composed of a pair of spicules. For more than a century it has been stated that each spicule comprises a single crystal of the CaCO3 mineral, calcite. We show that an additional mineral phase, amorphous calcium carbonate, is present in the sea urchin larval spicule, and that this inherently unstable mineral transforms into calcite with time. This observation significantly changes our concepts of mineral formation in this well-studied organism.

Increased calcium absorption from synthetic stable amorphous calcium carbonate: double-blind randomized crossover clinical trial in postmenopausal women.

PubMed

Vaisman, Nachum; Shaltiel, Galit; Daniely, Michal; Meiron, Oren E; Shechter, Assaf; Abrams, Steven A; Niv, Eva; Shapira, Yami; Sagi, Amir

2014-10-01

Calcium supplementation is a widely recognized strategy for achieving adequate calcium intake. We designed this blinded, randomized, crossover interventional trial to compare the bioavailability of a new stable synthetic amorphous calcium carbonate (ACC) with that of crystalline calcium carbonate (CCC) using the dual stable isotope technique. The study was conducted in the Unit of Clinical Nutrition, Tel Aviv Sourasky Medical Center, Israel. The study population included 15 early postmenopausal women aged 54.9 ± 2.8 (mean ± SD) years with no history of major medical illness or metabolic bone disorder, excess calcium intake, or vitamin D deficiency. Standardized breakfast was followed by randomly provided CCC or ACC capsules containing 192 mg elemental calcium labeled with 44Ca at intervals of at least 3 weeks. After swallowing the capsules, intravenous CaCl2 labeled with 42Ca on was administered on each occasion. Fractional calcium absorption (FCA) of ACC and CCC was calculated from the 24-hour urine collection following calcium administration. The results indicated that FCA of ACC was doubled (± 0.96 SD) on average compared to that of CCC (p < 0.02). The higher absorption of the synthetic stable ACC may serve as a more efficacious way of calcium supplementation. © 2014 American Society for Bone and Mineral Research.

Long term mechanical properties of alkali activated slag

NASA Astrophysics Data System (ADS)

Zhu, J.; Zheng, W. Z.; Xu, Z. Z.; Leng, Y. F.; Qin, C. Z.

2018-01-01

This article reports a study on the microstructural and long-term mechanical properties of the alkali activated slag up to 180 days, and cement paste is studied as the comparison. The mechanical properties including compressive strength, flexural strength, axis tensile strength and splitting tensile strength are analyzed. The results showed that the alkali activated slag had higher compressive and tensile strength, Slag is activated by potassium silicate (K2SiO3) and sodium hydroxide (NaOH) solutions for attaining silicate modulus of 1 using 12 potassium silicate and 5.35% sodium hydroxide. The volume dosage of water is 35% and 42%. The results indicate that alkali activated slag is a kind of rapid hardening and early strength cementitious material with excellent long-term mechanical properties. Single row of holes block compressive strength, single-hole block compressive strength and standard solid brick compressive strength basically meet engineering requirements. The microstructures of alkali activated slag are studied by X-ray diffraction (XRD). The hydration products of alkali-activated slag are assured as hydrated calcium silicate and hydrated calcium aluminate.

Dental materials. Amorphous intergranular phases control the properties of rodent tooth enamel.

PubMed

Gordon, Lyle M; Cohen, Michael J; MacRenaris, Keith W; Pasteris, Jill D; Seda, Takele; Joester, Derk

2015-02-13

Dental enamel, a hierarchical material composed primarily of hydroxylapatite nanowires, is susceptible to degradation by plaque biofilm-derived acids. The solubility of enamel strongly depends on the presence of Mg(2+), F(-), and CO3(2-). However, determining the distribution of these minor ions is challenging. We show—using atom probe tomography, x-ray absorption spectroscopy, and correlative techniques—that in unpigmented rodent enamel, Mg(2+) is predominantly present at grain boundaries as an intergranular phase of Mg-substituted amorphous calcium phosphate (Mg-ACP). In the pigmented enamel, a mixture of ferrihydrite and amorphous iron-calcium phosphate replaces the more soluble Mg-ACP, rendering it both harder and more resistant to acid attack. These results demonstrate the presence of enduring amorphous phases with a dramatic influence on the physical and chemical properties of the mature mineralized tissue. Copyright © 2015, American Association for the Advancement of Science.

A new interpretation of Serkowski's polarization law

NASA Astrophysics Data System (ADS)

Papoular, R.

2018-06-01

The basic tenets of the alternative interpretation to be presented here are that the spectral profiles of the star light polarization peaks observed in the visible and near IR are a result of the optical properties of silicate grains in the same spectral range, not of the grain size, provided it remains within the range of Rayleigh's approximation. The silicate properties are those obtained experimentally by Scott and Duley (1996) for the non-iron bearing amorphous forsterite and enstatite. The whole range of observed Serkowski polarization profiles can be simulated with mixtures made of forsterite plus an increasing fraction (0 to 0.5) of enstatite as the spectral peak shifts from 0.8 to 0.3 μm. Fits to individual observed polarization spectra are also demonstrated. The optical extinction of silicates in the vis/IR (the "transparency range") can be understood by analogy with the thoroughly studied amorphous hydrogenated carbons and amorphous silica. It is due to structural disorder (dangling bonds and coordination defects) and impurities, which give rise to electronic states in the forbidden gap of semi-conductors. Because they are partially localized, their extinction power is dramatically reduced and has been ignored or simply described by a low, flat plateau. As their number density depends on the environment, one expects variations in the ratio of optical extinction coefficients in the visible and mid-IR. It is also argued that the measured steep rise of extinction beyond 3 μm-1 into the UV is due to atomic transitions, and so cannot give rise to coherent molecular polarization, but only localized extinction.

Calcium-Magnesium-Alumino-Silicates (CMAS) Reaction Mechanisms and Resistance of Advanced Turbine Environmental Barrier Coatings for SiC/SiC Ceramic Matrix Composites

NASA Technical Reports Server (NTRS)

Zhu, Dongming; Costa, Gustavo; Harder, Bryan J.; Wiesner, Valerie L.; Hurst, Janet B.; Puleo, Bernadette J.

2017-01-01

Environmental barrier coatings (EBCs) and SiC/SiC ceramic matrix composites (CMCs) systems will play a crucial role in future turbine engines for hot-section component applications because of their ability to significantly increase engine operating temperatures, reduce engine weight and cooling requirements. The development of prime-reliant environmental barrier coatings is an essential requirement to enable the applications of the 2700-3000 F EBC - CMC systems. This presentation primarily focuses on the reaction mechanisms of advanced NASA environmental barrier coating systems, when in contact with Calcium-Magnesium Alumino-Silicates (CMAS) at high temperatures. Advanced oxide-silicate defect cluster environmental barrier coatings are being designed for ultimate balanced controls of the EBC temperature capability and CMAS reactivity, thus improving the CMAS resistance. Further CMAS mitigation strategies are also discussed.

Ph-activated nano-amorphous calcium phosphate-based cement to reduce dental enamel demineralization.

PubMed

Melo, Mary A S; Weir, Michael D; Passos, Vanara F; Powers, Michael; Xu, Hockin H K

2017-12-01

Enamel demineralization is destructive, esthetically compromised, and costly complications for orthodontic patients. Nano-sized amorphous calcium phosphate (NACP) has been explored to address this challenge. The 20% NACP-loaded ortho-cement notably exhibited favorable behavior on reducing demineralization of enamel around brackets in a caries model designed to simulate the carious attack. The 20% NACP-loaded ortho-cement markedly promotes higher calcium and phosphate release at a low pH, and the mineral loss was almost two fold lower and carious lesion depth decreased the by 1/3. This novel approach is promising co-adjuvant route for prevention of dental caries dissemination in millions of patients under orthodontic treatment.

An early-branching microbialite cyanobacterium forms intracellular carbonates.

PubMed

Couradeau, Estelle; Benzerara, Karim; Gérard, Emmanuelle; Moreira, David; Bernard, Sylvain; Brown, Gordon E; López-García, Purificación

2012-04-27

Cyanobacteria have affected major geochemical cycles (carbon, nitrogen, and oxygen) on Earth for billions of years. In particular, they have played a major role in the formation of calcium carbonates (i.e., calcification), which has been considered to be an extracellular process. We identified a cyanobacterium in modern microbialites in Lake Alchichica (Mexico) that forms intracellular amorphous calcium-magnesium-strontium-barium carbonate inclusions about 270 nanometers in average diameter, revealing an unexplored pathway for calcification. Phylogenetic analyses place this cyanobacterium within the deeply divergent order Gloeobacterales. The chemical composition and structure of the intracellular precipitates suggest some level of cellular control on the biomineralization process. This discovery expands the diversity of organisms capable of forming amorphous calcium carbonates.

Biogenic Fish-gut Calcium Carbonate is a Stable Amorphous Phase in the Gilt-head Seabream, Sparus aurata

PubMed Central

Foran, Elizabeth; Weiner, Steve; Fine, Maoz

2013-01-01

The main source of calcium carbonate (CaCO3) in the ocean comes from the shells of calcifying planktonic organisms, but substantial amounts of CaCO3 are also produced in fish intestines. The precipitation of CaCO3 assists fish in intestinal water absorption and aids in whole body Ca2+ homeostasis. Here we report that the product formed in the intestinal lumen of the gilt-head seabream, Sparus aurata, is an amorphous calcium carbonate (ACC) phase. With FTIR spectroscopy and SEM imaging, our study shows that the fish-derived carbonates from S. aurata are maintained as a stable amorphous phase throughout the intestinal tract. Moreover, intestinal deposits contained up to 54 mol% Mg2+, the highest concentration yet reported in biogenic ACC. Mg is most likely responsible for stabilizing this inherently unstable mineral. The fish carbonates also displayed initial rapid dissolution when exposed to seawater, exhibiting a significant increase in carbonate concentration. PMID:23609008

The organic matrix of gallstones

PubMed Central

Sutor, D. June; Wooley, Susan E.

1974-01-01

Dissolution of gallstones consisting of cholesterol, calcium carbonate, or calcium phosphate in different solvents left an amorphous organic gel-like substance (the matrix). Matrix from cholesterol stones could be colourless but was usually orange, yellow, or brown while that from calcium carbonate and calcium phosphate stones was almost invariably coloured black or dark brown. These pigments were also shown to be organic and amorphous. The amount of matrix present and its structure varied with the texture of the crystalline material. Irrespective of their composition, laminated pieces of material yielded compact laminated matrix of the same shape as the original piece and areas of loose crystalline material gave small pieces of non-cohesive matrix. Only large cholesterol crystals which usually radiate from the stone nucleus had no associated matrix. ImagesFig 1Fig 2Fig 3Fig 4Fig 5 PMID:4854981

The Search for Interstellar Sulfide Grains

NASA Technical Reports Server (NTRS)

Keller, Lindsay P.; Messenger, Scott

2010-01-01

The lifecycle of sulfur in the galaxy is poorly understood. Fe-sulfide grains are abundant in early solar system materials (e.g. meteorites and comets) and S is highly depleted from the gas phase in cold, dense molecular cloud environments. In stark contrast, sulfur is essentially undepleted from the gas phase in the diffuse interstellar medium, indicating that little sulfur is incorporated into solid grains in this environment. It is widely believed that sulfur is not a component of interstellar dust grains. This is a rather puzzling observation unless Fe-sulfides are not produced in significant quantities in stellar outflows, or their lifetime in the ISM is very short due to rapid destruction. Fe sulfide grains are ubiquitous in cometary samples where they are the dominant host of sulfur. The Fe-sulfides (primarily pyrrhotite; Fe(1-x)S) are common, both as discrete 0.5-10 micron-sized grains and as fine (5-10 nm) nanophase inclusions within amorphous silicate grains. Cometary dust particles contain high abundances of well-preserved presolar silicates and organic matter and we have suggested that they should contain presolar sulfides as well. This hypothesis is supported by the observation of abundant Fe-sulfides grains in dust around pre- and post-main sequence stars inferred from astronomical spectra showing a broad 23 micron IR feature due to FeS. Fe-sulfide grains also occur as inclusions in bona fide circumstellar amorphous silicate grains and as inclusions within deuterium-rich organic matter in cometary dust samples. Our irradiation experiments show that FeS is far more resistant to radiation damage than silicates. Consequently, we expect that Fe sulfide stardust should be as abundant as silicate stardust in solar system materials.

Evaluation of the phase properties of hydrating cement composite using simulated nanoindentation technique

NASA Astrophysics Data System (ADS)

Gautham, S.; Sindu, B. S.; Sasmal, Saptarshi

2017-10-01

Properties and distribution of the products formed during the hydration of cementitious composite at the microlevel are investigated using a nanoindentation technique. First, numerical nanoindentation using nonlinear contact mechanics is carried out on three different phase compositions of cement paste, viz. mono-phase Tri-calcium Silicate (C3S), Di-calcium Silicate (C2S) and Calcium-Silicate-Hydrate (CSH) individually), bi-phase (C3S-CSH, C2S-CSH) and multi-phase (more than 10 individual phases including water pores). To reflect the multi-phase characteristics of hydrating cement composite, a discretized multi-phase microstructural model of cement composite during the progression of hydration is developed. Further, a grid indentation technique for simulated nanoindentation is established, and employed to evaluate the mechanical characteristics of the hydrated multi-phase cement paste. The properties obtained from the numerical studies are compared with those obtained from experimental grid nanoindentation. The influence of composition and distribution of individual phase properties on the properties obtained from indentation are closely investigated. The study paves the way to establishing the procedure for simulated grid nanoindentation to evaluate the mechanical properties of heterogeneous composites, and facilitates the design of experimental nanoindentation.

Effect of ball milling on the physicochemical properties of atorvastatin calcium sesquihydrate: the dissolution kinetic behaviours of milled amorphous solids.

PubMed

Kobayashi, Makiko; Hattori, Yusuke; Sasaki, Tetsuo; Otsuka, Makoto

2017-01-01

The purposes of this study were to clarify the amorphization by ball milling of atorvastatin calcium sesquihydrate (AT) and to analyse the change in dissolution kinetics. The amorphous AT was prepared from crystal AT by ball milling and analysed in terms of the changes of its physicochemical properties by powder X-ray diffraction analysis (XRD), thermal analysis and infrared spectroscopy (IR). Moreover, to evaluate the usefulness of the amorphous form for pharmaceutical development, intrinsic solubility of the ground product was evaluated using a dissolution kinetic method. The XRD results indicated that crystalline AT was transformed into amorphous solids by more than 30-min milling. The thermal analysis result suggested that chemical potential of the ground AT are changed significantly by milling. The IR spectra of the AT showed the band shift from the amide group at 3406 cm -1 with an intermolecular hydrogen bond to a free amide group at 3365 cm -1 by milling. The dissolution of amorphous AT follows a dissolution kinetic model involving phase transformation. The initial dissolution rate of the ground product increased with the increase in milling time to reflect the increase in the intrinsic solubility based on the amorphous state. © 2016 Royal Pharmaceutical Society.

Calcium phosphate mineralization is widely applied in crustacean mandibles.

PubMed

Bentov, Shmuel; Aflalo, Eliahu D; Tynyakov, Jenny; Glazer, Lilah; Sagi, Amir

2016-02-24

Crustaceans, like most mineralized invertebrates, adopted calcium carbonate mineralization for bulk skeleton reinforcement. Here, we show that a major part of the crustacean class Malacostraca (which includes lobsters, crayfishes, prawns and shrimps) shifted toward the formation of calcium phosphate as the main mineral at specified locations of the mandibular teeth. In these structures, calcium phosphate is not merely co-precipitated with the bulk calcium carbonate but rather creates specialized structures in which a layer of calcium phosphate, frequently in the form of crystalline fluorapatite, is mounted over a calcareous "jaw". From a functional perspective, the co-existence of carbonate and phosphate mineralization demonstrates a biomineralization system that provides a versatile route to control the physico-chemical properties of skeletal elements. This system enables the deposition of amorphous calcium carbonate, amorphous calcium phosphate, calcite and apatite at various skeletal locations, as well as combinations of these minerals, to form graded composites materials. This study demonstrates the widespread occurrence of the dual mineralization strategy in the Malacostraca, suggesting that in terms of evolution, this feature of phosphatic teeth did not evolve independently in the different groups but rather represents an early common trait.

Calcium phosphate mineralization is widely applied in crustacean mandibles

PubMed Central

Bentov, Shmuel; Aflalo, Eliahu D.; Tynyakov, Jenny; Glazer, Lilah; Sagi, Amir

2016-01-01

Crustaceans, like most mineralized invertebrates, adopted calcium carbonate mineralization for bulk skeleton reinforcement. Here, we show that a major part of the crustacean class Malacostraca (which includes lobsters, crayfishes, prawns and shrimps) shifted toward the formation of calcium phosphate as the main mineral at specified locations of the mandibular teeth. In these structures, calcium phosphate is not merely co-precipitated with the bulk calcium carbonate but rather creates specialized structures in which a layer of calcium phosphate, frequently in the form of crystalline fluorapatite, is mounted over a calcareous “jaw”. From a functional perspective, the co-existence of carbonate and phosphate mineralization demonstrates a biomineralization system that provides a versatile route to control the physico-chemical properties of skeletal elements. This system enables the deposition of amorphous calcium carbonate, amorphous calcium phosphate, calcite and apatite at various skeletal locations, as well as combinations of these minerals, to form graded composites materials. This study demonstrates the widespread occurrence of the dual mineralization strategy in the Malacostraca, suggesting that in terms of evolution, this feature of phosphatic teeth did not evolve independently in the different groups but rather represents an early common trait. PMID:26906263

SIMULTANEOUS CONTROL OF HG(0), SO2, AND NOX BY NOVEL OXIDIZED CALCIUM-BASED SORBENTS

EPA Science Inventory

The paper gives results of an investigation of two classes of calcium (Ca)-based sorbents (hydrated limes and silicate compounds). {NOTE: Efforts to develop multipollutant control strategies have demonstrated that adding certain oxidants to different classes of Ca-based sorbents ...

SIMULTANEOUS CONTROL OF HGO, SO2, AND NOX BY NOVEL OXIDIZED CALCIUM-BASED SORBENTS

EPA Science Inventory

The paper gives results of an investigation of two classes of calcium (Ca)-based sorbents (hydrated limes and silicate compounds). (NOTE: Efforts to develop multipollutant control strategies have demonstrated that adding certain oxidants to different classes of Ca-based sorbents...

Disappearance of 19P/Borrelly's Silicate Feature in 2001 Apparition Is Attributed to Increase in Grain Size

NASA Astrophysics Data System (ADS)

Wooden, D. H.; Woodward, C. E.; Harker, D. E.

2003-05-01

We report on observations and analysis of HIFOGS 10 \\micron \\ spectrophotometry of short period comet 19P/Borrelly on 2003 October 13, 15 UT at the NASA IRTF. 19P/Borrelly is one of two short period comets, comet 4P/Faye being the other, to have a silicate feature detected (Hanner et al. 1996, Icarus, 124, 344). During Borrelly.s perihelion passage in 1994 December, a silicate feature was present with a flux-to-continuum ratio of 0.25. Two apparitions later in 2003 October, the silicate feature is absent. Thermal emission modeling (cf. Harker et al. 2002, ApJ, 580, 579) using amorphous olivine and amorphous carbon shows that a slight increase in grain size accounts for the disappearance of the silicate feature. Analysis of 19P/Borrelly suggests grain size, and not the absence of olivine minerals, may be responsible for the absence of silicate features in most short period comets. 19P/Borrelly is one of the more active short period comets. However, short period comets as a family are less active than long period comets. Short period comets probably originated in the Kuiper Belt and suffered collisions while in residence in the outer solar system. Upon evolution into orbits that take them through the inner solar system, the surfaces of short period comets are exposed to sunlight through their many perihelion passages. This is in contrast to long period comets which probably originated near Jupiter and were expelled to the Oort cloud where they have existed and been exposed to cosmic ray processing. By studying the grain properties in short period comets and comparing to long period comets, we compare the effects on the grain populations of different parent body evolution histories. Upcoming opportunities to study short and long period comets will be advertised. This research is supported in part by an NSF Grant to the University of Minnesota.

Aqueous solubility diagrams for cementitious waste stabilization systems. 3. Mechanism of zinc immobilizaton by calcium silicate hydrate.

PubMed

Tommaseo, C E; Kersten, M

2002-07-01

Zinc oxide was added during hydration of alite (C3S) as an analogue for solidification/stabilization by cement of metal-bearing hazardous waste. Curing of samples was stopped at various intervals between 8 h and 100 d, and the reaction products were analyzed by both X-ray diffraction (XRD) and X-ray absorption spectroscopy (EXAFS at Zn, Ca, and Si K-edges). Calcium zincate hydrate (CaZn2(OH)6 x 2H2O) initially formed together with calcium silicate hydrate (CSH) vanishes from X-ray diffractograms after 14 d, and no other crystalline Zn-bearing phase could be detected thereafter. EXAFS Zn K-edge data analysis reveals that Zn(O,OH)4 tetrahedra continue to determine the first shell coordination. However, a new Zn-Si bond appears in the second coordination shell as indicated by both Zn K-edge and Si K-edge EXAFS. Together with the Ca-Zn and Ca-Ca shells derived from the Ca K-edge EXAFS spectra, a structural model for the site occupation of Zn in CSH is proposed, whereby the Zn(O,OH)4 tetrahedra are bound in layer rather than interlayer positions substituting for the silicate bridging tetrahedra and/or at terminal silicate chain sites. This structural model enables ultimately the formulation of a thermodyamic Lippmann model to predict the aqueous solubility of Zn in solid solution with a CSH phase of a Ca/Si ratio fixed to unity.

Sediment-pore water interactions controlling cementation in the NanTroSEIZE drilling transects

NASA Astrophysics Data System (ADS)

Hong, W.; Spinelli, G. A.; Torres, M. E.

2012-12-01

One goal of the Nankai Trough Seismogenic Zone Experiment (NanTroSEIZE) is to understand how changes in subducting sediment control the transition from aseismic to seismogenic behavior in subduction zones. In the sediment entering the Nankai subduction zone, dramatic changes in physical and chemical properties occur across a diagenetic boundary; they are thought to affect sediment strength and deformation. The dissolution of disseminated volcanic ash and precipitation of silica cement may be responsible for these changes in physical properties, but the mechanism controlling cementation was unclear (Spinelli et al., 2007). In this study, we used CrunchFlow (Steefel, 2009) to simulate chemical reactions and fluid flow through 1-D sediment columns at Integrated Ocean Drilling Program (IODP) sites on the incoming plate in Nankai Trough. The simulations include the thermodynamics and kinetics of sediment-water interactions, advection of pore water and sediment due to compaction, and multi-component diffusion in an accumulating sediment column. Key reactions in the simulations are: ash dissolution, amorphous silica precipitation and dissolution, and zeolite precipitation. The rate of ash decomposition was constrained using Sr isotope data of Joseph et al. (2012). Our model reproduces the distinct diagenetic boundary observed in sediment and pore water chemistry, which defines two zones. Above this boundary (zone 1), dissolved and amorphous silicate contents are high and the potassium concentration remains near seawater values or gradually decreases toward the boundary. Below the boundary, both dissolved and amorphous silicate content drop rapidly, concomitant with a decrease in dissolved potassium. Our model shows that these changes in the system are driven by formation of clinoptilolite in response to changes in pore fluid pH. The low pH values (<7.6) above the diagenetic boundary accelerate ash decomposition and maintain clinoptilolite slightly undersaturated. The dissolved silicate released from ash alteration precipitates as cement, inhibiting consolidation. At or below the boundary, the increase in pH (>8.0), leads to oversaturation (and precipitation) of clinoptilolite. Strong demand of dissolved silicate due to clinoptilolite formation soon depletes the dissolved potassium and silicate; ash and silicate cement are forced to dissolve. The exact set of reactions resulting on the observed pH increase is still unclear, but it likely involves the carbon system. It is noteworthy that the diagenetic boundary at all sites in the incoming plate occurs at the same thermal maturity of the sediments (TTI=0.025), similar to observations on onshore sequences in Japan (Sasaki, 1986).

Fabrication and characterization of poly(DL-lactic-co-glycolic acid)/zirconia-hybridized amorphous calcium phosphate composites

PubMed Central

WHITED, BRYCE M.; GOLDSTEIN, AARON S.; SKRTIC, DRAGO; LOVE, BRIAN J.

2010-01-01

Several minerals, such as hydroxyapatite and β-tricalcium phosphate, have been incorporated into bioresorbable polyester bone scaffolds to increase the osteoconductivity both in vitro and in vivo. More soluble forms of calcium phosphate that release calcium and phosphate ions have been postulated as factors that increase osteoblast differentiation and mineralization. Recently, a zirconia-hybridized pyrophosphate-stabilized amorphous calcium phosphate (Zr-ACP) has been synthesized allowing controlled release of calcium and phosphate ions. When incorporated into bioresorbable scaffolds, Zr-ACP has the potential to induce osteoconductivity. In this study, 80–90% (w/v) porous poly(DL-LActic-co-glycolic acid) (PLGA) scaffolds were formed by thermal phase separation from dioxane while incorporating Zr-ACP. Scanning electron microscopy revealed a highly porous structure with a pore size ranging from a few μm to about 100 μm, smaller than we had hoped for. Zr-ACP particles were evenly dispersed in the composite structure and incorporated into the pore walls. The amorphous structure of the Zr-ACP was maintained during composite fabrication, as found by X-ray diffraction. Composite scaffolds had larger compressive yield strengths and moduli compared to pure polymer scaffolds. These initial efforts demonstrate that PLGA/Zr-ACP composites can be formed in ways that ultimately serve as promising bone scaffolds in tissue engineering. PMID:16768292

Cometary crystalline silicate before and after perihelion passage II

NASA Astrophysics Data System (ADS)

Ootsubo, Takafumi

2014-01-01

Crystalline silicate is often observed in comets as an 11.3-micron resonant emission feature, and may be used for probing the early solar nebula. Because the formation of the crystalline silicate requires high temperature, they are thought to have been born from amorphous silicate at the inner region, and then transported toward the outer regions where comets were born. This transportation can produce the difference in the crystalline fraction in the cometary silicate dust between two dynamical types of comets, Oort-cloud comets (OCs) and Ecliptic comets (ECs), due to the different heliocentric distances of their birth places. The study of peak wavelengths in crystalline features is important to investigate the conditions of the crystalline silicate formation as well. Thus far, we don't have enough observational samples of OCs. Fortunately, we can observe comet C/2012 K1 (PanSTARRS) along with C/2013 A1 (Siding Spring) in this semester. In particular, the comet C/2012 K1 (PanSTARRS) is a bright and good target for this silicate peak feature study. Observations at pre- and post-perihelion provide us precious information on the dust evolution of the comet.

Structure of Oxide Glass and Melts at High-Pressure: A View from Inelastic X-ray Scattering and 2D Solid-State NMR

NASA Astrophysics Data System (ADS)

Lee, S.; Mysen, B. O.; Fei, Y.; Cody, G. D.; Mao, H.; Eng, P.

2006-12-01

Full understanding of the atomic arrangement of oxides glasses and melts both at ambient and high-pressure has long been one of the fundamental and yet difficult problems in earth sciences, condensed matter physics as well as glass sciences. The structures of archetypal oxide glasses (e.g. SiO2 and B2O3) as well as complex silicate glasses (ternary and quaternary aluminosilicate glasses) at high pressure are essential to elucidate origins of anomalous macroscopic properties of melts and global geophysical processes in the Earth's interior. Recent progress in inelastic x-ray scattering (IXS) with high brilliance 3rd generation synchrotron x-rays combined with DAC techniques allows us to explore pressure-induced changes in the bonding nature of archetypal amorphous oxide, illustrating a new opportunity to study amorphous oxides with IXS (Lee SK et al. Nature Materials 2005, 4, p851). 2 dimensional solid-state NMR have offered much improved resolution over conventional 1D NMR, unveiling previously unknown structural details of amorphous silicates at high pressure (Lee SK. Geochim. Cosmochim. Acta 2005, 69, p3695; J. Phys. Chem. B. 2006, 110, p16408) Here, we report the synchrotron inelastic x-ray scattering results (oxygen and boron K-edge) for divers oxide glasses at pressure up to 40 GPa, revealing the nature of pressure-induced bonding changes and the structure. Direct in-situ measurements provide evidence for a continuous transformation with multiple densification mechanisms. 2D solid-state NMR spectra for silicate and germinate glasses shows detailed information about extent of disorder among framework units at high pressure. The chemical ordering among framework units leads to the formation of ^{[5,6]}Si-O-^{[4]}Si in silicates and ^{[5,6]}Al-O-^{[4]}Si in aluminosilicates. Whereas the densification mechanism can be dependent on the chemical composition and the fraction of non-bridging oxygen, the pressure dependence of both simple and complex multi-component silicate glasses showed similar characteristics: low pressure regime was marked with topological variation without coordination transformation and inter-mediate pressure region (about 5-10 GPa) was characterized by the largest (d(^{[4]}B or ^{[5,6]}Si)/dP) value. Finally high-pressure regime (above 10 GPa) was characterized by a larger energy penalty for coordination transformation than in intermediate pressure regime. These results provide improved prospect for the bonding nature of amorphous materials at high pressure using synchrotron inelastic x-ray scattering and 2D NMR and aid in understanding the microscopic origins of the properties of melts and geological processes in the Earth's interior.

Effects of calcium hydroxide addition on the physical and chemical properties of a calcium silicate-based sealer.

PubMed

Kuga, Milton Carlos; Duarte, Marco Antonio Hungaro; Sant'anna-Júnior, Arnaldo; Keine, Kátia Cristina; Faria, Gisele; Dantas, Andrea Abi Rached; Guiotti, Flávia Angélica

2014-06-01

Recently, various calcium silicate-based sealers have been introduced for use in root canal filling. The MTA Fillapex is one of these sealers, but some of its physicochemical properties are not in accordance with the ISO requirements. The aim of this study was to evaluate the flowability, pH level and calcium release of pure MTA Fillapex (MTAF) or containing 5% (MTAF5) or 10% (MTAF10) calcium hydroxide (CH), in weight, in comparison with AH Plus sealer. The flowability test was performed according to the ISO 6876:2001 requirements. For the pH level and calcium ion release analyses, the sealers were placed individually (n=10) in plastic tubes and immersed in deionized water. After 24 hours, 7 and 14 days, the water in which each specimen had been immersed was evaluated to determine the pH level changes and calcium released. Flowability, pH level and calcium release data were analyzed statistically by the ANOVA test (α=5%). In relation to flowability: MTAF>AH Plus>MTAF5>MTAF10. In relation to the pH level, for 24 h: MTAF5=MTAF10=MTAF>AH Plus; for 7 and 14 days: MTAF5=MTAF10>MTAF>AH Plus. For the calcium release, for all periods: MTAF>MTAF5=MTAF10>AH Plus. The addition of 5% CH to the MTA Fillapex (in weight) is an alternative to reduce the high flowability presented by the sealer, without interfering in its alkalization potential.

Physicochemical properties of calcium silicate-based formulations MTA Repair HP and MTA Vitalcem

PubMed Central

Guimarães, Bruno Martini; Prati, Carlo; Duarte, Marco Antonio Hungaro; Bramante, Clovis Monteiro; Gandolfi, Maria Giovanna

2018-01-01

Abstract Objective This study aimed to analyze the following physicochemical properties: radiopacity, final setting time, calcium release, pH change, solubility, water sorption, porosity, surface morphology, and apatite-forming ability of two calcium silicate-based materials. Material and methods We tested MTA Repair HP and MTA Vitalcem in comparison with conventional MTA, analyzing radiopacity and final setting time. Water absorption, interconnected pores and apparent porosity were measured after 24-h immersion in deionized water at 37°C. Calcium and pH were tested up to 28 d in deionized water. We analyzed data using two-way ANOVA with Student-Newman-Keuls tests (p<0.05). We performed morphological and chemical analyses of the material surfaces using ESEM/EDX after 28 d in HBSS. Results MTA Repair HP showed similar radiopacity to that of conventional MTA. All materials showed a marked alkalinizing activity within 3 h, which continued for 28 d. MTA Repair HP showed the highest calcium release at 28 d (p<0.05). MTA Vitalcem showed statistically higher water sorption and solubility values (p<0.05). All materials showed the ability to nucleate calcium phosphate on their surface after 28 d in HBSS. Conclusions MTA Repair HP and MTA Vitalcem had extended alkalinizing activity and calcium release that favored calcium phosphate nucleation. The presence of the plasticizer in MTA HP might increase its solubility and porosity. The radiopacifier calcium tungstate can be used to replace bismuth oxide. PMID:29641748

Amorphous Phases on the Surface of Mars

NASA Technical Reports Server (NTRS)

Rampe, E. B.; Morris, R. V.; Ruff, S. W.; Horgan, B.; Dehouck, E.; Achilles, C. N.; Ming, D. W.; Bish, D. L.; Chipera, S. J.

2014-01-01

Both primary (volcanic/impact glasses) and secondary (opal/silica, allophane, hisingerite, npOx, S-bearing) amorphous phases appear to be major components of martian surface materials based on orbital and in-situ measurements. A key observation is that whereas regional/global scale amorphous components include altered glass and npOx, local scale amorphous phases include hydrated silica/opal. This suggests widespread alteration at low water-to-rock ratios, perhaps due to snow/ice melt with variable pH, and localized alteration at high water-to-rock ratios. Orbital and in-situ measurements of the regional/global amorphous component on Mars suggests that it is made up of at least three phases: npOx, amorphous silicate (likely altered glass), and an amorphous S-bearing phase. Fundamental questions regarding the composition and the formation of the regional/global amorphous component(s) still remain: Do the phases form locally or have they been homogenized through aeolian activity and derived from the global dust? Is the parent glass volcanic, impact, or both? Are the phases separate or intimately mixed (e.g., as in palagonite)? When did the amorphous phases form? To address the question of source (local and/or global), we need to look for variations in the different phases within the amorphous component through continued modeling of the chemical composition of the amorphous phases in samples from Gale using CheMin and APXS data. If we find variations (e.g., a lack of or enrichment in amorphous silicate in some samples), this may imply a local source for some phases. Furthermore, the chemical composition of the weathering products may give insight into the formation mechanisms of the parent glass (e.g., impact glasses contain higher Al and lower Si [30], so we might expect allophane as a weathering product of impact glass). To address the question of whether these phases are separate or intimately mixed, we need to do laboratory studies of naturally altered samples made up of mixed phases (e.g., palagonite) and synthetic single phases to determine their short-range order structures and calculate their XRD patterns to use in models of CheMin data. Finally, to address the timing of the alteration, we need to study rocks on the martian surface of different ages that may contain glass (volcanic or impact) with MSL and future rovers to better understand how glass alters on the martian surface, if that alteration mechanism is universal, and if alteration spans across long periods of time or if there is a time past which unaltered glass remains.

Synthesis and structure of synthetically pure and deuterated amorphous (basic) calcium carbonates

DOE PAGES

Wang, Hsiu-Wen; Daemen, Luke L.; Cheshire, Michael C.; ...

2017-02-17

It is generally believed that H 2O and OH - are the key species stabilizing and controlling amorphous calcium carbonate “polyamorph” forms, and may in turn control the ultimate crystallization products during synthesis and in natural systems. Yet, the locations and hydrogen-bonding network of these species in ACC have never been measured directly using neutron diffraction. In this paper, we report a synthesis route that overcomes the existing challenges with respect to yield quantities and deuteration, both of which are critically necessary for high quality neutron studies.

New Silica Magnetite Sorbent: The Influence of Variations of Sodium Silicate Concentrations on Silica Magnetite Character

NASA Astrophysics Data System (ADS)

Azmiyawati, C.; Pratiwi, P. I.; Darmawan, A.

2018-04-01

The adsorption capacity of an adsorbent is determined by the adsorbent and the adsorbate properties. The character of the adsorbent will play a major role in its ability to adsorb the corresponding adsorbate. Therefore, in this study we looked at the effects of variations of sodium silicate concentrations on the resulting magnetite silica adsorbent properties. The application of silica coating on the magnetite was carried out through a sol-gel process with sodium silicate and HCl precursors. Based on the characterization data obtained, it was found that the silica coating on magnetite can increase the resistance to acid leaching, increase the particle size, but decrease the magnetic properties of the magnetite. Based on Gas Sorption Analyzer (GSA) and X-ray Difraction (XRD) data it can successively be determined that increase in concentration of sodium silicate will increase the surface area and amorphous structure of the Silica Magnetie.

Examination of Calcium Silicate Cements with Low-Viscosity Methyl Cellulose or Hydroxypropyl Cellulose Additive.

PubMed

Baba, Toshiaki; Tsujimoto, Yasuhisa

2016-01-01

The purpose of this study was to improve the operability of calcium silicate cements (CSCs) such as mineral trioxide aggregate (MTA) cement. The flow, working time, and setting time of CSCs with different compositions containing low-viscosity methyl cellulose (MC) or hydroxypropyl cellulose (HPC) additive were examined according to ISO 6876-2012; calcium ion release analysis was also conducted. MTA and low-heat Portland cement (LPC) including 20% fine particle zirconium oxide (ZO group), LPC including zirconium oxide and 2 wt% low-viscosity MC (MC group), and HPC (HPC group) were tested. MC and HPC groups exhibited significantly higher flow values and setting times than other groups ( p < 0.05). Additionally, flow values of these groups were higher than the ISO 6876-2012 reference values; furthermore, working times were over 10 min. Calcium ion release was retarded with ZO, MC, and HPC groups compared with MTA. The concentration of calcium ions was decreased by the addition of the MC or HPC group compared with the ZO group. When low-viscosity MC or HPC was added, the composition of CSCs changed, thus fulfilling the requirements for use as root canal sealer. Calcium ion release by CSCs was affected by changing the CSC composition via the addition of MC or HPC.

Examination of Calcium Silicate Cements with Low-Viscosity Methyl Cellulose or Hydroxypropyl Cellulose Additive

PubMed Central

Tsujimoto, Yasuhisa

2016-01-01

The purpose of this study was to improve the operability of calcium silicate cements (CSCs) such as mineral trioxide aggregate (MTA) cement. The flow, working time, and setting time of CSCs with different compositions containing low-viscosity methyl cellulose (MC) or hydroxypropyl cellulose (HPC) additive were examined according to ISO 6876-2012; calcium ion release analysis was also conducted. MTA and low-heat Portland cement (LPC) including 20% fine particle zirconium oxide (ZO group), LPC including zirconium oxide and 2 wt% low-viscosity MC (MC group), and HPC (HPC group) were tested. MC and HPC groups exhibited significantly higher flow values and setting times than other groups (p < 0.05). Additionally, flow values of these groups were higher than the ISO 6876-2012 reference values; furthermore, working times were over 10 min. Calcium ion release was retarded with ZO, MC, and HPC groups compared with MTA. The concentration of calcium ions was decreased by the addition of the MC or HPC group compared with the ZO group. When low-viscosity MC or HPC was added, the composition of CSCs changed, thus fulfilling the requirements for use as root canal sealer. Calcium ion release by CSCs was affected by changing the CSC composition via the addition of MC or HPC. PMID:27981048

Evolution of the magnesium incorporated amorphous calcium phosphate to nano-crystallized hydroxyapatite in alkaline solution

NASA Astrophysics Data System (ADS)

Zhang, Xiao-Juan; Lin, Dong-Yang; Yan, Xiao-Hui; Wang, Xiao-Xiang

2011-12-01

A homogeneous amorphous calcium phosphate (ACP) coating containing magnesium was achieved on titanium substrates by electrochemical deposition (ECD). Its amorphous structure is confirmed by transmission electron microscope (TEM) together with grazing reflection absorption infrared spectroscopy (IR) spectrometer. In the images of high-resolution transmission electron microscope (HRTEM), the ACP spheres are assembled by nano-particles with the diameter of 5-10 nm. In the alkaline environment, nucleation of hydroxyapatite (HAP) occurs on the surfaces of ACP spheres. By consuming the Ca and PO 4 ions inside the ACP spheres, the HAP nuclei grow outward. Confirmed by TEM, the ACP spheres converse to hollow HAP spheres composed of HAP nano-needles. The coating is finally constructed by the HAP nano-needles, which are themselves aggregated by numerous nano-particles.

Room temperature vortex fluidic synthesis of monodispersed amorphous proto-vaterite.

PubMed

Peng, Wenhong; Chen, Xianjue; Zhu, Shenmin; Guo, Cuiping; Raston, Colin L

2014-10-11

Monodispersed particles of amorphous calcium carbonate (ACC) 90 to 200 nm in diameter are accessible at room temperature in ethylene glycol and water using a vortex fluidic device (VFD). The ACC material is stable for at least two weeks under ambient conditions.

Transmission X-ray Diffraction (XRD) Patterns Relevant to the MSL Chemin Amorphous Component: Sulfates And Silicates

NASA Technical Reports Server (NTRS)

Morris, R. V.; Rampe, E. B.; Graff, T. G.; Archer, P. D., Jr.; Le, L.; Ming, D. W.; Sutter, B.

2015-01-01

The Mars Science Laboratory (MSL) CheMin instrument on the Curiosity rover is a transmission X-ray diffractometer (Co-Kalpha radiation source and a approx.5deg to approx.52deg 2theta range) where the analyzed powder samples are constrained to have discrete particle diameters <150 microns by a sieve. To date, diffraction patterns have been obtained for one basaltic soil (Rocknest (RN)) and four drill fines of coherent rock (John Klein (JK), Cumberland (CB), Windjana (WJ), and Confidence Hills (CH)). The CheMin instrument has detected and quantified the abundance of both primary igneous (e.g., feldspar, olivine, and pyroxene) and secondary (e.g., Ca-sulfates, hematite, akaganeite, and Fe-saponite) minerals. The diffraction patterns of all CheMin samples are also characterized by a broad diffraction band centered near 30deg 2theta and by increasing diffraction intensity (scattering continuum) from approx.15deg to approx.5deg, the 2theta minimum. Both the broad band and the scattering continuum are attributed to the presence of an XRD amorphous component. Estimates of amorphous component abundance, based on the XRD data itself and on mass-balance calculations using APXS data crystalline component chemistry derived from XRD data, martian meteorites, and/or stoichiometry [e.g., 6-9], range from approx.20 wt.% to approx.50 wt.% of bulk sample. The APXSbased calculations show that the amorphous component is rich in volatile elements (esp. SO3) and is not simply primary basaltic glass, which was used as a surrogate to model the broad band in the RN CheMin pattern. For RN, the entire volatile inventory (except minor anhydrite) is assigned to the amorphous component because no volatile-bearing crystalline phases were reported within detection limits [2]. For JK and CB, Fesaponite, basanite, and akaganeite are volatile-bearing crystalline components. Here we report transmission XRD patterns for sulfate and silicate phases relevant to interpretation of MSL-CheMin XRD amorphous components.

Porous, S-bearing silica in metal-sulfide nodules and in the interchondrule clastic matrix in two EH3 chondrites

NASA Astrophysics Data System (ADS)

Lehner, S. W.; Németh, P.; Petaev, M. I.; Buseck, P. R.

2017-11-01

Two new occurrences of porous, S-bearing, amorphous silica are described within metal-sulfide nodules (MSN) and as interchondrule patches in EH3 chondrites SAH 97072 and ALH 84170. This porous amorphous material, which was first reported from sulfide-bearing chondrules, consists of sinewy SiO2-rich areas containing S with minor Na or Ca as well as Fe, Mg, and Al. Some pores contain minerals including pyrite, pyrrhotite, and anhydrite. Most pores appear vacant or contain unidentified material that is unstable under analytical conditions. Niningerite, olivine, enstatite, albite, and kumdykolite occur enclosed within porous silica patches. Porous silica is commonly interfingered with cristobalite suggesting its amorphous structure resulted from high-temperature quenching. We interpret the S-bearing porous silica to be a product of silicate sulfidation, and the Na, Ca, Fe, Mg, and Al detectable within this material are chemical residues of sulfidized silicates and metal. The occurrence of porous silica in the cores of MSN, which are considered to be pre-accretionary objects, suggests the sulfidizing conditions occurred prior to final parent-body solidification. Ubiquitous S-bearing porous silica among sulfide-bearing chondrules, MSN, and in the interchondrule clastic matrix, suggests that similar sulfidizing conditions affected all the constituents of these EH3 chondrites.

Biological and therapeutic effects of ortho-silicic acid and some ortho-silicic acid-releasing compounds: New perspectives for therapy.

PubMed

Jurkić, Lela Munjas; Cepanec, Ivica; Pavelić, Sandra Kraljević; Pavelić, Krešimir

2013-01-08

Silicon (Si) is the most abundant element present in the Earth's crust besides oxygen. However, the exact biological roles of silicon remain unknown. Moreover, the ortho-silicic acid (H4SiO4), as a major form of bioavailable silicon for both humans and animals, has not been given adequate attention so far. Silicon has already been associated with bone mineralization, collagen synthesis, skin, hair and nails health atherosclerosis, Alzheimer disease, immune system enhancement, and with some other disorders or pharmacological effects. Beside the ortho-silicic acid and its stabilized formulations such as choline chloride-stabilized ortho-silicic acid and sodium or potassium silicates (e.g. M2SiO3; M= Na,K), the most important sources that release ortho-silicic acid as a bioavailable form of silicon are: colloidal silicic acid (hydrated silica gel), silica gel (amorphous silicon dioxide), and zeolites. Although all these compounds are characterized by substantial water insolubility, they release small, but significant, equilibrium concentration of ortho-silicic acid (H4SiO4) in contact with water and physiological fluids. Even though certain pharmacological effects of these compounds might be attributed to specific structural characteristics that result in profound adsorption and absorption properties, they all exhibit similar pharmacological profiles readily comparable to ortho-silicic acid effects. The most unusual ortho-silicic acid-releasing agents are certain types of zeolites, a class of aluminosilicates with well described ion(cation)-exchange properties. Numerous biological activities of some types of zeolites documented so far might probably be attributable to the ortho-silicic acid-releasing property. In this review, we therefore discuss biological and potential therapeutic effects of ortho-silicic acid and ortho-silicic acid -releasing silicon compounds as its major natural sources.

A Novel Polymer-Synthesized Ceramic Composite Based System for Bone Repair: Osteoblast Growth on Scaffolds with Varied Calcium Phosphate Content

DTIC Science & Technology

2005-01-01

demongtrated the synthesis of degradable scaffolds from PLAGA /calcium phosphate composite microspheres in which an amorphous calcium phosphate is...EXPERIMENTAL DETAILS Scaffold Preparation Scaffolds were prepared as described in detail previously [3]. Briefly, PLAGA /calcium phosphate composite...culture polystyrene (TCPS) 2- pure PLAGA microspheres 64 3- composite microsphere matrices with a low polymer/ceramic ratio 4- composite microsphere

Assessment of calcium addition on the removal of U(VI) in the alkaline conditions created by NH 3 gas

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

Katsenovich, Yelena; Cardona, Claudia; Szecsody, Jim

Remediation of uranium (U) contamination in the deep vadose zone (VZ) sediments abundant in calcite mineral is a challenging task considering the formation of highly stable and mobile uranyl complexes with carbonate and calcium in pore water composition. There is a concern that uranium contamination in the VZ can serve as a continued source for groundwater pollution, creating a risk to human health and the environment through the groundwater pathway. This requires in-situ remediation of the radionuclide-contaminated VZ to convert soluble U species to low solubility precipitates that are stable in the natural environment. Injection of reactive gasses (e.g., NHmore » 3) is a promising technology to decrease U mobility in the unsaturated zone without the addition of liquid amendments. The NH 3 injection creates alkaline conditions that can alter the sediment pore water composition due to a release of elements from minerals (via desorption and dissolution) that are present in the sediment. However, it is not known how VZ pore water constituents (Si, Al 3+, HCO 3 -, and Ca 2 +) would affect U(VI) removal/precipitation in alkaline conditions. This study quantified the role of major pore water constituents typically present in the arid and semi-arid environments of the western regions of the U.S and identified solid uranium-bearing phases that could potentially precipitate from solutions approximating pore water compositions after pH manipulations via ammonia gas injections. Triplicate samples were prepared using six Si (5, 50 100, 150, 200, and 250 mM), six HCO 3 - (0, 3, 25, 50, 75, and 100 mM), and two Ca 2+ (5 and 10 mM) concentrations. The concentration of aluminum and uranium was kept constant at 5 mM and 0.0084 mM, respectively, in all synthetic formulations tested. Results showed that the percentage of U(VI) removal was controlled by the Si/Al molar ratios and Ca 2+ concentrations. Regardless of the bicarbonate concentration tested, the percentage of U(VI) removed increased as the Si/Al ratios were increased. However, higher Ca concentrations correlated with higher U(VI) removal, ranging between 96% and 99%, at low Si/Al ratios. The SEM images of dried precipitates displayed dense amorphous regions high in silica content, where EDS elemental analysis unveiled higher U atomic percentages. The formation of uranyl silicate and carbonate minerals was also predicted by the speciation modeling. XRD analysis revealed the presence of uranyl carbonate mineral phases (andersonite, grimselite); however, uranyl silicates predicted (Na-boltwoodite) were not identified experimentally, possibly due to the amorphous nature of the silica solid phases observed in our experiments.« less

Assessment of calcium addition on the removal of U(VI) in the alkaline conditions created by NH 3 gas

DOE PAGES

Katsenovich, Yelena; Cardona, Claudia; Szecsody, Jim; ...

2018-03-06

Remediation of uranium (U) contamination in the deep vadose zone (VZ) sediments abundant in calcite mineral is a challenging task considering the formation of highly stable and mobile uranyl complexes with carbonate and calcium in pore water composition. There is a concern that uranium contamination in the VZ can serve as a continued source for groundwater pollution, creating a risk to human health and the environment through the groundwater pathway. This requires in-situ remediation of the radionuclide-contaminated VZ to convert soluble U species to low solubility precipitates that are stable in the natural environment. Injection of reactive gasses (e.g., NHmore » 3) is a promising technology to decrease U mobility in the unsaturated zone without the addition of liquid amendments. The NH 3 injection creates alkaline conditions that can alter the sediment pore water composition due to a release of elements from minerals (via desorption and dissolution) that are present in the sediment. However, it is not known how VZ pore water constituents (Si, Al 3+, HCO 3 -, and Ca 2 +) would affect U(VI) removal/precipitation in alkaline conditions. This study quantified the role of major pore water constituents typically present in the arid and semi-arid environments of the western regions of the U.S and identified solid uranium-bearing phases that could potentially precipitate from solutions approximating pore water compositions after pH manipulations via ammonia gas injections. Triplicate samples were prepared using six Si (5, 50 100, 150, 200, and 250 mM), six HCO 3 - (0, 3, 25, 50, 75, and 100 mM), and two Ca 2+ (5 and 10 mM) concentrations. The concentration of aluminum and uranium was kept constant at 5 mM and 0.0084 mM, respectively, in all synthetic formulations tested. Results showed that the percentage of U(VI) removal was controlled by the Si/Al molar ratios and Ca 2+ concentrations. Regardless of the bicarbonate concentration tested, the percentage of U(VI) removed increased as the Si/Al ratios were increased. However, higher Ca concentrations correlated with higher U(VI) removal, ranging between 96% and 99%, at low Si/Al ratios. The SEM images of dried precipitates displayed dense amorphous regions high in silica content, where EDS elemental analysis unveiled higher U atomic percentages. The formation of uranyl silicate and carbonate minerals was also predicted by the speciation modeling. XRD analysis revealed the presence of uranyl carbonate mineral phases (andersonite, grimselite); however, uranyl silicates predicted (Na-boltwoodite) were not identified experimentally, possibly due to the amorphous nature of the silica solid phases observed in our experiments.« less

Cellular control over spicule formation in sea urchin embryos: A structural approach.

PubMed

Beniash, E; Addadi, L; Weiner, S

1999-03-01

The spicules of the sea urchin embryo form in intracellular membrane-delineated compartments. Each spicule is composed of a single crystal of calcite and amorphous calcium carbonate. The latter transforms with time into calcite by overgrowth of the preexisting crystal. Relationships between the membrane surrounding the spiculogenic compartment and the spicule mineral phase were studied in the transmission electron microscope (TEM) using freeze-fracture. In all the replicas observed the spicules were tightly surrounded by the membrane. Furthermore, a variety of structures that are related to the material exchange process across the membrane were observed. The spiculogenic cells were separated from other cell types of the embryo, frozen, and freeze-dried on the TEM grids. The contents of electron-dense granules in the spiculogenic cells were shown by electron diffraction to be composed of amorphous calcium carbonate. These observations are consistent with the notion that the amorphous calcium carbonate-containing granules contain the precursor mineral phase for spicule formation and that the membrane surrounding the forming spicule is involved both in transport of material and in controlling spicule mineralization. Copyright 1999 Academic Press.

Electron Microscopic Analysis of Surface Inorganic Substances on Oral and Combustible Tobacco Products

PubMed Central

Halstead, Mary M.; Watson, Clifford H.; Pappas, R. Steven

2015-01-01

Though quantitative trace toxic metals analyses have been performed on tobacco products, little has been published on inorganic particulate constituents on and inside the products. We analyzed these constituents using scanning electron microscopy with energy dispersive x-ray spectroscopy (SEM-EDS). The nature of SEM-EDS instrumentation makes it an ideal choice for inorganic particulate analyses and yields relevant information to potential exposures during consumption of oral tobacco products, and possibly as a consequence of smoking. Aluminum silicates, silica, and calcium compounds were common inorganic particulate constituents of tobacco products. Aluminum silicates and silica from soil were found on external leaf surfaces. Phytolithic silica, found in the lumen of the plant leaf, is of biogenic origin. Calcium oxalate was also apparently of biogenic origin. Small mineral deposits on tobacco could have health implications. Minerals found on the surfaces of smokeless tobacco products could possibly abrade the oral mucosa and contribute to the oral inflammatory responses observed with smokeless tobacco product use. If micron and sub-micron size calcium particles on cigarette filler were transported in mainstream smoke, they could potentially induce a pulmonary irritant inflammation when inhaled. The transport of aluminum silicate and silica in smoke could potentially also contribute to chronic inflammatory disease. PMID:26286581

Push-out bond strength of three calcium silicate cements to root canal dentine after two different irrigation regimes.

PubMed

Çelik, Davut; Er, Kürşat; Serper, Ahmet; Taşdemir, Tamer; Ceyhanlı, Kadir Tolga

2014-05-01

The aim of this study was to compare the push-out bond strength of three calcium silicate cements to dentine after two different irrigation regimes. One hundred eighty 2-mm-thick root sections were prepared. The sections were divided into three main groups (n = 60). In group A, the sections were immersed in 1 % NaOCl for 3 min. In group B, the sections were immersed in 17 % EDTA for 3 min followed by 1 % NaOCl for the same period of time. In group C (control group), no irrigation was applied to the sections. The samples from each group were divided into four subgroups (n = 15). In subgroups A1, B1 and C1, DiaRoot BioAggregate; in subgroups A2, B2 and C2, MTA-Angelus and in subgroups A3, B3 and C3, MM-MTA were mixed with hand-mixing. In subgroups A4, B4 and C4, MM-MTA was mixed with auto-mixing. The mixed cements were then placed into cavities with a carrier. The samples were submitted to the push-out test and were loaded. All the data were analysed with one-way analysis of variance and the Tukey HSD multiple comparisons (p < 0.05). There were no statistically significant differences between the irrigation regimes regardless of the used materials. The resistance to displacement in subgroup B4 was significantly greater than that presented by subgroups A3, B3 and C3 (p < 0.05) while not different than all other groups. Irrigation regimes had not affected the push-out bond strength of the calcium silicate cements. Also, strength of auto-mixed MM-MTA was similar to the other cements. The novel calcium silicate cements would be a potentially useful material in endodontic procedures with favourable properties.

Biocompatibility and bioactivity of calcium silicate-based endodontic sealers in human dental pulp cells.

PubMed

Mestieri, Leticia Boldrin; Gomes-Cornélio, Ana Lívia; Rodrigues, Elisandra Márcia; Salles, Loise Pedrosa; Bosso-Martelo, Roberta; Guerreiro-Tanomaru, Juliane Maria; Tanomaru-Filho, Mário

2015-10-01

Mineral Trioxide Aggregate (MTA) is a calcium silicate-based material. New sealers have been developed based on calcium silicate as MTA Fillapex and MTA Plus. The aim of this study was to evaluate biocompatibility and bioactivity of these two calcium silicate-based sealers in culture of human dental pulp cells (hDPCs). The cells were isolated from third molars extracted from a 16-year-old patient. Pulp tissue was sectioned into fragments with approximately 1 mm3 and kept in supplemented medium to obtain hDPCs adherent cultures. Cell characterization assays were performed to prove the osteogenic potential. The evaluated materials were: MTA Plus (MTAP); MTA Fillapex (MTAF) and FillCanal (FC). Biocompatibility was evaluated with MTT and Neutral Red (NR) assays, after hDPCs exposure for 24 h to different dilutions of each sealer extract (1:2, 1:3 and 1:4). Unexposed cells were the positive control (CT). Bioactivity was assessed by alkaline phosphatase (ALP) enzymatic assay in cells exposed for one and three days to sealer extracts (1:4 dilution). All data were analyzed by ANOVA and Tukey post-test (p≤0.05%). MTT and NR results showed suitable cell viability rates for MTAP at all dilutions (90-135%). Cells exposed to MTAF and FC (1:2 and 1:4 dilutions) showed significant low viability rate when compared to CT in MTT. The NR results demonstrated cell viability for all materials tested. In MTAP group, the cells ALP activity was similar to CT in one and three days of exposure to the material. MTAF and FC groups demonstrated a decrease in ALP activity when compared to CT at both periods of cell exposure. The hDPCs were suitable for the evaluation of new endodontic materialsin vitro. MTAP may be considered a promising material for endodontic treatments.

Synthesis, mechanical properties, and in vitro biocompatibility with osteoblasts of calcium silicate-reduced graphene oxide composites.

PubMed

Mehrali, Mehdi; Moghaddam, Ehsan; Shirazi, Seyed Farid Seyed; Baradaran, Saeid; Mehrali, Mohammad; Latibari, Sara Tahan; Metselaar, Hendrik Simon Cornelis; Kadri, Nahrizul Adib; Zandi, Keivan; Osman, Noor Azuan Abu

2014-03-26

Calcium silicate (CaSiO3, CS) ceramics are promising bioactive materials for bone tissue engineering, particularly for bone repair. However, the low toughness of CS limits its application in load-bearing conditions. Recent findings indicating the promising biocompatibility of graphene imply that graphene can be used as an additive to improve the mechanical properties of composites. Here, we report a simple method for the synthesis of calcium silicate/reduced graphene oxide (CS/rGO) composites using a hydrothermal approach followed by hot isostatic pressing (HIP). Adding rGO to pure CS increased the hardness of the material by ∼40%, the elastic modulus by ∼52%, and the fracture toughness by ∼123%. Different toughening mechanisms were observed including crack bridging, crack branching, crack deflection, and rGO pull-out, thus increasing the resistance to crack propagation and leading to a considerable improvement in the fracture toughness of the composites. The formation of bone-like apatite on a range of CS/rGO composites with rGO weight percentages ranging from 0 to 1.5 has been investigated in simulated body fluid (SBF). The presence of a bone-like apatite layer on the composite surface after soaking in SBF was demonstrated by X-ray diffraction (XRD) and field emission scanning electron microscopy (FESEM). The biocompatibility of the CS/rGO composites was characterized using methyl thiazole tetrazolium (MTT) assays in vitro. The cell adhesion results showed that human osteoblast cells (hFOB) can adhere to and develop on the CS/rGO composites. In addition, the proliferation rate and alkaline phosphatase (ALP) activity of cells on the CS/rGO composites were improved compared with the pure CS ceramics. These results suggest that calcium silicate/reduced graphene oxide composites are promising materials for biomedical applications.

Incorporation of casein phosphopeptide-amorphous calcium phosphate into a glass-ionomer cement.

PubMed

Mazzaoui, S A; Burrow, M F; Tyas, M J; Dashper, S G; Eakins, D; Reynolds, E C

2003-11-01

Casein phosphopeptide-amorphous calcium phosphate (CPP-ACP) nanocomplexes have been shown to prevent demineralization and promote remineralization of enamel subsurface lesions in animal and in situ caries models. The aim of this study was to determine the effect of incorporating CPP-ACP into a self-cured glass-ionomer cement (GIC). Incorporation of 1.56% w/w CPP-ACP into the GIC significantly increased microtensile bond strength (33%) and compressive strength (23%) and significantly enhanced the release of calcium, phosphate, and fluoride ions at neutral and acidic pH. MALDI mass spectrometry also showed casein phosphopeptides from the CPP-ACP nanocomplexes to be released. The release of CPP-ACP and fluoride from the CPP-ACP-containing GIC was associated with enhanced protection of the adjacent dentin during acid challenge in vitro.

Influence of ethanol content in the precipitation medium on the composition, structure and reactivity of magnesium-calcium phosphate.

PubMed

Babaie, Elham; Zhou, Huan; Lin, Boren; Bhaduri, Sarit B

2015-08-01

Biocompatible amorphous magnesium calcium phosphate (AMCP) particles were synthesized using ethanol in precipitation medium from moderately supersaturated solution at pH10. Some synthesis parameters such as, (Mg+Ca):P, Mg:Ca ratio and different drying methods on the structure and stability of as-produced powder was studied and characterized using SEM, XRD and cell cytocompatibility. The results showed that depending on the Mg(2+) concentration, nano crystalline Struvite (MgNH4PO4·6H2O) can also be alternatively formed. However, the as-formed AMCP preserved its amorphous structure after 7 days of incubation in SBF for tested phosphate concentration, and equally ionic concentration of magnesium and calcium. Copyright © 2015 Elsevier B.V. All rights reserved.

Effects of calcium hydroxide addition on the physical and chemical properties of a calcium silicate-based sealer

PubMed Central

KUGA, Milton Carlos; DUARTE, Marco Antonio Hungaro; SANT'ANNA-JÚNIOR, Arnaldo; KEINE, Kátia Cristina; FARIA, Gisele; DANTAS, Andrea Abi Rached; GUIOTTI, Flávia Angélica

2014-01-01

Recently, various calcium silicate-based sealers have been introduced for use in root canal filling. The MTA Fillapex is one of these sealers, but some of its physicochemical properties are not in accordance with the ISO requirements. Objective The aim of this study was to evaluate the flowability, pH level and calcium release of pure MTA Fillapex (MTAF) or containing 5% (MTAF5) or 10% (MTAF10) calcium hydroxide (CH), in weight, in comparison with AH Plus sealer. Material and Methods The flowability test was performed according to the ISO 6876:2001 requirements. For the pH level and calcium ion release analyses, the sealers were placed individually (n=10) in plastic tubes and immersed in deionized water. After 24 hours, 7 and 14 days, the water in which each specimen had been immersed was evaluated to determine the pH level changes and calcium released. Flowability, pH level and calcium release data were analyzed statistically by the ANOVA test (α=5%). Results In relation to flowability: MTAF>AH Plus>MTAF5>MTAF10. In relation to the pH level, for 24 h: MTAF5=MTAF10=MTAF>AH Plus; for 7 and 14 days: MTAF5=MTAF10>MTAF>AH Plus. For the calcium release, for all periods: MTAF>MTAF5=MTAF10>AH Plus. Conclusions The addition of 5% CH to the MTA Fillapex (in weight) is an alternative to reduce the high flowability presented by the sealer, without interfering in its alkalization potential. PMID:25025558

The Role of Siliceous Hydrothermal Breccias in the Genesis of Volcanic Massive Sulphide Deposits - Ancient and Recent Systems

NASA Astrophysics Data System (ADS)

Costa, I. A.; Barriga, F. J.; Fouquet, Y.

2014-12-01

Siliceous hydrothermal breccias were sampled in two Mid-Atlantic Ridge active sites: Lucky Strike and Menez Gwen. These hydrothermal fields are located in the border of the Azorean plateau, southwest of the Azores islands where the alteration processes affecting basaltic rocks are prominent (Costa et al., 2003). The hydrothermal breccias are genetically related with the circulation of low temperature hydrothermal fluids in diffuse vents. The groundmass of these breccias precipitates from the fluid and consolidates the clastic fragments mostly composed of basalt. The main sources are the surrounding volcanic hills. Breccias are found near hydrothermal vents and may play an important role in the protection of subseafloor hydrothermal deposits forming an impermeable cap due to the high content in siliceous material. The amorphous silica tends to precipitate when the fluid is conductively cooled as proposed by Fouquet et al. (1998) after Fournier (1983). The process evolves gradually from an initial stage where we have just the fragments and circulating seawater. The ascending hydrothermal fluid mixes with seawater, which favours the precipitation of the sulphide components. Sealing of the initially loose fragments begins, the temperature rises below this crust, and the processes of mixing fluid circulation and conductive cooling are simultaneous. At this stage the fluid becomes oversaturated with respect to amorphous silica. This form of silica can precipitate in the open spaces of the porous sulphides and seal the system. Normally this can happen at low temperatures. At this stage the hydrothermal breccia is formed creating a progressively less permeable, eventually impermeable cap rock at the surface. Once the fluid is trapped under this impermeable layer, conductive cooling is enhanced and mixing with seawater is restricted, making the precipitation of amorphous silica more efficient. Since the first discovery and description of recent mineralized submarine hydrothermal deposits, comparison with ancient volcanic massive sulphide deposits is appropriate. The proposed model can explain some of the processes taking place in the early phase of formation of old deposits where equivalent siliceous material is found in the hanging wall of the ore bodies (e.g. Barriga and Fyfe, 1988).

Influence of Synthesis Mode of Supplement Based on Calcium Hydrosylicates on the Structure and Properties of Lime Compositions

NASA Astrophysics Data System (ADS)

Loganina, V. I.; Pyshkina, I. S.

2017-11-01

It was proposed to use synthesized calcium hydrosilicates in finishing lime dry mixes as a modifying supplement. The effect of substances containing amorphous silica which are used for synthesis on the activity of the modifying supplement was established. The effect of the synthesis mode of supplement on the structure formation of lime compositions was illustrated. It was found that the injection of supplements of hydrosilicates accelerates the increase of mechanical strength. The efficiency of the modifying supplements of amorphous silica, such as diatomite, in the synthesis was shown.

Effect of calcium source on structure and properties of sol-gel derived bioactive glasses.

PubMed

Yu, Bobo; Turdean-Ionescu, Claudia A; Martin, Richard A; Newport, Robert J; Hanna, John V; Smith, Mark E; Jones, Julian R

2012-12-18

The aim was to determine the most effective calcium precursor for synthesis of sol-gel hybrids and for improving homogeneity of sol-gel bioactive glasses. Sol-gel derived bioactive calcium silicate glasses are one of the most promising materials for bone regeneration. Inorganic/organic hybrid materials, which are synthesized by incorporating a polymer into the sol-gel process, have also recently been produced to improve toughness. Calcium nitrate is conventionally used as the calcium source, but it has several disadvantages. Calcium nitrate causes inhomogeneity by forming calcium-rich regions, and it requires high temperature treatment (>400 °C) for calcium to be incorporated into the silicate network. Nitrates are also toxic and need to be burnt off. Calcium nitrate therefore cannot be used in the synthesis of hybrids as the highest temperature used in the process is typically 40-60 °C. Therefore, a different precursor is needed that can incorporate calcium into the silica network and enhance the homogeneity of the glasses at low (room) temperature. In this work, calcium methoxyethoxide (CME) was used to synthesize sol-gel bioactive glasses with a range of final processing temperatures from 60 to 800 °C. Comparison is made between the use of CME and calcium chloride and calcium nitrate. Using advanced probe techniques, the temperature at which Ca is incorporated into the network was identified for 70S30C (70 mol % SiO(2), 30 mol % CaO) for each of the calcium precursors. When CaCl(2) was used, the Ca did not seem to enter the network at any of the temperatures used. In contrast, Ca from CME entered the silica network at room temperature, as confirmed by X-ray diffraction, (29)Si magic angle spinning nuclear magnetic resonance spectroscopy, and dissolution studies. CME should be used in preference to calcium salts for hybrid synthesis and may improve homogeneity of sol-gel glasses.

Irradiation Effects in Fosterrite and the Nature of Interstellar Grains: A Coordinated Spectroscopy and Electron Microscopy Study

NASA Technical Reports Server (NTRS)

Keller, Lindsay P.; Christoffersen, R.

2007-01-01

Crystalline and amorphous silicates condense in the outflows of low mass evolved stars and massive red supergiant stars and are injected into the interstellar medium (ISM) where they are rendered almost completely amorphous by a multitude of destructive processes (e.g. shock, grain-grain collisions, and irradiation). Irradiation effects in particular may have played an important role in the genesis and modification of primitive grains in cometary dust, but unraveling those effects requires controlled experiments under appropriate conditions and with an emphasis on materials relevant to the ISM. Here we report our infrared (IR) microspectroscopy and trans-mission electron microscope (TEM) measurements on forsterite that was amorphized through irradiation by high energy heavy ions.

HST-STIS spectra and the redness of Saturn's rings

NASA Astrophysics Data System (ADS)

Cuzzi, Jeffrey N.; French, Richard G.; Hendrix, Amanda R.; Olson, Daniel M.; Roush, Ted; Vahidinia, Sanaz

2018-07-01

We have observed the main rings of Saturn with the Space Telescope Imaging Spectrometer (STIS) on the Hubble Space Telescope (HST), covering the spectral region from 180-570 nm (including for the first time the critical near-UV range 190-340 nm) with very good signal to noise ratio and a radial resolution of approximately 160-330 km. After correcting for an unexpected grating scatter problem associated with the bright, red, extended planet-ring target, we obtained complete I/F spectra for each major ring region. We have interpreted the spectra in terms of the ring particle material composition using a combination of traditional "Hapke" theory and a new correction for shadowing on the rough, re-entrant ring particle surfaces, along with a correction for the nonclassical scattering of the ring layer itself. We tested a variety of UV absorbers: iron (including nano-iron) grains, hematite, "planetary silicates", organic carbon-ring tholins of varying aromaticity, and amorphous carbon. The A and B rings can contain no more NH3 than about 10-4 by volume. We conclude that the best spectral fit for the well-known, unusually red color of the A and B rings is provided by a sub-percent mass fraction of organic tholins. It appears that the most likely regolith configuration for the A and B Rings is a heterogeneous "intimate mixture", dominated by relatively pure water ice, with some 2-40% of the grains containing roughly 5-10% tholin by volume (the amount depending on whether silicates are present), but it is hard to allow much amorphous carbon to be present in the B Ring material at least. These predictions of compositional heterogeneity can be tested by Cassini direct compositional measurements. There is some suggestion that the tholin properties differ slightly between the A and B rings. We show that tholins of this type, in the abundance we predict, would be difficult to detect at near-IR wavelengths. The C Ring particles have lower albedos, and the best fit models require a significantly higher abundance of silicates and (more importantly) "neutral" absorber which we model as amorphous carbon, plausibly representing meteoritic infall. Because of our new treatment of shadowing, our estimates of the abundance of amorphous carbon in the C Ring particles are lower (1-5% in the particle regoliths) than previously obtained. The relative abundance of silicate and carbonaceous materials in the C Ring remains uncertain due to uncertainties in how to model the C ring particle phase function.

Overview of the amorphous precursor phase strategy in biomineralization

NASA Astrophysics Data System (ADS)

Weiner, Steve; Mahamid, Julia; Politi, Yael; Ma, Yurong; Addadi, Lia

2009-06-01

It was assumed for a long time that organisms produce minerals directly from a saturated solution. A few exceptions were known, including the well documented mineralized teeth of the chiton. In 1997 it was demon-strated that sea urchin larvae form their calcitic spicules by first depositing a highly unstable mineral phase called amorphous calcium carbonate. This strategy has since been shown to be used by animals from other phyla and for both aragonite and calcite. Recent evidence shows that vertebrate bone mineral may also be formed via a precursor phase of amorphous calcium carbonate. This strategy thus appears to be widespread. The challenge now is to understand the mechanisms by which these unstable phases are initially formed, how they are temporarily stabilized and how they are destabilized and transform into a crystalline mature product.

INNOVATIVE TECHNOLOGY FOR RECYCLING OF MANURE PHOSPHORUS WITH RAPID AMORPHOUS PHOSPHATE PRECIPITATION

EPA Science Inventory

Phosphorus (P) recovery from liquid swine manure is an attractive technology when soils in the farm are saturated with P and on-farm land application is not an option. A technology was developed for recovery of soluble P from liquid swine manure as amorphous calcium phosphate (AC...

Thermal infrared reflectance and emission spectroscopy of quartzofeldspathic glasses

USGS Publications Warehouse

Byrnes, J.M.; Ramsey, M.S.; King, P.L.; Lee, R.J.

2007-01-01

This investigation seeks to better understand the thermal infrared (TIR) spectral characteristics of naturally-occurring amorphous materials through laboratory synthesis and analysis of glasses. Because spectra of glass phases differ markedly from their mineral counterparts, examination of glasses is important to accurately determine the composition of amorphous surface materials using remote sensing datasets. Quantitatively characterizing TIR (5-25 ??m) spectral changes that accompany structural changes between glasses and mineral crystals provides the means to understand natural glasses on Earth and Mars. A suite of glasses with compositions analogous to common terrestrial volcanic glasses was created and analyzed using TIR reflectance and emission techniques. Documented spectral characteristics provide a basis for comparison with TIR spectra of other amorphous materials (glasses, clays, etc.). Our results provide the means to better detect and characterize glasses associated with terrestrial volcanoes, as well as contribute toward understanding the nature of amorphous silicates detected on Mars. Copyright 2007 by the American Geophysical Union.

Durability of pulp fiber-cement composites

NASA Astrophysics Data System (ADS)

Mohr, Benjamin J.

Wood pulp fibers are a unique reinforcing material as they are non-hazardous, renewable, and readily available at relatively low cost compared to other commercially available fibers. Today, pulp fiber-cement composites can be found in products such as extruded non-pressure pipes and non-structural building materials, mainly thin-sheet products. Although natural fibers have been used historically to reinforce various building materials, little scientific effort has been devoted to the examination of natural fibers to reinforce engineering materials until recently. The need for this type of fundamental research has been emphasized by widespread awareness of moisture-related failures of some engineered materials; these failures have led to the filing of national- and state-level class action lawsuits against several manufacturers. Thus, if pulp fiber-cement composites are to be used for exterior structural applications, the effects of cyclical wet/dry (rain/heat) exposure on performance must be known. Pulp fiber-cement composites have been tested in flexure to examine the progression of strength and toughness degradation. Based on scanning electron microscopy (SEM), environmental scanning electron microscopy (ESEM), energy dispersive spectroscopy (EDS), a three-part model describing the mechanisms of progressive degradation has been proposed: (1) initial fiber-cement/fiber interlayer debonding, (2) reprecipitation of crystalline and amorphous ettringite within the void space at the former fiber-cement interface, and (3) fiber embrittlement due to reprecipitation of calcium hydroxide filling the spaces within the fiber cell wall structure. Finally, as a means to mitigate kraft pulp fiber-cement composite degradation, the effects of partial portland cement replacement with various supplementary cementitious materials (SCMs) has been investigated for their effect on mitigating kraft pulp fiber-cement composite mechanical property degradation (i.e., strength and toughness losses) during wet/dry cycling. SCMs have been found to be effective in mitigating composite degradation through several processes, including a reduction in the calcium hydroxide content, stabilization of monosulfate by maintaining pore solution pH, and a decrease in ettringite reprecipitation accomplished by increased binding of aluminum in calcium aluminate phases and calcium in the calcium silicate hydrate (C-S-H) phase.

Ability of a beta-casein phosphopeptide to modulate the precipitation of calcium phosphate by forming amorphous dicalcium phosphate nanoclusters.

PubMed Central

Holt, C; Wahlgren, N M; Drakenberg, T

1996-01-01

The ability of casein in the form of colloidal-sized casein micelles to modulate the phase separation of calcium phosphate during milk secretion is adapted to produce nanometre-sized particles of calcium phosphate stabilized by a casein phosphopeptide (nanoclusters). The nanoclusters were prepared from an undersaturated solution of salts and the peptide by raising the pH homogeneously from about 5.5 to 6.7 with urea plus urease. Chemical analysis and IR spectroscopy showed that they comprise an amorphous dicalcium phosophate bound to the phosphopeptide. Multinuclear NMR spectroscopy of the cluster solutions showed that the small ions and free peptide in the solution were in a state of dynamic exchange with the nanoclusters. The peptide is linked to the calcium phosphate through its sequence of phosphorylated residues, but, in a proportion of adsorbed conformational states, the termini retain the conformational freedom of the unbound peptide. The ability of casein to form nanoclusters in milk suggests a more general mechanism for avoiding pathological calcification and regulating calcium flow in tissues and biological fluids exposed to or containing high concentrations of calcium. PMID:8615755

Structure and function of matrix proteins and peptides in the biomineral formation in crustaceans.

PubMed

Nagasawa, Hiromichi

2011-01-01

Crustaceans have hard cuticle with layered structure, which is composed mainly of chitin, proteins, and calcium carbonate. Crustaceans grow by shedding the old cuticle and replacing it with a new one. Decalcification in the cuticle during the pre-molt stage and concomitant calcification in the stomach to form gastroliths observed in some crustacean species are triggered by the molting hormone. Various proteins and peptides have been identified from calcified cuticle and gastroliths, and their functions have been examined in terms of calcification and interaction with chitin. Acidic nature of matrix proteins is important for recruitment of calcium ions and interaction with calcium carbonate. Examination of the relationship between amino acid sequence containing acidic amino acid residues and calcification inhibitory activity revealed that the potency did not depend on the sequence but on the number of acidic amino acid residues. Calcium carbonate in the calcified tissues of crustaceans is amorphous in many cases. Crustaceans take a strategy to induce and maintain amorphous calcium carbonate by using low-molecular-weight phosphorus compounds.

Application of Quantitative Analytical Electron Microscopy to the Mineral Content of Insect Cuticle

NASA Astrophysics Data System (ADS)

Rasch, Ron; Cribb, Bronwen W.; Barry, John; Palmer, Christopher M.

2003-04-01

Quantification of calcium in the cuticle of the fly larva Exeretonevra angustifrons was undertaken at the micron scale using wavelength dispersive X-ray microanalysis, analytical standards, and a full matrix correction. Calcium and phosphorus were found to be present in the exoskeleton in a ratio that indicates amorphous calcium phosphate. This was confirmed through electron diffraction of the calcium-containing tissue. Due to the pragmatic difficulties of measuring light elements, it is not uncommon in the field of entomology to neglect the use of matrix corrections when performing microanalysis of bulk insect specimens. To determine, firstly, whether such a strategy affects the outcome and secondly, which matrix correction is preferable, phi-rho (z) and ZAF matrix corrections were contrasted with each other and without matrix correction. The best estimate of the mineral phase was found to be given by using the phi-rho (z) correction. When no correction was made, the ratio of Ca to P fell outside the range for amorphous calcium phosphate, possibly leading to flawed interpretation of the mineral form when used on its own.

Synthesis of β-Calcium Pyrophosphate by sol-gel method

NASA Astrophysics Data System (ADS)

Windarti, T.; Taslimah; Haris, A.; Astuti, Y.; Darmawan, A.

2017-02-01

Beta calcium pyrophosphate [β-CPP, β-Ca2P2O7] can be used as bone graft extender in posterolateral lumbar fusion. In this research, β-CPP was synthesized by sol-gel method using phosphorus pentaoxide [P2O5] and calcium nitrate tetrahydrate [Ca(NO3)2.4H2O] as phosphorus and calcium precursors. The reaction was carried out in ethanol medium with Ca/P ratio of 1.67. After 21 hours of reaction and 20 hours of drying at 80°C, white powder of amorphous calcium phosphate (ACP) was produced. Transformation of ACP to β-CPP was undertaken by firring at 400-800°C for 8 hours. Transformations of amorphous to microcrystalline, semicrystalline and crystalline structures occur at 400, 600 and 800°C, respectively. The β-CPP with the crystallite size of 61.71 nm, Ca/P ratio of 0.89 and Ca/O ratio of 0.21 was achieved by firing at 800°C. Morphology changes due to firing in which irregular shape of β-CPP at 400° changed to regular cuboid at 600 °C and above.

Osteoblast response to zirconia-hybridized pyrophosphate-stabilized amorphous calcium phosphate

PubMed Central

Whited, Bryce M.; Skrtic, Drago; Love, Brian J.

2006-01-01

Calcium phosphate bioceramics, such as hydroxyapatite, have long been used as bone substitutes because of their proven biocompatibility and bone binding properties in vivo. Recently, a zirconia-hybridized pyrophosphate-stabilized amorphous calcium phosphate (Zr-ACP) has been synthesized, which is more soluble than hydroxyapatite and allows for controlled release of calcium and phosphate ions. These ions have been postulated to increase osteoblast differentiation and mineralization in vitro. The focus of this work is to elucidate the physicochemical properties of Zr-ACP and to measure cell response to Zr-ACP in vitro using a MC3T3-E1 mouse calvarial-derived osteoprogenitor cell line. Cells were cultured in osteogenic medium and mineral was added to culture at different stages in cell maturation. Culture in the presence of Zr-ACP showed significant increases in cell proliferation, alkaline phosphatase activity (ALP), and osteopontin (OPN) synthesis, whereas collagen synthesis was unaffected. In addition, calcium and phosphate ion concentrations and medium pH were found to transiently increase with the addition of Zr-ACP, and are hypothesized to be responsible for the osteogenic effect of Zr-ACP. PMID:16278876

An Observational Test for Shock-induced Crystallization of Cometary Silicates

NASA Technical Reports Server (NTRS)

Nuth, J. A.; Johnson, N. M.

2003-01-01

Crystalline silicates have been observed in comets and in protostellar nebulae, and there are currently at least two explanations for their formation: thermal annealing in the inner nebula, followed by transport to the regions of cometary formation and in-situ shock processing of amorphous grains at 5 - 10 AU in the Solar Nebula. The tests suggested to date to validate these models have not yet been carried out: some of these tests require a longterm commitment to observe both the dust and gas compositions in a large number of comets. Here we suggest a simpler test.

Solubility and bioavailability of stabilized amorphous calcium carbonate.

PubMed

Meiron, Oren E; Bar-David, Elad; Aflalo, Eliahu D; Shechter, Assaf; Stepensky, David; Berman, Amir; Sagi, Amir

2011-02-01

Since its role in the prevention of osteoporosis in humans was proven some 30 years ago, calcium bioavailability has been the subject of numerous scientific studies. Recent technology allowing the production of a stable amorphous calcium carbonate (ACC) now enables a bioavailability analysis of this unique form of calcium. This study thus compares the solubility and fractional absorption of ACC, ACC with chitosan (ACC-C), and crystalline calcium carbonate (CCC). Solubility was evaluated by dissolving these preparations in dilute phosphoric acid. The results demonstrated that both ACC and ACC-C are more soluble than CCC. Fractional absorption was evaluated by intrinsically labeling calcium carbonate preparations with (45)Ca, orally administrated to rats using gelatin capsules. Fractional absorption was determined by evaluating the percentage of the administrated radioactive dose per milliliter that was measured in the serum, calcium absorption in the femur, and whole-body retention over a 34-hour period. Calcium serum analysis revealed that calcium absorption from ACC and ACC-C preparations was up to 40% higher than from CCC, whereas retention of ACC and ACC-C was up to 26.5% higher than CCC. Absorbed calcium in the femurs of ACC-administrated rats was 30% higher than in CCC-treated animals, whereas 15% more calcium was absorbed following ACC-C treatment than following CCC treatment. This study demonstrates the enhanced solubility and bioavailability of ACC over CCC. The use of stable ACC as a highly bioavailable dietary source for calcium is proposed based on the findings of this study. Copyright © 2011 American Society for Bone and Mineral Research.

In-situ hybridization of calcium silicate and hydroxyapatite-gelatin nanocomposites enhances physical property and in vitro osteogenesis.

PubMed

Chiu, Chi-Kai; Lee, Dong Joon; Chen, Hsin; Chow, Laurence C; Ko, Ching-Chang

2015-02-01

Low mechanical strengths and inadequate bioactive material-tissue interactions of current synthetic materials limit their clinical applications in bone regeneration. Here, we demonstrate gelatin modified siloxane-calcium silicate (GEMOSIL-CS), a nanocomposite made of gelatinous hydroxyapatite with in situ pozzolanic formation of calcium silicate (CS) interacting among gelatin, silica and Calcium Hydroxide (Ca(OH)2). It is shown the formation of CS matrices, which chemically bonds to the gelatinous hydroxyapatite, provided hygroscopic reinforcement mechanism and promoted both in vitro and in vivo osteogenic properties of GEMOSIL-CS. The formation of CS was identified by Fourier transform infrared spectroscopy (FTIR) and powder X-ray diffraction. The interfacial bindings within nanocomposites were studied by FTIR and thermogravimetric analysis. Both gelatin and CS have been found critical to the structure integrity and mechanical strengths (93 MPa in compressive strength and 58.9 MPa in biaxial strength). The GEMOSIL-CS was biocompatible and osteoconductive as result of type I collagen secretion and mineralized nodule formation from MC3T3 osteoblasts. SEM and TEM indicated the secretion of collagen fibers and mineral particles as the evidence of mineralization in the early stage of osteogenic differentiation. In vivo bone formation capability was performed by implanting GEMOSIL-CS into rat calvarial defects for 12 weeks and the result showed comparable new bone formation between GEMOSIL-CS group (20%) and the control (20.19%). The major advantage of GEMOSIL-CS composites is in situ self-hardening in ambient or aqueous environment at room temperature providing a simple, fast and cheap method to produce porous scaffolds.

Insights into Silicate and Oxide Melt Structure from Amorphous, Non-Glass-Forming Materials

NASA Astrophysics Data System (ADS)

Stebbins, J. F.

2015-12-01

Many silicate and oxide liquids of interest in the Earth sciences and in technology cannot readily be quenched to glasses, either because of low silica contents (and hence low viscosity at the melting point and accompanying liquid 'fragility') or because of liquid-liquid unmixing at high temperature. Although in-situ, high temperature structural tools have been in use for decades and are rapidly developing, many methods are still most informative for glass samples quenched to ambient pressure and temperature, e.g. high-resolution solid-state NMR. Amorphous oxides, including alumina and silicate compositions, have widespread technological applications. These are generally deposited by a variety of high-energy sputtering methods, as films of thicknesses of 10's to 100's of nm. Using Al-27, Si-29, and O-17 NMR, we have recently shown that for such films, very similar short-range structure is seen in materials made by very different kinetic pathways, such as sol-gel synthesis vs. ion-beam sputtering. This path-independent structure suggests that these materials pass through transient equilibrium states during their formation, probably that of deeply supercooled liquids just above glass transition temperatures. In the HfO2-SiO2 and ZrO2-SiO2 systems, for example, samples have well-resolved O-17 NMR spectra, allowing quantitation of O sites with only Hf(Zr) neighbors (so-called "free" oxide ions), with mixed Hf(Zr) and Si neighbors, and Si only. The observed oxygen speciation agrees well with a simple thermodynamic model of one of the most fundamental equilibria in silicate systems, namely the reaction of bridging (Si-O-Si) and "free" (e.g. OHf3 and OHf4) oxide ions to produce "non-bridging" oxygens (e.g. Si-OHf2). This new approach to sampling such structural equilibria in compositions far outside the range of normal glass-forming liquids may provide new insights into more geological compositions as well, as well as in more general models of silicate melt chemistry.

Experimental constraints on the degree of melting beneath tectonic plates

NASA Astrophysics Data System (ADS)

Clark, A. N.; Lesher, C. E.

2017-12-01

Determining the volume and geometric distribution of silicate melts is fundamentally important to understand the current structure of the Earth as well as the dynamics of the Earth's interior. Regions in the upper mantle and crust that have lower velocities than the 1D global average are commonly attributed to the presence of silicate melts. Constraining melt fraction and distribution from seismic data requires a robust equation of state for silicate melts. Commonly, silicate melts are modeled at high pressure using equations of state developed for crystalline materials (e.g. the Birch-Murnaghan equation of state). However, amorphous silicates (glasses and melts), which lack long-range ordering, violate Birch's law at high pressures and high temperatures (Clark et al., 2016). We present a new model for seismic velocity reductions that accounts for the violation of Birch's law (anomalous compressibility) observed in amorphous silicates, rendering compressional wave velocities more sensitive to melt fraction and distribution than previous estimates. Forward modeling that combines our experimental data with the analytical solution of Takei (2002) predicts comparable velocity reductions for compressional and shear waves for partially molten mantle. Additionally, models that use crystalline equations of state to determine melt fraction at high pressure may overestimate melt fraction by 20% at pressures corresponding to the lithosphere-asthenosphere boundary (LAB) with the overestimation increasing with depth (e.g. a factor of 2 at the transition zone). By applying our results to recent seismic studies below the western Pacific plate that have reported low velocity regions associated with the lithosphere - asthenosphere boundary (LAB), we predict melt present at <5% distributed in near-textural equilibrium. These findings reconcile seismic observations for the LAB regionally and locally, and favor models of strong coupling across the LAB rather than melt channeling due to shear deformation. Clark, A. N., Lesher, C. E., Jacobsen, S. D., and Wang, Y., 2016, Journal of Geophysical Research: Solid Earth, v. 121, no. 6, p. 4232-4248. Takei, Y., 2002, Journal of Geophysical Research: Solid Earth (1978-2012), v. 107, no. B2, p. 6-12.

Structure and physical stability of hydrates and thermotropic mesophase of calcium benzoate.

PubMed

Terakita, Akira; Byrn, Stephen R

2006-05-01

The aim of this study is to investigate the hydration and the dehydration processes of calcium benzoate hydrates (trihydrate and monohydrate), thermotropic mesophases (dehydrated mesophase and lyophilized mesophase) and amorphous state, and the influence of their molecular order on those processes. X-ray analysis revealed that trihydrate has a planar structure composed of two types of planes-one from benzoic acid, water, and calcium ion and another from benzoic acid and water-and that both planes are linked by three water molecules. It was found that calcium benzoate was able to exist as thermotropic mesophases by dehydration of trihydrate and lyophilization. These mesophases were characterized by polarizing-light microscopy (PLM), X-ray powder diffraction (XRPD), differential thermal analysis (DTA), thermogravimetric analysis (TGA), and scanning electron microscopy (SEM). Both mesophases prepared by two procedures showed some similar physical properties, but lyophilized mesophase seemed to have molecular structure with higher order than dehydrated mesophase. The mesophases exhibited different hydration behavior. The dehydrated mesophase showed a stepwise rehydration process where it became monohydrate first and then trihydrate. The lyophilized mesophase became trihydrate without appearance of monohydrate. An amorphous form could also be prepared and it rehydrated first to the monohydrate and then trihydrate. The results suggest that the more disordered dehydrated mesophase and amorphous state change to monohydrate whereas the more ordered lyophilized mesophase cannot change to monohydrate but only to trihydrate.

Water quality characterization in some birimian aquifers of the Birim Basin, Ghana

USGS Publications Warehouse

Bruce, B.-Y.; Yidana, S.M.; Anku, Y.; Akabzaa, T.; Asiedu, D.

2009-01-01

The objective of this study was to determine the main controls on the hydrochemistry of groundwater in the study area. Mass balance modeling was used simultaneously with multivariate R-mode hierarchical cluster analysis to determine the significant sources of variation in the hydrochemistry. Two water types have been revealed in this area: (1) waters influenced more significantly by the weathering of silicate minerals from the underlying geology, and are rich in silica, sodium, calcium, bicarbonate, and magnesium ions, and (2) waters that have been influenced by the effects of fertilizers and other anthropogenic activities in the area. Mineral speciation and silicate mineral stability diagrams generated from the data suggest that montmorillonite, probably derived from the incongruent dissolution of feldspars and micas, is the most stable silicate phase in the groundwater. The apparent incongruent weathering of silicate minerals in the groundwater system has led to the enrichment of sodium, calcium, magnesium and bicarbonate ions as well as silica, leading to the supersaturation of calcite, aragonite, dolomite and quartz. Stability in the montmorillonite field suggests restricted flow conditions whereby groundwater residence time is relatively high, leading to greater contact of groundwater with the rock to enhance weathering. Cation exchange processes have also been determined to play minor roles in the hydrochemistry.

Spectroscopic study of biologically active glasses

NASA Astrophysics Data System (ADS)

Szumera, M.; Wacławska, I.; Mozgawa, W.; Sitarz, M.

2005-06-01

It is known that the chemical activity phenomenon is characteristic for some inorganic glasses and they are able to participate in biological processes of living organisms (plants, animals and human bodies). An example here is the selective removal of silicate-phosphate glass components under the influence of biological solutions, which has been applied in designing glasses acting as ecological fertilizers of controlled release rate of the nutrients for plants. The structure of model silicate-phosphate glasses containing the different amounts of the glass network formers, i.e. Ca 2+ and Mg 2+, as a binding components were studied. These elements besides other are indispensable of the normal growth of plants. In order to establish the function and position occupied by the particular components in the glass structure, the glasses were examined by FTIR spectroscopy (with spectra decomposition) and XRD methods. It has been found that the increasing amount of MgO in the structure of silicate-phosphate glasses causes the formation of domains the structure of which changes systematically from a structure of the cristobalite type to a structure corresponding to forsterite type. Whilst the increasing content of CaO in the structure of silicate-phosphate glasses causes the formation of domains the structure of which changes from a structure typical for cristobalite through one similar to the structure of calcium orthophosphate, to a structure corresponding to calcium silicates. The changing character of domains structure is the reason of different chemical activity of glasses.

Cytotoxicities and genotoxicities of cements based on calcium silicate and of dental formocresol.

PubMed

Ko, Hyunjung; Jeong, Youngdan; Kim, Miri

2017-03-01

Increasing interest is being paid to the toxicities of dental materials. The purpose of this study was to determine the cytotoxicities and genotoxicities of endodontic compounds to Chinese hamster ovary (CHO-K1) reproductive cells. Cultured CHO-K1 cells were treated with dental formocresol, two types of calcium hydroxide paste, and two types of mineral trioxide aggregate cement for 24h. A 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide assay was performed on each culture, and the micronucleus frequency was determined by performing a micronucleus assay. Alkaline comet assay and γ-H2AX immunofluorescence assay were used to detect DNA damage. Out of the five materials tested, only dental formocresol significantly increased DNA damage. The mineral trioxide aggregate cements based on calcium silicate were not found to be potentially genotoxic. The data suggest that dental formocresol should not be recommended for use in vital pulp therapy on young teeth. Copyright © 2017 Elsevier B.V. All rights reserved.

Effect of amorphous phases during the hydraulic conversion of α-TCP into calcium-deficient hydroxyapatite.

PubMed

Hurle, Katrin; Neubauer, Juergen; Bohner, Marc; Doebelin, Nicola; Goetz-Neunhoeffer, Friedlinde

2014-09-01

Powders of α-tricalcium phosphate (α-TCP), which readily react with water to form calcium-deficient hydroxyapatite (CDHA), are frequently used in bone cements. As, for clinical applications, it is important to adjust the setting reaction of the cements to a reasonable reaction time, exact knowledge of the hydration mechanism is essential. It is known that prolonged milling results in partial amorphization of α-TCP powders and that dissolution of the amorphous phase significantly accelerates the hydration, but it is not clear yet when the amorphous phase reacts in comparison to the crystalline α-TCP. Therefore the aim of this study was to investigate the development of quantitative phase content of α-TCP samples during hydration. For this purpose, three α-TCP powders, containing 0, 16 and 71wt.% of amorphous phase (ATCP), were mixed with either deionized water or a 0.1M Na2HPO4 aqueous solution. The crystalline evolution of the paste was assessed quantitatively during the first 48h of hydration at 23°C by G-factor quantification. The present investigations demonstrate that ATCP reacted earlier than crystalline α-TCP. The results also suggest the formation of an X-ray amorphous phase during the hydraulic conversion formation of α-TCP into CDHA. Copyright © 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Iron (III) Matrix Effects on Mineralization and Immobilization of Actinides

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

Cynthia-May S. Gong; Tyler A. Sullens; Kenneth R. Czerwinski

2006-01-01

Abstract - A number of models for the Yucca Mountain Project nuclear waste repository use studies of actinide sorption onto well-defined iron hydroxide materials. In the case of a waste containment leak, however, a complex interaction between dissolved waste forms and failed containment vessel components can lead to immediate precipitation of migratory iron and uranyl in the silicate rich near-field environment. Use of the Fe(III) and UO22+ complexing agent acetohydroxamic acid (AHA) as a colorimetric agent for visible spectrophotometry is well-known. Using the second derivative of these spectra a distinct shift in iron complexation in the presence of silicate ismore » seen that is not seen with uranyl or alone. Silica also decreases the ability of uranyl and ferric solutions to absorb hydroxide, hastening precipitation. These ferric silicate precipitates are highly amorphous and soluble. Precipitates formed in the presence of uranyl below ~1 mol% exhibit lower solubility than precipitates from up to 50 mol % and of uranyl silicates alone.« less

Insights into the martian hydrosphere from the nakhlites

NASA Astrophysics Data System (ADS)

Tomkinson, T.; Mark, D. F.; Lee, M.; Lindgren, P.; Stuart, F.

2011-12-01

The nakhlite meteorites contain minerals including clays, salts and carbonates that crystallized from water within an impact-induced hydrothermal system or subsurface aquifer [1,2]. These minerals can be used to explore the longevity, scale and evolution of the aqueous system. However, such work has proven to be challenging owing to their very fine crystal size and their compositional complexity. In this study we have used a suite of techniques including CT tomography, scanning and transmission electron microscopy and Ar/Ar dating to explore the history of secondary mineralization in the nakhlites. In total there are thirteen nakhlites, however, this study has focused on Nakhla as it is the only fall. To further understand their alteration relationships we also plan to study Lafayette, MIL 003346, Yamato 000593, 000749 and NWA 5790. In contrast to previous studies that have used polished thin sections, we have examined secondary minerals exposed on freshly produced fracture surfaces from the interior of the Nakhla meteorite. This technique has revealed six textures that have not previously been described. (1) Areas of nanocrystalline/amorphous growth of sheeted silicates appearing to nucleate from underlying Cl and C rich fibrous material. (2) Underlying material which forms on the olivine grains surface with a nanoscale fibrous structure contains intergrown <5 μm sized euhedral calcium sulphate crystals. (3) The overlying sheeted silicates are also cross-cut by veins of this Cl and C enriched fibrous material. (4) A concentrically Si, Cl, Ca, Mn and Fe zoned region of alteration with a diameter of ~90 μm that has also been observed potentially sourcing enrichments from an underlying halite grain and augite and magnetite inclusions formed from symplectic exsolution in the host olivine [3]. Additionally, we have observed (5) radial growth structures emanating from halite grains and (6) etch pits in the surfaces of olivines. We will also present preliminary Ar/Ar ages for the K-bearing alteration material within the nakhlites. The textures that we have observed suggest that the sheeted silicate material formed either during fluctuations in fluid compositions or as a result of these newly discovered sites of nucleation growth from the underlying Cl and C enriched fibrous material. The presence of the fibrous material cross-cutting the silicate could indicate the following: a subsequent injection of a saline fluid, an expansion of the fibrous material rupturing the silicate, or the remobilisation of the fibrous material. The sharp contacts of the silicate with these cross cutting veins of fibrous material suggest that this material (likely brine) was exposed to only very low temperatures [4] thus not remobilising and equilibrating with the surrounding material. Some of the features that we have found would have been lost in conventional thin section manufacture and may explain why they have not been observed previously.

Silicate Mineralogy of the Dust in the Inner Coma of Comet C/1995 01 (Hale-Bopp) Pre- and Post-Perihelion

NASA Technical Reports Server (NTRS)

Wooden, Diane H.; Harker, David E.; Woodward, Charles E.; Butner, Harold M.; Koike, Chiyoe; Witteborn, Fred C.; McMurtry, Craig M.

1998-01-01

We present 7.6 - 13.3 microns infrared (IR) spectrophotometry (R approx. = 180 - 350) of the 10 microns silicate emission from dust in the inner coma (i.e., within a diameter of 3in.) of comet C/1995 O1 (Hale-Bopp) at four temporal epochs from 1996 October through 1997 June during Hale-Bopp s approach to, arrival at, and recession from perihelion. The HIFOGS spectra at large heliocentric distances exhibit strong emission peaks from 9.9 - 10.1 microns and at 11.2 microns. The HIFOGS spectra of Hale-Bopp taken 1996 October 07 - 14 UT are identical in shape to the ISO SWS spectrum at 2.8 AU obtained on 1996 October 06 UT. Magnesium-rich olivine was unambiguously identified due to presence of the expected 11.2 microns peak along with the matching far-IR 18 microns, 23 microns, and 33 microns peaks in the ISO SWS spectrum. In contrast, to large heliocentric distances, we find that the silicate feature at small heliocentric distances (tau(sub lambda) less than or = 1.7 AU) exhibits strong peaks at 9.3 microns, 9.9 - 10.1 microns, and 11.2 microns, and weak at 10.5 microns and 11.8 microns. We will show that the dramatic increase of the 9.3 microns and 10.0 microns peaks close to perihelion leads to the hypothesis that there are two crystalline grain components with significantly different temperatures. The hotter mineral species (including olivines) radiate over a large range of heliocentric distances at detectable leve!s. The cooler mineral species (pyroxenes) radiate on the Wien side of the blackbody, too faint to detect in the mid-infrared spectra, until close to the sun when this species radiates on the Reyleigh-Jeans tail and becomes apparent. Decomposition of the observed silicate emission features into mineral components through comparison of the height and shape of the silicate feature ("Flux/cont") derived from the cometary spectra, to optical extinctions (Qext) derived from laboratory measurements of terrestrial silicate minerals and interplanetary dust particles (IDPs) is successful for a combination of warm grains (consisting of olivines, amorphous olivines, amorphous pyroxenes, and layer-lattice silicates) and cool grains (crystalline pyroxenes).

Transmission electron microscopy of coatings formed by plasma electrolytic oxidation of titanium.

PubMed

Matykina, E; Arrabal, R; Skeldon, P; Thompson, G E

2009-05-01

Transmission electron microscopy and supporting film analyses are used to investigate the changes in composition, morphology and structure of coatings formed on titanium during DC plasma electrolytic oxidation in a calcium- and phosphorus-containing electrolyte. The coatings are of potential interest as bioactive surfaces. The initial barrier film, of mixed amorphous and nanocrystalline structure, formed below the sparking voltage of 180 V, incorporates small amounts of phosphorus and calcium species, with phosphorus confined to the outer approximately 63% of the coating thickness. On commencement of sparking, calcium- and phosphorus-rich amorphous material forms at the coating surface, with local heating promoting crystallization in underlying and adjacent anodic titania. The amorphous material thickens with increased treatment time, comprising almost the whole of the approximately 5.7-microm-thick coating formed at 340 V. At this stage, the coating is approximately 4.4 times thicker than the oxidized titanium, with a near-surface composition of about 12 at.% Ti, 58 at.% O, 19 at.% P and 11 at.% Ca. Further, the amount of titanium consumed in forming the coating is similar to that calculated from the anodizing charge, although there may be non-Faradaic contributions to the coating growth.

High chloride content calcium silicate glasses.

PubMed

Chen, Xiaojing; Karpukhina, Natalia; Brauer, Delia S; Hill, Robert G

2017-03-08

Chloride is known to volatilize from silicate glass melts and until now, only a limited number of studies on oxychloride silicate glasses have been reported. In this paper we have synthesized silicate glasses that retain large amounts of CaCl 2 . The CaCl 2 has been added to the calcium metasilicate composition (CaO·SiO 2 ). Glasses were produced via a melt quench route and an average of 70% of the chloride was retained after melting. Up to 31.6 mol% CaCl 2 has been successfully incorporated into these silicate glasses without the occurrence of crystallization. 29 Si MAS-NMR spectra showed the silicon being present mainly as a Q 2 silicate species. This suggests that chloride formed Cl-Ca(n) species, rather than Si-Cl bonds. Upon increasing the CaCl 2 content, the T g reduced markedly from 782 °C to 370 °C. Glass density and glass crystallization temperature decreased linearly with an increase in the CaCl 2 content. However, both linear regressions revealed a breakpoint at a CaCl 2 content just below 20 mol%. This might be attributed to a significant change in the structure and is also correlated with the nature of the crystallizing phases formed upon heat treatment. The glasses with less than 19.2 mol% CaCl 2 crystallized to wollastonite, whilst the compositions with CaCl 2 content equal to or greater than 19.2 mol% are thought to crystallize to CaCl 2 . In practice, the crystallization of CaCl 2 could not occur until the crystallization temperature fell below the melting point of CaCl 2 . The implications of the results along with the high chloride retention are discussed.

Microstructure and mechanical properties of stainless steel/calcium silicate composites manufactured by selective laser melting.

PubMed

Zheng, Zeng; Wang, Lianfeng; Jia, Min; Cheng, Lingyu; Yan, Biao

2017-02-01

Selective laser melting (SLM) is raised as one kind of additive manufacturing (AM) which is based on the discrete-stacking concept. This technique can fabricate advanced composites with desirable properties directly from 3D CAD data. In this research, 316L stainless steel (316L SS) and different fractions of calcium silicate (CaSiO 3 ) composites (weight fractions of calcium silicate are 0%, 5%,10% and 15%, respectively) were prepared by SLM technique with a purpose to develop biomedical metallic materials. The relative density, tensile, microhardness and elastic modulus of the composites were tested, their microstructures and fracture morphologies were observed using optical microscope (OM), scanning electron microscopy (SEM) and X-ray diffraction (XRD). It was found that the addition of CaSiO 3 particles influenced the microstructure and mechanical properties of specimens significantly. The CaSiO 3 precipitates from the overlap of adjacent tracks and became the origin of the defects. The tensile strength of specimens range 320-722MPa. The microhardness and elastic modulus are around 250HV and 215GPa respectively. These composites were ductile materials and the fracture mode of the composites was mixed mode of ductile and brittle fracture. The 316L SS/CaSiO 3 composites can be a potential biomedical metallic materials in the medical field. Copyright © 2016. Published by Elsevier B.V.

Experimental Calcium Silicate-Based Cement with and without Zirconium Oxide Modulates Fibroblasts Viability.

PubMed

Slompo, Camila; Peres-Buzalaf, Camila; Gasque, Kellen Cristina da Silva; Damante, Carla Andreotti; Ordinola-Zapata, Ronald; Duarte, Marco Antonio Hungaro; de Oliveira, Rodrigo Cardoso

2015-01-01

The aim of this study was to verify whether the use of zirconium oxide as a radiopacifier of an experimental calcium silicate-based cement (WPCZO) leads to cytotoxicity. Fibroblasts were treated with different concentrations (10 mg/mL, 1 mg/mL, and 0.1 mg/mL) of the cements diluted in Dulbecco's modified Eagle's medium (DMEM) for periods of 12, 24, and 48 h. Groups tested were white Portland cement (WPC), white Portland cement with zirconium oxide (WPCZO), and white mineral trioxide aggregate Angelus (MTA). Control group cells were not treated. The cytotoxicity was evaluated through mitochondrial-activity (MTT) and cell-density (crystal violet) assays. All cements showed low cytotoxicity. In general, at the concentration of 10 mg/mL there was an increase in viability of those groups treated with WPC and WPCZO when compared to the control group (p<0.05). A similar profile for the absorbance values was noted among the groups: 10 mg/mL presented an increase in viability compared to the control group. On the other hand, smaller concentrations presented a similar or lower viability compared to the control group, in general. A new dental material composed of calcium silicate-based cement with 20% zirconium oxide as the radiopacifier showed low cytotoxicity as a promising material to be exploited for root-end filling.

Calcium Silicate/Chitosan-Coated Electrospun Poly (Lactic Acid) Fibers for Bone Tissue Engineering.

PubMed

Su, Chu-Jung; Tu, Ming-Gene; Wei, Li-Ju; Hsu, Tuan-Ti; Kao, Chia-Tze; Chen, Tsui-Han; Huang, Tsui-Hsien

2017-05-05

Electrospinning technology allows fabrication of nano- or microfibrous fibers with inorganic and organic matrix and it is widely applied in bone tissue engineering as it allows precise control over the shapes and structures of the fibers. Natural bone has an ordered composition of organic fibers with dispersion of inorganic apatite among them. In this study, poly (lactic acid) (PLA) mats were fabricated with electrospinning and coated with chitosan (CH)/calcium silicate (CS) mixer. The microstructure, chemical component, and contact angle of CS/CH-PLA composites were analyzed by scanning electron microscopy, X-ray diffraction, and Fourier transform infrared spectroscopy. In vitro, various CS/CH-coated PLA mats increased the formation of hydroxyapatite on the specimens' surface when soaked in cell cultured medium. During culture, several biological characteristics of the human mesenchymal stem cells (hMSCs) cultured on CS/CH-PLA groups were promoted as compared to those on pure PLA mat. Increased secretion levels of Collagen I and fibronectin were observed in calcium silicate-powder content. Furthermore, with comparison to PLA mats without CS/CH, CS10 and CS15 mats markedly enhanced the proliferation of hMSCs and their osteogenesis properties, which was characterized by osteogenic-related gene expression. These results clearly demonstrated that the biodegradable and electroactive CS/CH-PLA composite mats are an ideal and suitable candidate for bone tissue engineering.

Electron Microscopic Analysis of Surface Inorganic Substances on Oral and Combustible Tobacco Products.

PubMed

Halstead, Mary M; Watson, Clifford H; Pappas, R Steven

2015-01-01

Although quantitative trace toxic metal analyses have been performed on tobacco products, little has been published on inorganic particulate constituents on and inside the products. We analyzed these constituents using scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDS). The nature of SEM-EDS instrumentation makes it an ideal choice for inorganic particulate analyses and yields relevant information to potential exposures during consumption of oral tobacco products, and possibly as a consequence of smoking. Aluminum silicates, silica and calcium compounds were common inorganic particulate constituents of tobacco products. Aluminum silicates and silica from soil were found on external leaf surfaces. Phytolithic silica, found in the lumen of the plant leaf, is of biogenic origin. Calcium oxalate was also apparently of biogenic origin. Small mineral deposits on tobacco could have health implications. Minerals found on the surfaces of smokeless tobacco products could possibly abrade the oral mucosa and contribute to the oral inflammatory responses observed with smokeless tobacco product use. If micron and sub-micron size calcium particles on cigarette filler were transported in mainstream smoke, they could potentially induce a pulmonary irritant inflammation when inhaled. The transport of aluminum silicate and silica in smoke could potentially also contribute to chronic inflammatory disease. Published by Oxford University Press 2015. This work is written by (a) US Government employee(s) and is in the public domain in the US.

Reconstruction of radial bone defect in rat by calcium silicate biomaterials.

PubMed

Oryan, Ahmad; Alidadi, Soodeh

2018-05-15

Despite many attempts, an appropriate therapeutic method has not yet been found to enhance bone formation, mechanical strength and structural and functional performances of large bone defects. In the present study, the bone regenerative potential of calcium silicate (CS) biomaterials combined with chitosan (CH) as calcium silicate/chitosan (CSC) scaffold was investigated in a critical radial bone defect in a rat model. The bioimplants were bilaterally implanted in the defects of 20 adult Sprague-Dawley rats. The rats were euthanized and the bone specimens were harvested at the 56th postoperative day. The healed radial bones were evaluated by three-dimensional CT, radiology, histomorphometric analysis, biomechanics, and scanning electron microscopy. The XRD analysis of the CS biomaterial showed its similarity to wollastonite (β-SiCO 3 ). The degradation rate of the CSC scaffold was much higher and it induced milder inflammatory reaction when compared to the CH alone. More bone formation and higher biomechanical performance were observed in the CSC treated group in comparison with the CH treated ones in histological, CT scan and biomechanical examinations. Scanning electron microscopic observation demonstrated the formation of more hydroxyapatite crystals in the defects treated with CSC. This study showed that the CSC biomaterials could be used as proper biodegradable materials in the field of bone reconstruction and tissue engineering. Copyright © 2018 Elsevier Inc. All rights reserved.

Chitosan-coated mesoporous microspheres of calcium silicate hydrate: environmentally friendly synthesis and application as a highly efficient adsorbent for heavy metal ions.

PubMed

Zhao, Jing; Zhu, Ying-Jie; Wu, Jin; Zheng, Jian-Qiang; Zhao, Xin-Yu; Lu, Bing-Qiang; Chen, Feng

2014-03-15

Chitosan-coated calcium silicate hydrate (CSH/chitosan) mesoporous microspheres formed by self-assembly of nanosheets have been synthesized in aqueous solution under ambient conditions without using any toxic surfactant or organic solvent. The method reported herein has advantages of simplicity, low cost and being environmentally friendly. The BET specific surface area of CSH/chitosan mesoporous microspheres is measured to be as high as ~356 m(2) g(-1), which is considerably high among calcium silicate materials. The as-prepared CSH/chitosan mesoporous microspheres are promising adsorbent and exhibit a quick and highly efficient adsorption behavior toward heavy metal ions of Ni(2+), Zn(2+), Cr(3+), Pb(2+) Cu(2+) and Cd(2+) in aqueous solution. The adsorption kinetics can be well fitted by the pseudo second-order model. The maximum adsorption amounts of Ni(2+), Zn(2+), Pb(2+), Cu(2+) and Cd(2+) on CSH/chitosan mesoporous microspheres are extremely high, which are 406.6, 400, 796, 425 and 578 mg/g, respectively. The CSH/chitosan adsorbent exhibits the highest affinity for Pb(2+) ions among five heavy metal ions. The adsorption capacities of the CSH/chitosan adsorbent toward heavy metal ions are relatively high compared with those reported in the literature. Copyright © 2013 Elsevier Inc. All rights reserved.

Dynamical behaviors of structural, constrained and free water in calcium- and magnesium-silicate-hydrate gels

DOE PAGES

Le, Peisi; Fratini, Emiliano; Ito, Kanae; ...

2016-01-28

We present the hypothesis that the mechanical properties of cement pastes depend strongly on their porosities. In a saturated paste, the porosity links to the free water volume after hydration. Structural water, constrained water, and free water have different dynamical behavior. Hence, it should be possible to extract information on pore system by exploiting the water dynamics. With our experiments we investigated the slow dynamics of hydration water confined in calcium- and magnesium-silicate-hydrate (C-S-H and M-S-H) gels using high-resolution quasi-elastic neutron scattering (QENS) technique. C-S-H and M-S-H are the chemical binders present in calcium rich and magnesium rich cements. Wemore » measured three M-S-H samples: pure M-S-H, M-S-H with aluminum-silicate nanotubes (ASN), and M-S-H with carboxyl group functionalized ASN (ASN-COOH). A C-S-H sample with the same water content (i.e. 0.3) is also studied for comparison. We found that structural water in the gels contributes to the elastic component of the QENS spectrum, while constrained water and free water contribute the quasi-elastic component. The quantitative analysis suggests that the three components vary for different samples and indicate the variance in the system porosity, which controls the mechanical properties of cement pastes.« less

TheraCal LC: From Biochemical and Bioactive Properties to Clinical Applications

PubMed Central

Rabi, Tarek

2018-01-01

Background Direct pulp capping is a popular treatment modality among dentists. TheraCal LC is a calcium silicate-based material that is designed as a direct/indirect pulp capping material. The material might be very attractive for clinicians because of its ease of handling. Unlike other calcium silicate-based materials, TheraCal LC is resin-based and does not require any conditioning of the dentine surface. The material can be bonded with different types of adhesives directly after application. There has been considerable research performed on this material since its launching; however, there are no review articles that collates information and data obtained from these studies. This review discusses the various characteristics of the material with the aim of establishing a better understanding for its clinical use. Methods A search was conducted using search engines (PubMed and Cochrane databases) in addition to reference mining of the articles that was used to locate other papers. The process of searching for the relevant studies was performed using the keywords pulp protection, pulp capping, TheraCal, and calcium silicates. Only articles in English published in peer-reviewed journals were included in the review. Conclusion This review underlines the fact that further in vitro and in vivo studies are required before TheraCal LC can be used as a direct pulp capping material. PMID:29785184

Compressive strength and magnetic properties of calcium silicate-zirconia-iron (III) oxide composite cements

NASA Astrophysics Data System (ADS)

Ridzwan, Hendrie Johann Muhamad; Shamsudin, Roslinda; Ismail, Hamisah; Yusof, Mohd Reusmaazran; Hamid, Muhammad Azmi Abdul; Awang, Rozidawati Binti

2018-04-01

In this study, ZrO2 microparticles and γ-Fe2O3 nanoparticles have been added into calcium silicate based cements. The purpose of this experiment was to investigate the compressive strength and magnetic properties of the prepared composite cement. Calcium silicate (CAS) powder was prepared by hydrothermal method. SiO2 and CaO obtained from rice husk ash and limestone respectively were autoclaved at 135 °C for 8 h and sintered at 950°C to obtain CAS powder. SiO2:CaO ratio was set at 45:55. CAS/ZrO2 sample were prepared with varying ZrO2 microparticles concentrations by 0-40 wt. %. Compressive strength value of CAS/ZrO2 cements range from 1.44 to 2.44 MPa. CAS/ZrO2/γ-Fe2O3 sample with 40 wt. % ZrO2 were prepared with varying γ-Fe2O3 nanoparticles concentrations (1-5 wt. %). The additions of γ-Fe2O3 nanoparticles showed up to twofold increase in the compressive strength of the cement. X-Ray diffraction (XRD) results confirm the formation of mixed phases in the produced composite cements. Vibrating sample magnetometer (VSM) analysis revealed that the ferromagnetic behaviour has been observed in CAS/ZrO2/γ-Fe2O3 composite cements.

Dynamical behaviors of structural, constrained and free water in calcium- and magnesium-silicate-hydrate gels

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

Le, Peisi; Fratini, Emiliano; Ito, Kanae

We present the hypothesis that the mechanical properties of cement pastes depend strongly on their porosities. In a saturated paste, the porosity links to the free water volume after hydration. Structural water, constrained water, and free water have different dynamical behavior. Hence, it should be possible to extract information on pore system by exploiting the water dynamics. With our experiments we investigated the slow dynamics of hydration water confined in calcium- and magnesium-silicate-hydrate (C-S-H and M-S-H) gels using high-resolution quasi-elastic neutron scattering (QENS) technique. C-S-H and M-S-H are the chemical binders present in calcium rich and magnesium rich cements. Wemore » measured three M-S-H samples: pure M-S-H, M-S-H with aluminum-silicate nanotubes (ASN), and M-S-H with carboxyl group functionalized ASN (ASN-COOH). A C-S-H sample with the same water content (i.e. 0.3) is also studied for comparison. We found that structural water in the gels contributes to the elastic component of the QENS spectrum, while constrained water and free water contribute the quasi-elastic component. The quantitative analysis suggests that the three components vary for different samples and indicate the variance in the system porosity, which controls the mechanical properties of cement pastes.« less

From crystalline to amorphous calcium pyrophosphates: A solid state Nuclear Magnetic Resonance perspective.

PubMed

Gras, Pierre; Baker, Annabelle; Combes, Christèle; Rey, Christian; Sarda, Stéphanie; Wright, Adrian J; Smith, Mark E; Hanna, John V; Gervais, Christel; Laurencin, Danielle; Bonhomme, Christian

2016-02-01

Hydrated calcium pyrophosphates (CPP, Ca2P2O7·nH2O) are a fundamental family of materials among osteoarticular pathologic calcifications. In this contribution, a comprehensive multinuclear NMR (Nuclear Magnetic Resonance) study of four crystalline and two amorphous phases of this family is presented. (1)H, (31)P and (43)Ca MAS (Magic Angle Spinning) NMR spectra were recorded, leading to informative fingerprints characterizing each compound. In particular, different (1)H and (43)Ca solid state NMR signatures were observed for the amorphous phases, depending on the synthetic procedure used. The NMR parameters of the crystalline phases were determined using the GIPAW (Gauge Including Projected Augmented Wave) DFT approach, based on first-principles calculations. In some cases, relaxed structures were found to improve the agreement between experimental and calculated values, demonstrating the importance of proton positions and pyrophosphate local geometry in this particular NMR crystallography approach. Such calculations serve as a basis for the future ab initio modeling of the amorphous CPP phases. The general concept of NMR crystallography is applied to the detailed study of calcium pyrophosphates (CPP), whether hydrated or not, and whether crystalline or amorphous. CPP are a fundamental family of materials among osteoarticular pathologic calcifications. Their prevalence increases with age, impacting on 17.5% of the population after the age of 80. They are frequently involved or associated with acute articular arthritis such as pseudogout. Current treatments are mainly directed at relieving the symptoms of joint inflammation but not at inhibiting CPP formation nor at dissolving these crystals. The combination of advanced NMR techniques, modeling and DFT based calculation of NMR parameters allows new original insights in the detailed structural description of this important class of biomaterials. Copyright © 2016. Published by Elsevier Ltd.

X-ray diffraction investigation of amorphous calcium phosphate and hydroxyapatite under ultra-high hydrostatic pressure

NASA Astrophysics Data System (ADS)

Lam, Elisa; Gu, Qinfen; Swedlund, Peter J.; Marchesseau, Sylvie; Hemar, Yacine

2015-11-01

The changes in the crystal structures of synthetically prepared amorphous calcium phosphate (ACP) and hydroxyapatite (HAP) in water (1:1 mass ratio) were studied by synchrotron X-ray diffraction (XRD) under ultra-high hydrostatic pressures as high as 2.34 GPa for ACP and 4 GPa for HAP. At ambient pressure, the XRD patterns of the ACP and HAP samples in capillary tubes and their environmental scanning electron micrographs indicated amorphous and crystalline characteristics for ACP and HAP, respectively. At pressures greater than 0.25 GPa, an additional broad peak was observed in the XRD pattern of the ACP phase, indicating a partial phase transition from an amorphous phase to a new high-pressure amorphous phase. The peak areas and positions of the ACP phase, as obtained through fitting of the experimental data, indicated that the ACP exhibited increased pseudo-crystalline behavior at pressures greater than 0.96 GPa. Conversely, no structural changes were observed for the HAP phase up to the highest applied pressure of 4 GPa. For HAP, a unit-cell reduction during compression was evidenced by a reduction in both refined lattice parameters a and c. Both ACP and HAP reverted to their original structures when the pressure was fully released to ambient pressure.

Amorphous calcium carbonate particles form coral skeletons

NASA Astrophysics Data System (ADS)

Mass, Tali; Giuffre, Anthony J.; Sun, Chang-Yu; Stifler, Cayla A.; Frazier, Matthew J.; Neder, Maayan; Tamura, Nobumichi; Stan, Camelia V.; Marcus, Matthew A.; Gilbert, Pupa U. P. A.

2017-09-01

Do corals form their skeletons by precipitation from solution or by attachment of amorphous precursor particles as observed in other minerals and biominerals? The classical model assumes precipitation in contrast with observed “vital effects,” that is, deviations from elemental and isotopic compositions at thermodynamic equilibrium. Here, we show direct spectromicroscopy evidence in Stylophora pistillata corals that two amorphous precursors exist, one hydrated and one anhydrous amorphous calcium carbonate (ACC); that these are formed in the tissue as 400-nm particles; and that they attach to the surface of coral skeletons, remain amorphous for hours, and finally, crystallize into aragonite (CaCO3). We show in both coral and synthetic aragonite spherulites that crystal growth by attachment of ACC particles is more than 100 times faster than ion-by-ion growth from solution. Fast growth provides a distinct physiological advantage to corals in the rigors of the reef, a crowded and fiercely competitive ecosystem. Corals are affected by warming-induced bleaching and postmortem dissolution, but the finding here that ACC particles are formed inside tissue may make coral skeleton formation less susceptible to ocean acidification than previously assumed. If this is how other corals form their skeletons, perhaps this is how a few corals survived past CO2 increases, such as the Paleocene-Eocene Thermal Maximum that occurred 56 Mya.

Amorphous calcium carbonate particles form coral skeletons.

PubMed

Mass, Tali; Giuffre, Anthony J; Sun, Chang-Yu; Stifler, Cayla A; Frazier, Matthew J; Neder, Maayan; Tamura, Nobumichi; Stan, Camelia V; Marcus, Matthew A; Gilbert, Pupa U P A

2017-09-12

Do corals form their skeletons by precipitation from solution or by attachment of amorphous precursor particles as observed in other minerals and biominerals? The classical model assumes precipitation in contrast with observed "vital effects," that is, deviations from elemental and isotopic compositions at thermodynamic equilibrium. Here, we show direct spectromicroscopy evidence in Stylophora pistillata corals that two amorphous precursors exist, one hydrated and one anhydrous amorphous calcium carbonate (ACC); that these are formed in the tissue as 400-nm particles; and that they attach to the surface of coral skeletons, remain amorphous for hours, and finally, crystallize into aragonite (CaCO 3 ). We show in both coral and synthetic aragonite spherulites that crystal growth by attachment of ACC particles is more than 100 times faster than ion-by-ion growth from solution. Fast growth provides a distinct physiological advantage to corals in the rigors of the reef, a crowded and fiercely competitive ecosystem. Corals are affected by warming-induced bleaching and postmortem dissolution, but the finding here that ACC particles are formed inside tissue may make coral skeleton formation less susceptible to ocean acidification than previously assumed. If this is how other corals form their skeletons, perhaps this is how a few corals survived past CO 2 increases, such as the Paleocene-Eocene Thermal Maximum that occurred 56 Mya.

Physicochemical characterization of atorvastatin calcium/ezetimibe amorphous nano-solid dispersions prepared by electrospraying method.

PubMed

Jahangiri, Azin; Barzegar-Jalali, Mohammad; Javadzadeh, Yousef; Hamishehkar, Hamed; Adibkia, Khosro

2017-09-01

In the present study, electrospraying was applied as a novel method for the fabrication of amorphous nano-solid dispersions (N-SDs) of atorvastatin calcium (ATV), ezetimibe (EZT), and ATV/EZT combination as poorly water-soluble drugs. N-SDs were prepared using polyvinylpyrrolidone K30 as an amorphous carrier in 1:1 and 1:5 drug to polymer ratios and the total solid (including drug and polymer) concentrations of 10 and 20% (w/v). The prepared formulations were further investigated for their morphological, physicochemical, and dissolution properties. Scanning electron microscopy studies indicated that the morphology and diameter of the electrosprayed samples (ESs) were influenced by the solution concentration and drug:polymer ratio, so that an increase in the solution concentration resulted in fiber formation while an increase in the polymer ratio led to enhancement of the particle diameter. Differential scanning calorimetry and X-ray powder diffraction studies together with in vitro dissolution test revealed that the ESs were present in an amorphous form with improved dissolution properties. Infrared spectroscopic studies showed hydrogen-bonding interaction between the drug and polymer in ESs. Since the electrospraying method benefits from the both amorphization and nanosizing effect, this novel approach seems to be an efficient method for the fabrication of N-SDs of poorly water-soluble drugs.

Amorphous calcium carbonate particles form coral skeletons

PubMed Central

Mass, Tali; Giuffre, Anthony J.; Sun, Chang-Yu; Stifler, Cayla A.; Frazier, Matthew J.; Neder, Maayan; Tamura, Nobumichi; Stan, Camelia V.; Marcus, Matthew A.

2017-01-01

Do corals form their skeletons by precipitation from solution or by attachment of amorphous precursor particles as observed in other minerals and biominerals? The classical model assumes precipitation in contrast with observed “vital effects,” that is, deviations from elemental and isotopic compositions at thermodynamic equilibrium. Here, we show direct spectromicroscopy evidence in Stylophora pistillata corals that two amorphous precursors exist, one hydrated and one anhydrous amorphous calcium carbonate (ACC); that these are formed in the tissue as 400-nm particles; and that they attach to the surface of coral skeletons, remain amorphous for hours, and finally, crystallize into aragonite (CaCO3). We show in both coral and synthetic aragonite spherulites that crystal growth by attachment of ACC particles is more than 100 times faster than ion-by-ion growth from solution. Fast growth provides a distinct physiological advantage to corals in the rigors of the reef, a crowded and fiercely competitive ecosystem. Corals are affected by warming-induced bleaching and postmortem dissolution, but the finding here that ACC particles are formed inside tissue may make coral skeleton formation less susceptible to ocean acidification than previously assumed. If this is how other corals form their skeletons, perhaps this is how a few corals survived past CO2 increases, such as the Paleocene–Eocene Thermal Maximum that occurred 56 Mya. PMID:28847944

[Endodontics in motion: new concepts, materials and techniques 1. Hydraulic Calcium Silicate Cements].

PubMed

Moinzadeh, A T; Jongsma, L; de Groot-Kuin, D; Cristescu, R; Neirynck, N; Camilleri, J

2015-01-01

Hydraulic Calcium Silicate Cements (HCSCs) constitute a group of materials that have become increasingly popular in endodontics since the introduction of Mineral Trioxide Aggregate (MTA) in the 1990s. MTA is Portland cement to which bismuth oxide has been added to increase its radiopacity. The most important property of MTA is its capacity to set in water or a humid environment. However, MTA also has important limitations, for example, it's difficult to work with and can discolour teeth. Recently, numerous products based on HCSC chemistry, which can be considered as modifications of MTA intended to reduce its limitations, have become available on the market. Despite their potential advantages, all of these materials have their own specific limitations that are currently insufficiently known and investigated.

Controls on ground-water chemistry in the Horse Heaven Hills, south-central Washington

USGS Publications Warehouse

Steinkampf, W.C.; Bortleson, Gilbert C.; Packard, F.A.

1985-01-01

Miocene basaltic aquifers are the source of domestic and municipal water, and about 20,000 acre-feet of irrigation water annually, in the Horse Heaven Hills in south-central Washington State. Groundwater chemical variations derive from the hydraulic characteristics is of the geohydrologic system, from groundwater basalt reactions, and from irrigation. Some dissolved species concentrations increase with residence time; others decrease. Recharge area groundwaters are calcium magnesium sodium bicarbonate waters with sodium-adsorption ratios (SAR's) less than 1.0. They evolve to sodium potassium bicarbonate waters with SAR 's as high as 17. Glassy and cryptocrystalline phases of the basalt are the main sources of dissolved sodium. They dissolve by silicate hydrolysis in carbon dioxide charged waters that recharge the aquifer system. Dissolved silicon, iron, and aluminum concentrations are controlled by the solubilities of amorphous secondary alteration products, which order to silica phases, oxyhydroxides, and smectite. Carbonate mineral precipitation is induced by increasing pH from the hydrolysis reaction. Sodium and potassium concentrations increase until clinoptilolite saturation is reached and precipitation begins. Deviations from the general variation patterns are due to localized geologic structures which distort the groundwater flow system, and to the irrigation use of Columbia River water. (USGS)

Nanosized amorphous calcium carbonate stabilized by poly(ethylene oxide)-b-poly(acrylic acid) block copolymers.

PubMed

Guillemet, Baptiste; Faatz, Michael; Gröhn, Franziska; Wegner, Gerhard; Gnanou, Yves

2006-02-14

Particles of amorphous calcium carbonate (ACC), formed in situ from calcium chloride by the slow release of carbon dioxide by alkaline hydrolysis of dimethyl carbonate in water, are stabilized against coalescence in the presence of very small amounts of double hydrophilic block copolymers (DHBCs) composed of poly(ethylene oxide) (PEO) and poly(acrylic acid) (PAA) blocks. Under optimized conditions, spherical particles of ACC with diameters less than 100 nm and narrow size distribution are obtained at a concentration of only 3 ppm of PEO-b-PAA as additive. Equivalent triblock or star DHBCs are compared to diblock copolymers. The results are interpreted assuming an interaction of the PAA blocks with the surface of the liquid droplets of the concentrated CaCO3 phase, formed by phase separation from the initially homogeneous reaction mixture. The adsorption layer of the block copolymer protects the liquid precursor of ACC from coalescence and/or coagulation.

Polymeric dental composites based on remineralizing amorphous calcium phosphate fillers

PubMed Central

Skrtic, Drago; Antonucci, Joseph M.

2017-01-01

For over two decades we have systematically explored structure-composition-property relationships of amorphous calcium phosphate (ACP)-based polymeric dental composites. The appeal of these bioactive materials stems from their intrinsic ability to prevent demineralization and/or restore defective tooth structures via sustained release of remineralizing calcium and phosphate ions. Due to the compositional similarity of the ACP to biological tooth mineral, ACP-based composites should exhibit excellent biocompatibility. Research described in this article has already yielded remineralizing sealants and orthodontic adhesives as well as a prototype root canal sealer. Our work has also contributed to a better understanding on how polymer matrix structure and filler/matrix interactions affect the critical properties of these polymeric composites and their overall performance. The addition of antimicrobial compounds to the formulation of ACP composites could increase their medical and dental regenerative treatment applications, thereby benefiting an even greater number of patients. PMID:29599572

New approaches to enhanced remineralization of tooth enamel.

PubMed

Cochrane, N J; Cai, F; Huq, N L; Burrow, M F; Reynolds, E C

2010-11-01

Dental caries is a highly prevalent diet-related disease and is a major public health problem. A goal of modern dentistry is to manage non-cavitated caries lesions non-invasively through remineralization in an attempt to prevent disease progression and improve aesthetics, strength, and function. Remineralization is defined as the process whereby calcium and phosphate ions are supplied from a source external to the tooth to promote ion deposition into crystal voids in demineralized enamel, to produce net mineral gain. Recently, a range of novel calcium-phosphate-based remineralization delivery systems has been developed for clinical application. These delivery systems include crystalline, unstabilized amorphous, or stabilized amorphous formulations of calcium phosphate. These systems are reviewed, and the technology with the most scientific evidence to support its clinical use is the remineralizing system utilizing casein phosphopeptides to stabilize and deliver bioavailable calcium, phosphate, and fluoride ions. The recent clinical evidence for this technology is presented and the mechanism of action discussed. Biomimetic approaches to stabilization of bioavailable calcium, phosphate, and fluoride ions and the localization of these ions to non-cavitated caries lesions for controlled remineralization show promise for the non-invasive management of dental caries.

Dust in the Small Magellanic Cloud

NASA Technical Reports Server (NTRS)

Rodrigues, C. V.; Coyne, G. V.; Magalhaes, A. M.

1995-01-01

We discuss simultaneous dust model fits to our extinction and polarization data for the Small Magellanic Cloud (SMC) using existing dust models. Dust model fits to the wavelength dependent polarization are possible for stars with small lambda(sub max). They generally imply size distributions which are narrower and have smaller average sizes compared to those in the Galaxy. The best fits for the extinction curves are obtained with a power law size distribution. The typical, monotonic SMC extinction curve can be well fit with graphite and silicate grains if a small fraction of the SMC carbon is locked up in the grains. Amorphous carbon and silicate grains also fit the data well.

Interfacial Connection Mechanisms in Calcium-Silicate-Hydrates/Polymer Nanocomposites: A Molecular Dynamics Study.

PubMed

Zhou, Yang; Hou, Dongshuai; Manzano, Hegoi; Orozco, Carlos A; Geng, Guoqing; Monteiro, Paulo J M; Liu, Jiaping

2017-11-22

Properties of organic/inorganic composites can be highly dependent on the interfacial connections. In this work, molecular dynamics, using pair-potential-based force fields, was employed to investigate the structure, dynamics, and stability of interfacial connections between calcium-silicate-hydrates (C-S-H) and organic functional groups of three different polymer species. The calculation results suggest that the affinity between C-S-H and polymers is influenced by the polarity of the functional groups and the diffusivity and aggregation tendency of the polymers. In the interfaces, the calcium counterions from C-S-H act as the coordination atoms in bridging the double-bonded oxygen atoms in the carboxyl groups (-COOH), and the Ca-O connection plays a dominant role in binding poly(acrylic acid) (PAA) due to the high bond strength defined by time-correlated function. The defective calcium-silicate chains provide significant numbers of nonbridging oxygen sites to accept H-bonds from -COOH groups. As compared with PAA, the interfacial interactions are much weaker between C-S-H and poly(vinyl alcohol) (PVA) or poly(ethylene glycol) (PEG). Predominate percentage of the -OH groups in the PVA form H-bonds with inter- and intramolecule, which results in the polymer intertwining and reduces the probability of H-bond connections between PVA and C-S-H. On the other hand, the inert functional groups (C-O-C) in poly(ethylene glycol) (PEG) make this polymer exhibit unfolded configurations and move freely with little restrictions. The interaction mechanisms interpreted in this organic-inorganic interface can give fundamental insights into the polymer modification of C-S-H and further implications to improving cement-based materials from the genetic level.

Cytotoxicity and osteogenic potential of silicate calcium cements as potential protective materials for pulpal revascularization.

PubMed

Bortoluzzi, Eduardo A; Niu, Li-Na; Palani, Chithra D; El-Awady, Ahmed R; Hammond, Barry D; Pei, Dan-Dan; Tian, Fu-Cong; Cutler, Christopher W; Pashley, David H; Tay, Franklin R

2015-12-01

In pulpal revascularization, a protective material is placed coronal to the blood clot to prevent recontamination and to facilitate osteogenic differentiation of mesenchymal stem cells to produce new dental tissues. Although mineral trioxide aggregate (MTA) has been the material of choice for clot protection, it is easily displaced into the clot during condensation. The present study evaluated the effects of recently introduced calcium silicate cements (Biodentine and TheraCal LC) on the viability and osteogenic differentiation of human dental pulp stem cells (hDPSCs) by comparing with MTA Angelus. Cell viability was assessed using XTT assay and flow cytometry. The osteogenic potential of hDPSCs exposed to calcium silicate cements was examined using qRT-PCR for osteogenic gene expressions, alkaline phosphatase enzyme activity, Alizarin red S staining and transmission electron microscopy of extracellular calcium deposits. Parametric statistical methods were employed for analyses of significant difference among groups, with α=0.05. The cytotoxic effects of Biodentine and TheraCal LC on hDPSCs were time- and concentration-dependent. Osteogenic differentiation of hDPSCs was enhanced after exposure to Biodentine that was depleted of its cytotoxic components. This effect was less readily observed in hDPSCs exposed to TheraCal LC, although both cements supported extracellular mineralization better than the positive control (zinc oxide-eugenol-based cement). A favorable tissue response is anticipated to occur with the use of Biodentine as a blood clot-protecting material for pulpal revascularization. Further investigations with the use of in vivo animal models are required to validate the potential adverse biological effects of TheraCal LC on hDPSCs. Copyright © 2015 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Cytotoxicity and Osteogenic Potential of Silicate Calcium Cements as Potential Protective Materials for Pulpal Revascularization

PubMed Central

Bortoluzzi, Eduardo A.; Niu, Li-na; Palani, Chithra D.; El-Awady, Ahmed R.; Hammond, Barry D.; Pei, Dan-dan; Tian, Fu-cong; Cutler, Christopher W.; Pashley, David H.; Tay, Franklin R.

2016-01-01

Objectives In pulpal revascularization, a protective material is placed coronal to the blood clot to prevent recontamination and to facilitate osteogenic differentiation of mesenchynal stem cells to produce new dental tissues. Although mineral trioxide aggregate (MTA) has been the material of choice for clot protection, it is easily displaced into the clot during condensation. The present study evaluated the effects of recently-introduced calcium silicate cements (Biodentine and TheraCal LC) on the viability and osteogenic differentiation of human dental pulp stem cells (hDPSCs) by comparing with MTA Angelus. Methods Cell viability was assessed using XTT assay and flow cytometry. The osteogenic potential of hDPSCs exposed to calcium silicate cements was examined using qRT-PCR for osteogeic gene expressions, alkaline phosphatase enzyme activity, Alizarin red S staining and transmission electron microscopy of extracellular calcium deposits. Parametric statistical methods were employed for analyses of significant difference among groups, with α=0.05. Results The cytotoxic effects of Biodentine and TheraCal LC on hDPSCs were time- and concentration-dependent. Osteogenic differentiation of hDPSCs was enhanced after exposure to Biodentine that was depleted of its cytotoxic components. This effect was less readily observed in hDPSCs exposed to TheraCal LC, although both cements supported extracelluar mineralization better than the positive control (zinc oxide-eugenol–based cement). Significance A favorable tissue response is anticipated to occur with the use of Biodentine as a blood clot-protecting material for pulpal revascularizaiton. Further investigations with the use of in vivo animal models are required to validate the potential adverse biological effects of TheraCal LC on hDPSCs. PMID:26494267

Preparation and properties of calcium-silicate filled resins for dental restoration. Part II: Micro-mechanical behaviour to primed mineral-depleted dentine.

PubMed

Profeta, Andrea Corrado

2014-11-01

Evaluating microtensile bond strength (μTBS) and Knoop micro-hardness (KHN) of resin bonded-dentine interfaces created with two methacrylate-based systems either incorporating Bioglass 45S5 (3-E&RA/BG) or MTA (3-E&RA/WMTA). Solvated resins (50% ethanol/50% co-monomers) were used as primers while their neat counterparts were filled with the two calcium-silicate compounds. Application of neat resin adhesive with no filler served as control (3-E&RA). μTBS, KHN analysis and confocal tandem scanning microscopy (TSM) micropermeability were carried out after 24 h and 10 months of storage in phosphate buffer solution (DPBS). Scanning electron microscopy (SEM) was also performed after debonding. High μTBS values were achieved in all groups after 24 h of DPBS storage. On the contrary, solely the specimens created using 3-E&RA/BG and 3-E&RA/WMTA agents showed no significant reduction in terms of μTBS even after 10 months in DPBS; similarly, they did not restore the average superficial micro-hardness to the level of sound dentine, but maintained unchanged KHN values, and no statistical decrease was found following 10 months of DPBS storage. The only statistically significant changes occurred in the resin-dentine interfaces bonded with 3-E&RA that were subjected to a reduction of both μTBS and KHN values with ageing. In terms of micropermeability, adverse results were obtained with 3-E&RA while 3-E&RA/BG and 3-E&RA/WMTA demonstrated a beneficial effect after prolonged DPBS storage. Calcium-silicate filled composite resins performed better than a current etch-and-rinse adhesive and had a therapeutic/protective effect on the micro-mechanical properties of mineral-depleted resin-dentine interfaces. The incorporation of calcium-silicates into dental restorative and bonding agents can create more biomimetic (life-like) restorations. This will not only enable these materials to mimic the physical characteristics of the tooth structure, but will also stabilize and protect the remaining dental hard tissues.

DNA adsorption onto glass surfaces

NASA Astrophysics Data System (ADS)

Carlson, Krista Lynn

Streaming potential measurements were performed on microspheres of silica, lime silicate (SLS) and calcium aluminate (CA) glasses containing silica and iron oxide (CASi and CAFe). The silicate based glasses exhibited acidic surfaces with isoelectric points (IEP) around a pH of 3 while the calcium aluminates displayed more basic surfaces with IEP ranging from 8--9.5. The surface of the calcium aluminate microspheres containing silica reacted with the background electrolyte, altering the measured zeta potential values and inhibiting electrolyte flow past the sample at ˜ pH 4 due to formation of a solid plug. DNA adsorption experiments were performed using the microspheres and a commercially available silicate based DNA isolation filter using a known quantity of DNA suspended in a chaotropic agent free 0.35 wt% Tris(hydroxymethyl)aminomethane (Tris) buffer solution. The microspheres and commercial filter were also used to isolate DNA from macrophage cells in the presence of chaotropic agents. UV absorbance at ˜260 nm and gel electrophoresis were used to quantify the amount and size of the DNA strands that adsorbed to the microsphere surfaces. In both experiments, the 43--106 microm CAFe microspheres adsorbed the largest quantity of DNA. However, the 43--106 microm SLS microspheres isolated more DNA from the cells than the <43 microm CAFe microspheres, indicating that microsphere size contributes to isolation ability. The UV absorbance of DNA at ˜260 nm was slightly altered due to the dissolution of the calcium aluminate glasses during the adsorption process. Inductively coupled plasma-optical emission spectroscopy (ICP-OES) determined that calcium and aluminum ions leached from the CA and CAFe microsphere surfaces during these experiments. Circular dichroism (CD) spectroscopy showed that the leached ions had no effect on the conformation of the DNA, and therefore would not be expected to interfere in downstream applications such as DNA replication. The 0.35 wt% Tris solution completely inhibited the formation of the hydrated crystalline layer that develops when the calcium aluminate glassess are incubated in deionized water. A Tris concentration of 0.24 wt% allowed for the formation of both hexagonal and cubic hydrates, however they were severely distorted and present in low amounts such that they were undectable by XRD.

Effect of desensitizing toothpastes on dentine hypersensitivity: A systematic review and meta-analysis.

PubMed

Hu, Meng-Long; Zheng, Gang; Zhang, You-Dong; Yan, Xiang; Li, Xiao-Chan; Lin, Hong

2018-05-19

To evaluate the desensitizing effect of toothpastes that contain ingredients that act against dentine hypersensitivity (DH) and to compare this effect with negative controls. Five databases were searched to identify relevant articles published up to November 27, 2017. Randomized controlled trials (RCTs) comparing desensitizing toothpastes with a toothpastes without desensitizing component in adult patients that suffer from DH were included. The risk of bias was assessed according to the Cochrane guidelines, and the quality of the evidence was evaluated using the GRADE tool. Inverse variance random-effects meta-analyses of standardized mean differences (SMD) and 95% confidence intervals (CIs) were calculated using RevMan 5.3 software. 53 RCTs with 4796 patients were finally included in the meta-analysis. The toothpastes that contain active desensitization ingredients showed a better desensitizing effect on DH than the negative control, except the strontium- and amorphous calcium phosphate-containing toothpastes. The amorphous calcium phosphate-containing toothpaste had very low-quality evidence, the strontium, potassium and strontium, and potassium and stannous fluoride-containing toothpastes had low-quality evidence, and the other five toothpastes had moderate quality evidence. Our result support the premise that toothpastes containing potassium, stannous fluoride, potassium and strontium, potassium and stannous fluoride, calcium sodium phosphosilicate, arginine, and nano-hydroxyapatite relieve the symptoms of DH, but does not advise the use of toothpastes that contain strontium and amorphous calcium phosphate. Furthermore, high-quality studies are needed to confirm our results. (PROSPERO CRD42018085639). Copyright © 2018 Elsevier Ltd. All rights reserved.

Properties of Tricalcium Silicate Sealers.

PubMed

Khalil, Issam; Naaman, Alfred; Camilleri, Josette

2016-10-01

Sealers based on tricalcium silicate cement aim at an interaction of the sealer with the root canal wall, alkalinity with potential antimicrobial activity, and the ability to set in a wet field. The aim of this study was to characterize and investigate the properties of a new tricalcium silicate-based sealer and verify its compliance to ISO 6876 (2012). A new tricalcium silicate-based sealer (Bio MM; St Joseph University, Beirut, Lebanon), BioRoot RCS (Septodont, St Maure de Fosses, France), and AH Plus (Dentsply, DeTrey, Konstanz, Germany) were investigated. Characterization using scanning electron microscopy, energy-dispersive spectroscopy, and X-ray diffraction analysis was performed. Furthermore, sealer setting time, flow, film thickness, and radiopacity were performed following ISO specifications. pH and ion leaching in solution were assessed by pH analysis and inductively coupled plasma. Bio MM and BioRoot RCS were both composed of tricalcium silicate and tantalum oxide in Bio MM and zirconium oxide in BioRoot RCS. In addition, the Bio MM contained calcium carbonate and a phosphate phase. The inorganic components of AH Plus were calcium tungstate and zirconium oxide. AH Plus complied with the ISO norms for both flow and film thickness. BioRoot RCS and Bio MM exhibited a lower flow and a higher film thickness than that specified for sealer cements in ISO 6876. All test sealers exhibited adequate radiopacity. Bio MM interacted with physiologic solution, thus showing potential for bioactivity. Sealer properties were acceptable and comparable with other sealers available clinically. Copyright © 2016 American Association of Endodontists. Published by Elsevier Inc. All rights reserved.

Advanced ceramic coating development for industrial/utility gas turbines

NASA Technical Reports Server (NTRS)

Vogan, J. W.; Stetson, A. R.

1982-01-01

A program was conducted with the objective of developing advanced thermal barrier coating (TBC) systems. Coating application was by plasma spray. Duplex, triplex and graded coatings were tested. Coating systems incorporated both NiCrAly and CoCrAly bond coats. Four ceramic overlays were tested: ZrO2.82O3; CaO.TiO2; 2CaO.SiO2; and MgO.Al2O3. The best overall results were obtained with a CaO.TiO2 coating applied to a NiCrAly bond coat. This coating was less sensitive than the ZrO2.8Y2O3 coating to process variables and part geometry. Testing with fuels contaminated with compounds containing sulfur, phosphorus and alkali metals showed the zirconia coatings were destabilized. The calcium titanate coatings were not affected by these contaminants. However, when fuels were used containing 50 ppm of vanadium and 150 ppm of magnesium, heavy deposits were formed on the test specimens and combustor components that required frequent cleaning of the test rig. During the program Mars engine first-stage turbine blades were coated and installed for an engine cyclic endurance run with the zirconia, calcium titanate, and calcium silicate coatings. Heavy spalling developed with the calcium silicate system. The zirconia and calcium titanate systems survived the full test duration. It was concluded that these two TBC's showed potential for application in gas turbines.

Calcium-Magnesium-Aluminosilicate (CMAS) Reactions and Degradation Mechanisms of Advanced Environmental Barrier Coatings

NASA Technical Reports Server (NTRS)

Ahlborg, Nadia L.; Zhu, Dongming

2013-01-01

The thermochemical reactions between calcium-magnesium-aluminosilicate- (CMAS-) based road sand and several advanced turbine engine environmental barrier coating (EBC) materials were studied. The phase stability, reaction kinetics and degradation mechanisms of rare earth (RE)-silicates Yb2SiO5, Y2Si2O7, and RE-oxide doped HfO2 and ZrO2 under the CMAS infiltration condition at 1500 C were investigated, and the microstructure and phase characteristics of CMAS-EBC specimens were examined using Scanning Electron Microscopy (SEM) and X-ray Diffraction (XRD). Experimental results showed that the CMAS dissolved RE-silicates to form crystalline, highly non-stoichiometric apatite phases, and in particular attacking the silicate grain boundaries. Cross-section images show that the CMAS reacted with specimens and deeply penetrated into the EBC grain boundaries and formed extensive low-melting eutectic phases, causing grain boundary recession with increasing testing time in the silicate materials. The preliminary results also showed that CMAS reactions also formed low melting grain boundary phases in the higher concentration RE-oxide doped HfO2 systems. The effect of the test temperature on CMAS reactions of the EBC materials will also be discussed. The faster diffusion exhibited by apatite and RE-doped oxide phases and the formation of extensive grain boundary low-melting phases may limit the CMAS resistance of some of the environmental barrier coatings at high temperatures.

Hydrochemical characterization of groundwater in the Akyem area, Ghana

USGS Publications Warehouse

Banoeng-Yakubo, B.; Yidana, S.M.; Anku, Y.; Akabzaa, T.; Asiedu, D.

2008-01-01

The Akyem area is a small farming community located in southeastern Ghana. Groundwater samples from wells in the area were analyzed for concentrations of the major ions, silica, electrical conductivity and pH. The objective was to determine the main controls on the hydrochemistry of ground-water. Mass balance modeling was used together with multivariate R-mode hierarchical cluster analysis to determine the significant sources of variation in the hydrochemistry. Two water types exist in this area. The first is influenced most by the weathering of silicate minerals from the underlying geology, and is thus rich in silica, sodium, calcium, bicarbonate, and magnesium ions. The second is water that has been influenced by the effects of fertilizers and other anthropogenic activities in the area. Mineral speciation and silicate mineral stability diagrams suggest that montmorillonite, probably derived from the incongruent dissolution of feldspars and micas, is the most stable silicate phase in the groundwaters. The apparent incongruent weathering of silicate minerals in the groundwater system has led to the enrichment of sodium, calcium, magnesium and bicarbonate ions as well as silica, leading to the supersaturation of calcite, aragonite, dolomite and quartz. Stability in the montmorillonite field suggests restricted flow conditions and a long groundwater residence time, leading to greater exposure of the rock to weathering. Cation exchange processes appear to play minor roles in the hydrochemistry of groundwater.

THE COMPOSITION OF INTERSTELLAR GRAINS TOWARD ζ OPHIUCHI: CONSTRAINING THE ELEMENTAL BUDGET NEAR THE DIFFUSE-DENSE CLOUD TRANSITION

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

Poteet, Charles A.; Whittet, Douglas C. B.; Draine, Bruce T., E-mail: charles.poteet@gmail.com

2015-03-10

We investigate the composition of interstellar grains along the line of sight toward ζ Ophiuchi, a well-studied environment near the diffuse-dense cloud transition. A spectral decomposition analysis of the solid-state absorbers is performed using archival spectroscopic observations from the Spitzer Space Telescope and Infrared Space Observatory. We find strong evidence for the presence of sub-micron-sized amorphous silicate grains, principally comprised of olivine-like composition, with no convincing evidence of H{sub 2}O ice mantles. However, tentative evidence for thick H{sub 2}O ice mantles on large (a ≈ 2.8 μm) grains is presented. Solid-state abundances of elemental Mg, Si, Fe, and O aremore » inferred from our analysis and compared to standard reference abundances. We find that nearly all of the Mg and Si atoms along the line of sight reside in amorphous silicate grains, while a substantial fraction of the elemental Fe resides in compounds other than silicates. Moreover, we find that the total abundance of elemental O is largely inconsistent with the adopted reference abundances, indicating that as much as ∼156 ppm of interstellar O is missing along the line of sight. After taking into account additional limits on the abundance of elemental O in other O-bearing solids, we conclude that any missing reservoir of elemental O must reside on large grains that are nearly opaque to infrared radiation.« less

Formation of a low-crystalline Zn-silicate in a stream in SW Sardinia, Italy

USGS Publications Warehouse

Wanty, Richard B.; De Giudici, G.; Onnis, P.; Rutherford, D.; Kimball, B.A.; Podda, F.; Cidu, R.; Lattanzi, P.; Medas, D.

2013-01-01

n southwestern Sardinia, Italy, the Rio Naracauli drains a catchment that includes several abandoned mines. The drainage from the mines and associated waste rocks has led to extreme concentrations of dissolved Zn, but because of the near-neutral pH, concentrations of other metals remain low. In the reach from approximately 2300 to 3000 m downstream from the headwaters area, an amorphous Zn-silicate precipitates from the water. In this reach, concentrations of both Zn and silica remain nearly constant, but the loads (measured in mass/time) of both increase, suggesting that new Zn and silica are supplied to the stream, likely from emerging groundwater. Zinc isotope signatures of the solid are heavier than the dissolved Zn by about 0.5 permil in 66/64Zn, suggesting that an extracellular biologically mediated adsorption process may be involved in the formation of the Zn-silicate.

Effect of Fe2O3 on the physical and structural properties of bismuth silicate glasses

NASA Astrophysics Data System (ADS)

Parmar, Rajesh; Kundu, R. S.; Punia, R.; Aghamkar, P.; Kishore, N.

2013-06-01

Iron containing bismuth silicate glasses with compositions 70SiO2ṡ(100-x)Bi2O3ṡxFe2O3 have been prepared using conventional melt-quenching method and their amorphous nature has been investigated using XRD. Density has been measured using Archimedes' principle and molar volume (Vm) have also been estimated. With increase in Fe2O3 content, there is a decrease in density and molar volume of the glass samples. The glass transition temperature (Tg) have been determined using Differential Scanning Calorimetry (DSC) and are observed to increase with increase in Fe2O3 content. In the present glass system bismuth and iron plays the role of network modifier and the symmetry of silicate network goes on increasing with Fe2O3 content and it modifies the physical and structural properties of these glasses.

Uptake of Silicon by Sugarcane from Applied Sources May Not Reflect Plant-Available Soil Silicon and Total Silicon Content of Sources.

PubMed

Keeping, Malcolm G

2017-01-01

Soils of the tropics and sub-tropics are typically acid and depleted of soluble sources of silicon (Si) due to weathering and leaching associated with high rainfall and temperatures. Together with intensive cropping, this leads to marginal or deficient plant Si levels in Si-accumulating crops such as rice and sugarcane. Although such deficiencies can be corrected with exogenous application of Si sources, there is controversy over the effectiveness of sources in relation to their total Si content, and their capacity to raise soil and plant Si concentrations. This study tested the hypothesis that the total Si content and provision of plant-available Si from six sources directly affects subsequent plant Si uptake as reflected in leaf Si concentration. Two trials with potted cane plants were established with the following Si sources as treatments: calcium silicate slag, fused magnesium (thermo) phosphate, volcanic rock dust, magnesium silicate, and granular potassium silicate. Silicon sources were applied at rates intended to achieve equivalent elemental soil Si concentrations; controls were untreated or lime-treated. Analyses were conducted to determine soil and leaf elemental concentrations. Among the sources, calcium silicate produced the highest leaf Si concentrations, yet lower plant-available soil Si concentrations than the thermophosphate. The latter, with slightly higher total Si than the slag, produced substantially greater increases in soil Si than all other products, yet did not significantly raise leaf Si above the controls. All other sources did not significantly increase soil or leaf Si concentrations, despite their high Si content. Hence, the total Si content of sources does not necessarily concur with a product's provision of soluble soil Si and subsequent plant uptake. Furthermore, even where soil pH was raised, plant uptake from thermophosphate was well below expectation, possibly due to its limited liming capacity. The ability of the calcium silicate to provide Si while simultaneously and significantly increasing soil pH, and thereby reducing reaction of Si with exchangeable Al 3+ , is proposed as a potential explanation for the greater Si uptake into the shoot from this source.

Uptake of Silicon by Sugarcane from Applied Sources May Not Reflect Plant-Available Soil Silicon and Total Silicon Content of Sources

PubMed Central

Keeping, Malcolm G.

2017-01-01

Soils of the tropics and sub-tropics are typically acid and depleted of soluble sources of silicon (Si) due to weathering and leaching associated with high rainfall and temperatures. Together with intensive cropping, this leads to marginal or deficient plant Si levels in Si-accumulating crops such as rice and sugarcane. Although such deficiencies can be corrected with exogenous application of Si sources, there is controversy over the effectiveness of sources in relation to their total Si content, and their capacity to raise soil and plant Si concentrations. This study tested the hypothesis that the total Si content and provision of plant-available Si from six sources directly affects subsequent plant Si uptake as reflected in leaf Si concentration. Two trials with potted cane plants were established with the following Si sources as treatments: calcium silicate slag, fused magnesium (thermo) phosphate, volcanic rock dust, magnesium silicate, and granular potassium silicate. Silicon sources were applied at rates intended to achieve equivalent elemental soil Si concentrations; controls were untreated or lime-treated. Analyses were conducted to determine soil and leaf elemental concentrations. Among the sources, calcium silicate produced the highest leaf Si concentrations, yet lower plant-available soil Si concentrations than the thermophosphate. The latter, with slightly higher total Si than the slag, produced substantially greater increases in soil Si than all other products, yet did not significantly raise leaf Si above the controls. All other sources did not significantly increase soil or leaf Si concentrations, despite their high Si content. Hence, the total Si content of sources does not necessarily concur with a product's provision of soluble soil Si and subsequent plant uptake. Furthermore, even where soil pH was raised, plant uptake from thermophosphate was well below expectation, possibly due to its limited liming capacity. The ability of the calcium silicate to provide Si while simultaneously and significantly increasing soil pH, and thereby reducing reaction of Si with exchangeable Al3+, is proposed as a potential explanation for the greater Si uptake into the shoot from this source. PMID:28555144

The geologic classification of the meteorites

USGS Publications Warehouse

Elston, Donald Parker

1968-01-01

The meteorite classes of Prior and Mason are assigned to three proposed genetic groups on the basis of a combination of compositional, mineralogical, and elemental characteristics: l) the calcium-poor, volatile-rich carbonaceous chondrites and achondrites; 2) the calcium-poor, volatile-poor chondrites (enstatite, bronzite, hypersthene, and pigeonite), achondrites (enstatite, hypersthene, and pigeonite), stonyirons (pallasites, siderophyre), and irons; and, 3) the calcium-rich (basaltic) achondrites. Chondrites are correlated with calcium-poor achondrites and the silicate phase of the pallasitic meteorites on Fe contents of olivine and pyroxene; and with metal of the stony-irons and irons on the basis of trace elements (Ga and Ge). Transitions in structure and texture between the chondrites and achondrites are recognized. The Van Schmus-Wood chemical-petrologic classification of the chondrites has been modified and expanded to a mineralogic-petrologic classification of the chondrites and calcium-poor achondrites. Chondrites apparently are the first rocks of the solar system. Paragenetic and textural relations in the Murray carbonaceous chondrite shed new light on the manner of accretion, and on the character of dispersed solid materials ('dust', and chondrules and metal) that existed in the solar system before accretion. Two pre-accretionary mineral assemblages (components) are recognized in the carbonaceous chondrites and in the unequilibrated volatile-poor chondrites. They are: 1) a 'low temperature' water-, rare gas-, and carbon-bearing component; and, 2) a high temperature anhydrous silicate and metal component. Paragenetic relations indicate that component 2 materials predate chondrite formation. An accretionary assemblage (component 3) also is recognized in the carbonaceous chondrites and in the unequilibrated volatile-poor chondrites. Component 3 consists of very fine grains of olivine and pyroxene, which occur as pervasive disseminations, as small irregular aggregates of grains, and as large subround to round, finely granular accretional chondrules. Evidence in Murray indicates that component 3 silicates precipitated abruptly and at low pressures, possibly from a high temperature gas, in an environment that contained dispersed component 1 and 2 materials. All component 3 aggregates in Murray contain component 1 material, most commonly as flakes, and locally as tiny granules and larger spherules, some of which are hollow and some of which were broken prior to their mechanical incorporation in accretionary chondrules. Accretion may have occurred as ices associated with dispersed water-bearing component 1 materials temporarily melted during the precipitation of component 3 silicates, and then abruptly refroze to form an icy cementing material. Group 1 materials may be cometary, and group 2 materials may be asteroidal. Schematic models are proposed. Evidence is reviewed for the lunar origin of the pyroxeneplagioclase achondrites. On the basis of natural remanent magnetism, it is suggested that the very scarce diopside-olivine achondrites may be samples from Mars. A classification of the meteorite breccias, including the calcium-poor and calcium-rich mesosiderites, and irons that contain silicate fragments, is proposed. A fragmentation history of the meteorites is outlined on the basis of evidence in the polymict breccias, and from gas retention ages in stones and exposure ages in irons. Cometal impacts appear to have caused the initial fragmentation, stud possibly the perturbation of orbits, of two inferred asteroidal bodies (enstatite and bronzite), one and possibly both events occurring before 2000 m.y. ago. Several impacts apparently occurred on the inferred hypersthene body in the interval 1000 to 2000 m.y. ago. Major breakups of the three bodies apparently occurred as the result of interasteroidal collisions at about 900 m.y. ago, and 600 to 700 m.y. ago. The breakups were followed by a number of fr

Bonelike apatite formation on ethylene-vinyl alcohol copolymer modified with silane coupling agent and calcium silicate solutions.

PubMed

Oyane, Ayako; Kawashita, Masakazu; Nakanishi, Kazuki; Kokubo, Tadashi; Minoda, Masahiko; Miyamoto, Takeaki; Nakamura, Takashi

2003-05-01

An ethylene-vinyl alcohol copolymer (EVOH) was treated with a silane coupling agent and calcium silicate solutions, and then soaked in a simulated body fluid (SBF) with ion concentrations approximately equal to those of human blood plasma. A smooth and uniform bonelike apatite layer was successfully formed on both the EVOH plate and the EVOH-knitted fibers in SBF within 2 days. Part of the structure of the resulting apatite-EVOH fiber composite was similar to that of natural bone. If this kind of composite can be fabricated into a three-dimensional structure similar to natural bone, the resultant composite is expected to exhibit both mechanical properties analogous to those of natural bone and bone-bonding ability. Hence, it has great potential as a bone substitute. Copyright 2003 Elsevier Science Ltd.

Thermodynamics and kinetics of the sulfation of porous calcium silicate

NASA Technical Reports Server (NTRS)

Miller, R. A.; Kohl, F. J.

1981-01-01

The sulfation of plasma sprayed calcium silicate in flowing SO2/air mixtures at 900 and 1000 C was investigated thermogravimetrically. Reaction products were analyzed using electron microprobe and X-ray diffraction analysis techniques, and results were compared with thermodynamic predictions. The percentage, by volume, of SO2 in air was varied between 0.036 and 10 percent. At 10 percent SO2 the weight gain curve displays a concave downward shoulder early in the sulfation process. An analytical model was developed which treats the initial process as one which decays exponentially with increasing time and the subsequent process as one which decays exponentially with increasing weight gain. At lower SO2 levels the initial rate is controlled by the reactant flow rate. At 1100 C and 0.036 percent SO2 there is no reaction, in agreement with thermodynamic predictions.

Amorphous Calcium Carbonate in Biomineralization: Stable and Precursor Phases

NASA Astrophysics Data System (ADS)

Weiner, S.

2003-12-01

The biological formation of the crystalline polymorphs of calcium carbonate, aragonite and calcite, is widespread. The less stable polymorphs, vaterite and monohydrocalcite are also formed by some organisms. Surprisingly, the highly unstable phase, amorphous calcium carbonate (ACC), is formed by a variety of organisms from different phyla. Most of these are stable at least within the lifetime of the organism. The stable forms all have a stoichiometry of CaCO3.H2O. Despite the fact that they do not diffract X-rays. Studies of their short range order by EXAFS, reveal species specific variations in the number and distances of atoms that surround the calcium ion. Proteins extracted from stable biogenic ACC are able to stabilize the phase in vitro. ACC has also been identified as a transient precursor phase during the formation of the calcitic larval spicule of the sea urchin and the formation of the larval shell of a bivalve. The transient form has little or no water associated with the CaCO3. Preliminary EXAFS data suggest that the short range order of the sea urchin spicule transient ACC resembles calcite. Proteins extracted from these spicules are able to stabilize ACC provided Mg is present in the solution. As the mollusks and the echinoderms are on two different branches of the animal phylogenetic tree, it is conceivable that the strategy of using ACC as a precursor phase at least for larval mineralization may be widespread. It has yet to be shown that it is used by adults of either phylum. The manner in which organisms precipitate, stabilize and destabilize if necessary, this highly metastable phase of calcium carbonate presents many fascinating and enigmatic questions, whose solutions could well contribute to a better understanding of basic processes in biomineralization. For more details and references, see Addadi, L., Raz, S. and Weiner, S. (2003). Taking advantage of disorder: Amorphous calcium carbonate and its roles in biomineralization. Adv. Mat.15, 959-970.

Machining of a bioactive nanocomposite orthopedic fixation device.

PubMed

Sparnell, Amie; Aniket; El-Ghannam, Ahmed

2012-08-01

Bioactive ceramics bond to bone and enhance bone formation. However, they have poor mechanical properties which restrict their machinability as well as their application as load bearing implants. The goal of this study was to machine bioactive fixation screws using a silica-calcium phosphate nanocomposite (SCPC50). The effect of compact pressure, holding time, and thermal treatment on the microstructure, machinability, and mechanical properties of SCPC50 cylinders were investigated. Samples prepared by powder metallurgy technique at compact pressure range of 100-300 MPa and treated at 900°C/1 h scored a poor machinability rating of (1/5) due to the significant formation of amorphous silicate phase at the grain boundaries. On the other hand, lowering of compact pressure and sintering temperature to 30 MPa/3 h and 700°C/2 h, respectively, minimized the formation of the amorphous phase and raised the machinability rating to (5/5). The modulus of elasticity and ultimate strength of machinable SCPC50 were 10.8 ± 2.0 GPa and 72.8 ± 22.8 MPa, respectively, which are comparable to the corresponding values for adult human cortical bone. qRT-PCR analyses showed that bone cells attached to SCPC50 significantly upregulated osteocalcin mRNA expression as compared to the cells on Ti-6Al-4V. Moreover, cells attached to SCPC50 produced mineralized bone-like tissue within 8 days. On the other hand, cells attached to Ti-6Al-4V failed to produce bone mineral under the same experimental conditions. Results of the study suggest that machinable SCPC50 has the potential to serve as an attractive new material for orthopedic fixation devices. Copyright © 2012 Wiley Periodicals, Inc.

Influence of Silicate Concentration in Electrolyte on the Growth and Performance of Plasma Electrolytic Oxidation Coatings Prepared on Low Carbon Steel

NASA Astrophysics Data System (ADS)

Yang, Wenbin; Peng, Zhenjun; Liu, Baixing; Liu, Weimin; Liang, Jun

2018-04-01

Plasma electrolytic oxidation (PEO) coatings were prepared on low carbon steel from electrolytes with different silicate concentrations. The microstructure, elemental and phase compositions of the PEO coatings were analyzed by scanning electron microscope, energy-dispersive spectrometer, and x-ray diffraction, respectively. The adhesion of PEO coatings with low carbon steel substrate was qualitatively examined by thermal shock tests. The tribological properties were evaluated by a reciprocating tribometer sliding against a Si3N4 ceramic ball. The corrosion behaviors of PEO coatings were investigated in 3.5 wt.% NaCl solution by electrochemical impedance spectra and potentiodynamic polarization. Results indicated that all the PEO coatings were comprised of amorphous SiO2 and Fe-containing oxides; however, the silicate concentration in electrolyte showed significant influence on the growth and the performance of PEO coatings. The PEO coating prepared from the electrolyte with silicate concentration of 30 g/L had the highest Fe content because the substrate was more readily oxidized and showed a dense structure, resulting in the best comprehensive performance of adhesion, wear resistance, and corrosion resistance.

Influence of Silicate Concentration in Electrolyte on the Growth and Performance of Plasma Electrolytic Oxidation Coatings Prepared on Low Carbon Steel

NASA Astrophysics Data System (ADS)

Yang, Wenbin; Peng, Zhenjun; Liu, Baixing; Liu, Weimin; Liang, Jun

2018-05-01

Plasma electrolytic oxidation (PEO) coatings were prepared on low carbon steel from electrolytes with different silicate concentrations. The microstructure, elemental and phase compositions of the PEO coatings were analyzed by scanning electron microscope, energy-dispersive spectrometer, and x-ray diffraction, respectively. The adhesion of PEO coatings with low carbon steel substrate was qualitatively examined by thermal shock tests. The tribological properties were evaluated by a reciprocating tribometer sliding against a Si3N4 ceramic ball. The corrosion behaviors of PEO coatings were investigated in 3.5 wt.% NaCl solution by electrochemical impedance spectra and potentiodynamic polarization. Results indicated that all the PEO coatings were comprised of amorphous SiO2 and Fe-containing oxides; however, the silicate concentration in electrolyte showed significant influence on the growth and the performance of PEO coatings. The PEO coating prepared from the electrolyte with silicate concentration of 30 g/L had the highest Fe content because the substrate was more readily oxidized and showed a dense structure, resulting in the best comprehensive performance of adhesion, wear resistance, and corrosion resistance.

On the metallicity dependence of crystalline silicates in oxygen-rich asymptotic giant branch stars and red supergiants

NASA Astrophysics Data System (ADS)

Jones, O. C.; Kemper, F.; Sargent, B. A.; McDonald, I.; Gielen, C.; Woods, Paul M.; Sloan, G. C.; Boyer, M. L.; Zijlstra, A. A.; Clayton, G. C.; Kraemer, K. E.; Srinivasan, S.; Ruffle, P. M. E.

2012-12-01

We investigate the occurrence of crystalline silicates in oxygen-rich evolved stars across a range of metallicities and mass-loss rates. It has been suggested that the crystalline silicate feature strength increases with increasing mass-loss rate, implying a correlation between lattice structure and wind density. To test this, we analyse Spitzer Infrared Spectrograph and Infrared Space Observatory Short Wavelength Spectrometer spectra of 217 oxygen-rich asymptotic giant branch and 98 red supergiants in the Milky Way, the Large and Small Magellanic Clouds, and Galactic globular clusters. These encompass a range of spectral morphologies from the spectrally rich which exhibit a wealth of crystalline and amorphous silicate features to 'naked' (dust-free) stars. We combine spectroscopic and photometric observations with the GRAMS grid of radiative transfer models to derive (dust) mass-loss rates and temperature. We then measure the strength of the crystalline silicate bands at 23, 28 and 33 μm. We detect crystalline silicates in stars with dust mass-loss rates which span over 3 dex, down to rates of ˜10-9 M⊙ yr-1. Detections of crystalline silicates are more prevalent in higher mass-loss rate objects, though the highest mass-loss rate objects do not show the 23-μm feature, possibly due to the low temperature of the forsterite grains or it may indicate that the 23-μm band is going into absorption due to high column density. Furthermore, we detect a change in the crystalline silicate mineralogy with metallicity, with enstatite seen increasingly at low metallicity.

Ultra-Small-Angle X-ray Scattering – X-ray Photon Correlation Spectroscopy Studies of Incipient Structural Changes in Amorphous Calcium Phosphate Based Dental Composites

PubMed Central

Zhang, F.; Allen, A.J.; Levine, L.E.; Espinal, L.; Antonucci, J.M.; Skrtic, D.; O’Donnell, J.N.R.; Ilavsky, J.

2012-01-01

The local structural changes in amorphous calcium phosphate (ACP) based dental composites were studied under isothermal conditions using both static, bulk measurement techniques and a recently developed methodology based on combined ultra-small angle X-ray scattering – X-ray photon correlation spectroscopy (USAXS-XPCS), which permits a dynamic approach. While results from conventional bulk measurements do not show clear signs of structural change, USAXS-XPCS results reveal unambiguous evidence for local structural variations on a similar time scale to that of water loss in the ACP fillers. A thermal-expansion based simulation indicates that thermal behavior alone does not account for the observed dynamics. Together, these results suggest that changes in the water content of ACP affect the composite morphology due to changes in ACP structure that occur without an amorphous-to-crystalline conversion. It is also noted that biomedical materials research could benefit greatly from USAXS-XPCS, a dynamic approach. PMID:22374649

Q-Speciation and Network Structure Evolution in Invert Calcium Silicate Glasses.

PubMed

Kaseman, Derrick C; Retsinas, A; Kalampounias, A G; Papatheodorou, G N; Sen, S

2015-07-02

Binary silicate glasses in the system CaO-SiO2 are synthesized over an extended composition range (42 mol % ≤ CaO ≤ 61 mol %), using container-less aerodynamic levitation techniques and CO2-laser heating. The compositional evolution of Q speciation in these glasses is quantified using (29)Si and (17)O magic angle spinning nuclear magnetic resonance spectroscopy. The results indicate progressive depolymerization of the silicate network upon addition of CaO and significant deviation of the Q speciation from the binary model. The equilibrium constants for the various Q species disproportionation reactions for these glasses are found to be similar to (much smaller than) those characteristic of Li (Mg)-silicate glasses, consistent with the corresponding trends in the field strengths of these modifier cations. Increasing CaO concentration results in an increase in the packing density and structural rigidity of these glasses and consequently in their glass transition temperature Tg. This apparent role reversal of conventional network-modifying cations in invert alkaline-earth silicate glasses are compared and contrasted with that in their alkali silicate counterparts.

Amorphous calcium carbonate particles form coral skeletons

DOE PAGES

Mass, Tali; Giuffre, Anthony J.; Sun, Chang -Yu; ...

2017-08-28

Do corals form their skeletons by precipitation from solution or by attachment of amorphous precursor particles as observed in other minerals and biominerals? The classical model assumes precipitation in contrast with observed “vital effects,” that is, deviations from elemental and isotopic compositions at thermodynamic equilibrium. Here, we show direct spectromicroscopy evidence in Stylophora pistillata corals that two amorphous precursors exist, one hydrated and one anhydrous amorphous calcium carbonate (ACC); that these are formed in the tissue as 400-nm particles; and that they attach to the surface of coral skeletons, remain amorphous for hours, and finally, crystallize into aragonite (CaCO 3).more » We show in both coral and synthetic aragonite spherulites that crystal growth by attachment of ACC particles is more than 100 times faster than ion-by-ion growth from solution. Fast growth provides a distinct physiological advantage to corals in the rigors of the reef, a crowded and fiercely competitive ecosystem. Corals are affected by warming-induced bleaching and postmortem dissolution, but the finding here that ACC particles are formed inside tissue may make coral skeleton formation less susceptible to ocean acidification than previously assumed. If this is how other corals form their skeletons, perhaps this is how a few corals survived past CO 2 increases, such as the Paleocene–Eocene Thermal Maximum that occurred 56 Mya.« less

Amorphous calcium carbonate particles form coral skeletons

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

Mass, Tali; Giuffre, Anthony J.; Sun, Chang -Yu

Do corals form their skeletons by precipitation from solution or by attachment of amorphous precursor particles as observed in other minerals and biominerals? The classical model assumes precipitation in contrast with observed “vital effects,” that is, deviations from elemental and isotopic compositions at thermodynamic equilibrium. Here, we show direct spectromicroscopy evidence in Stylophora pistillata corals that two amorphous precursors exist, one hydrated and one anhydrous amorphous calcium carbonate (ACC); that these are formed in the tissue as 400-nm particles; and that they attach to the surface of coral skeletons, remain amorphous for hours, and finally, crystallize into aragonite (CaCO 3).more » We show in both coral and synthetic aragonite spherulites that crystal growth by attachment of ACC particles is more than 100 times faster than ion-by-ion growth from solution. Fast growth provides a distinct physiological advantage to corals in the rigors of the reef, a crowded and fiercely competitive ecosystem. Corals are affected by warming-induced bleaching and postmortem dissolution, but the finding here that ACC particles are formed inside tissue may make coral skeleton formation less susceptible to ocean acidification than previously assumed. If this is how other corals form their skeletons, perhaps this is how a few corals survived past CO 2 increases, such as the Paleocene–Eocene Thermal Maximum that occurred 56 Mya.« less

Analysis of the effect of CPP-ACP tooth mousse on enamel remineralization by circularly polarized images.

PubMed

Wu, Guotao; Liu, Xinqiang; Hou, Yongfu

2010-09-01

To evaluate the effect of casein phosphopeptide-amorphous calcium phosphate tooth mousse on the remineralization of bovine incisor by circularly polarized images. Eighty bovine incisors, each with a 4 x 4 mm artificially demineralized area, were used. The samples were divided into four groups: Group A, casein phosphopeptide-amorphous calcium phosphate tooth mousse; Group B, fluoride toothpaste; Group C, casein phosphopeptide-amorphous calcium phosphate tooth mousse and fluoride toothpaste; and Group D, no treatment. Circularly polarized images were taken after the specimens were treated for 3, 6, 9, or 12 weeks, and the size of the demineralized area and the mean grey level were measured. Data analysis was done using repeated measures variance analysis. Pearson correlation coefficients were computed to evaluate the correlation between the size of the demineralized area and the mean grey level. In all four groups, the size of the demineralized area and the mean grey level declined with time. The size of the demineralized area of Group C was significantly smaller than that of Group A at the end of the third and sixth weeks (P = .039, P = .000, respectively), and the mean grey level of Group C was lower than that of Group A at the end of the 6th and 12th weeks (P = .037, P = .004, respectively). At the end of the 6th, 9th, and 12th weeks, the size of the demineralized area of Group C was smaller (P = .000, P = .005, P = .005, respectively) and the mean grey level was lower (P = .000) than those of Group B. No statistically significant correlations were detected between the size of the demineralized area and the mean grey level. Casein phosphopeptide-amorphous calcium phosphate tooth mousse can reduce the size and mean grey level of demineralized areas and promote the remineralization of bovine enamel. Combined application with fluoride toothpaste strengthens the effect.

Dust in the Solar System - Properties and Origins

NASA Technical Reports Server (NTRS)

Messenger, Scott; Keller, Lindsay; Nakamura-Messenger, Keiko

2013-01-01

Interplanetary dust pervades the inner Solar System, giving rise to a prominent glow above the horizon at sunrise and sunset known as the zodiacal light. This dust derives from the disintegration of comets as they approach the Sun and from collisions among main-belt asteroids. The Earth accretes roughly 4x10(exp 6) kg/year of 1 - 1,000 micron dust particles as they spiral into the Sun under the influence of Poynting-Robertson drag and solar wind drag. Samples of these grains have been collected from deep sea sediments, Antarctic ice and by high-altitude aircraft and balloon flights. Interplanetary dust particles (IDPs) collected in the stratosphere have been classified by their IR spectra into olivine, pyroxene, and hydrated silicate-dominated classes. Most IDPs have bulk major and minor element abundances that are similar to carbonaceous chondrite meteorites. Hydrated silicate-rich IDPs are thought to derive from asteroids based on their mineralogy and low atmospheric entry velocities estimated from peak temperatures reached during atmospheric entry. Anhydrous IDPs are typically aggregates of 0.1 - approx. 1 micron Mg-rich olivine and pyroxene, amorphous silicates (GEMS), Fe, Nisulfides and rare spinel and oxides bound together by carbonaceous material. These IDPs are often argued to derive from comets based on compositional similarities and high atmospheric entry velocities that imply high eccentricity orbits. Infrared spectra obtained from anhydrous IDPs closely match remote IR spectra obtained from comets. The most primitive (anhydrous) IDPs appear to have escaped the parent-body thermal and aqueous alteration that has affected meteorites. These samples thus consist entirely of grains that formed in the ancient solar nebula and pre-solar interstellar and circumstellar environments. Isotopic studies of IDPs have identified silicate stardust grains that formed in the outflows of red giant and asymptotic giant branch stars and supernovae]. These stardust grains include both amorphous and crystalline silicates. The organic matter in these samples also exhibits highly anomalous H, C, and N isotopic compositions that are consistent with formation in low temperature environments at the outermost regions of the solar nebula or presolar cold molecular cloud. The scientific frontiers for these samples include working toward a better understanding of the origins of the solar system amorphous and crystalline grains in IDPs and the very challenging task of determining the chemical composition of sub-micron organic grains. Laboratory studies of ancient and present-day dust in the Solar System thus reveal in exquisite detail the chemistry, mineralogy and isotopic properties of materials that derive from a range of astrophysical environments. These studies are an important complement to astronomical observations that help to place the laboratory observations into broader context.

Composition characteristics and regularities of dissolving of hydroxyapatite materials obtained in water solutions with varied content of silicate ions

NASA Astrophysics Data System (ADS)

Solonenko, A. P.

2018-01-01

Research aimed at developing new bioactive materials for the repair of defects in bone tissues, do not lose relevance due to the strengthening of the regenerative approach in medicine. From this point of view, materials based on calcium phosphates, including silicate ions, consider as one of the most promising group of substances. Methods of synthesis and properties of hydroxyapatite doped with various amounts of SiO4 4- ions are described in literature. In the present work synthesis of a solid phase in the systems Ca(NO3)2 - (NH4)2HPO4 - Na2SiO3 - NH4OH - H2O (Cca/CP = 1.70) performed with a wide range of sodium silicate additive concentration (y = CSi/CP = 0 ÷ 5). It is established that under the studied conditions at y ≥ 0.3 highly dispersed poorly crystallized apatite containing isomorphic impurities of CO3 2- and SiO4 4- precipitates in a mixture with calcium hydrosilicate and SiO2. It is shown that the resulting composites can gradually dissolve in physiological solution and initiate passive formation of the mineral component of hard tissues.

Silica in alkaline brines

USGS Publications Warehouse

Jones, B.F.; Rettig, S.L.; Eugster, H.P.

1967-01-01

Analysis of sodium carbonate-bicarbonate brines from closed basins in volcanic terranes of Oregon and Kenya reveals silica contents of up to 2700 parts per million at pH's higher than 10. These high concentrations of SiO 2 can be attributed to reaction of waters with silicates, and subsequent evaporative concentration accompanied by a rise in pH. Supersaturation with respect to amorphous silica may occur and persist for brines that are out of contact with silicate muds and undersaturated with respect to trona; correlation of SiO2 with concentration of Na and total CO2 support this interpretation. Addition of moredilute waters to alkaline brines may lower the pH and cause inorganic precipitation of substantial amounts of silica.

Mid-infrared interferometric variability of DG Tau: implications for the inner-disk structure .

NASA Astrophysics Data System (ADS)

Ábrahám, P.; Varga, J.; Gabányi, K. É.; Chen, L.; Kóspál, Á.; Ratzka, Th.; van Boekel, R.; Mosoni, L.; Henning, Th.

DG Tau is a low-mass young star whose strongly accreting disk shows a variable 10 mu m silicate feature, that may even turn temporarily from emission to absorption. Aiming to find the physical reason of this variability, we analysed multiepoch VLTI/MIDI interferometric observations. We found that the inner disk within 3 au radius exhibits a 10 mu m absorption feature related to amorphous silicate grains, while the outer disk displays a variable crystalline feature in emission, similar in shape to the spectrum of comet Hale-Bopp. The variability may be related to a fluctuating amount of dusty material above the disk surface, possibly due to turbulence.

ATP-stabilized amorphous calcium carbonate nanospheres and their application in protein adsorption.

PubMed

Qi, Chao; Zhu, Ying-Jie; Lu, Bing-Qiang; Zhao, Xin-Yu; Zhao, Jing; Chen, Feng; Wu, Jin

2014-05-28

Calcium carbonate is a common substance found in rocks worldwide, and is the main biomineral formed in shells of marine organisms and snails, pearls and eggshells. Amorphous calcium carbonate (ACC) is the least stable polymorph of calcium carbonate, which is so unstable under normal conditions that it is difficult to be prepared in vitro because it rapidly crystallizes to form one of the more stable polymorphs in aqueous solution. Herein, we report the successful synthesis of highly stable ACC nanospheres in vitro using adenosine 5'-triphosphate disodium salt (ATP) as a stabilizer. The effect of ATP on the stability of ACC nanospheres is investigated. Our experiments show that ATP plays an unique role in the stabilization of ACC nanospheres in aqueous solution. Moreover, the as-prepared ACC nanospheres are highly stable in phosphate buffered saline for a relatively long period of time (12 days) even under relatively high concentrations of calcium and phosphate ions. The cytotoxicity tests show that the as-prepared highly stable ACC nanospheres have excellent biocompatibility. The highly stable ACC nanospheres have high protein adsorption capacity, implying that they are promising for applications in biomedical fields such as drug delivery and protein adsorption. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Developing a novel magnesium glycerophosphate/silicate-based organic-inorganic composite cement for bone repair.

PubMed

Ding, Zhengwen; Li, Hong; Wei, Jie; Li, Ruijiang; Yan, Yonggang

2018-06-01

Considering that the phospholipids and glycerophosphoric acid are the basic materials throughout the metabolism of the whole life period and the bone is composed of organic polymer collagen and inorganic mineral apatite, a novel self-setting composite of magnesium glycerophosphate (MG) and di-calcium silicate(C2S)/tri-calcium silicate(C3S) was developed as bio-cement for bone repair, reconstruction and regeneration. The composite was prepared by mixing the MG, C2S and C3S with the certain ratios, and using the deionized water and phosphoric acid solution as mixed liquid. The combination and formation of the composites was characterized by FTIR, XPS and XRD. The physicochemical properties were studied by setting time, compressive strength, pH value, weight loss in the PBS and surface change by SEM-EDX. The biocompatibility was evaluated by cell culture in the leaching solution of the composites. The preliminary results showed that when di- and tri-calcium silicate contact with water, there are lots of Ca(OH) 2 generated making the pH value of solution is higher than 9 which is helpful for the formation of hydroxyapatite(HA) that is the main bone material. The new organic-inorganic self-setting bio-cements showed initial setting time is ranged from 20 min to 85 min and the compressive strength reached 30 MPa on the 7th days, suitable as the bone fillers. The weight loss was 20% in the first week, and 25% in the 4th week. Meanwhile, the new HA precipitated on the composite surface during the incubation in the SBF showed bioactivity. The cell cultured in the leaching liquid of the composite showed high proliferation inferring the new bio-cement has good biocompatibility to the cells. Copyright © 2018 Elsevier B.V. All rights reserved.

A SOFIA FORCAST Grism Study of the Mineralogy of Dust in the Winds of Proto-planetary Nebulae: RV Tauri Stars and SRd Variables

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

Arneson, R. A.; Gehrz, R. D.; Woodward, C. E.

We present a SOFIA FORCAST grism spectroscopic survey to examine the mineralogy of the circumstellar dust in a sample of post-asymptotic giant branch (post-AGB) yellow supergiants that are believed to be the precursors of planetary nebulae. Our mineralogical model of each star indicates the presence of both carbon-rich and oxygen-rich dust species—contrary to simple dredge-up models—with a majority of the dust in the form of amorphous carbon and graphite. The oxygen-rich dust is primarily in the form of amorphous silicates. The spectra do not exhibit any prominent crystalline silicate emission features. For most of the systems, our analysis suggests thatmore » the grains are relatively large and have undergone significant processing, supporting the hypothesis that the dust is confined to a Keplerian disk and that we are viewing the heavily processed, central regions of the disk from a nearly face-on orientation. These results help to determine the physical properties of the post-AGB circumstellar environment and to constrain models of post-AGB mass loss and planetary nebula formation.« less

Physico-chemical mechanisms involved in the acceleration of the hydration of calcium sulfoaluminate cement by lithium ions

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

Cau Dit Coumes, Céline, E-mail: celine.cau-dit-coumes@cea.fr; Dhoury, Mélanie; Champenois, Jean-Baptiste

This work investigates the influence of lithium ions on the hydration at 25 °C of two calcium sulfoaluminate (CSA) cements comprising 0 or 10% gypsum. Small concentrations of lithium salts (LiOH, LiNO{sub 3}) accelerate the early hydration of both CSA cements either in paste or in diluted and stirred suspension. The effect of the lithium cation is much stronger than its counter-ion. Hydration is accelerated by an increase in the lithium concentration up to 30 μmol Li/g of the used CSA cement (with a high ye'elimite content), and then levels off. The postulated mechanism relies on a fast precipitation ofmore » amorphous Li-containing Al(OH){sub 3}, which acts as seeds for accelerating the precipitation of amorphous Al(OH){sub 3} that speeds up the whole hydration process. This process seems to be closely related to the one involved in the acceleration of the hydration of calcium aluminate cement by lithium ions.« less

A safer disposal of hazardous phosphate coating sludge by formation of an amorphous calcium phosphate matrix.

PubMed

Navarro-Blasco, I; Duran, A; Pérez-Nicolás, M; Fernández, J M; Sirera, R; Alvarez, J I

2015-08-15

Phosphate coating hazardous wastes originated from the automotive industry were efficiently encapsulated by an acid-base reaction between phosphates present in the sludge and calcium aluminate cement, yielding very inert and stable monolithic blocks of amorphous calcium phosphate (ACP). Two different compositions of industrial sludge were characterized and loaded in ratios ranging from 10 to 50 wt.%. Setting times and compressive strengths were recorded to establish the feasibility of this method to achieve a good handling and a safe landfilling of these samples. Short solidification periods were found and leaching tests showed an excellent retention for toxic metals (Zn, Ni, Cu, Cr and Mn) and for organic matter. Retentions over 99.9% for Zn and Mn were observed even for loadings as high as 50 wt.% of the wastes. The formation of ACP phase of low porosity and high stability accounted for the effective immobilization of the hazardous components of the wastes. Copyright © 2015 Elsevier Ltd. All rights reserved.

Method for scavenging mercury

DOEpatents

Chang, Shih-ger [El Cerrito, CA; Liu, Shou-heng [Kaohsiung, TW; Liu, Zhao-rong [Beijing, CN; Yan, Naiqiang [Berkeley, CA

2009-01-20

Disclosed herein is a method for removing mercury from a gas stream comprising contacting the gas stream with a getter composition comprising bromine, bromochloride, sulphur bromide, sulphur dichloride or sulphur monochloride and mixtures thereof. In one preferred embodiment the getter composition is adsorbed onto a sorbent. The sorbent may be selected from the group consisting of flyash, limestone, lime, calcium sulphate, calcium sulfite, activated carbon, charcoal, silicate, alumina and mixtures thereof. Preferred is flyash, activated carbon and silica.

Method for scavenging mercury

DOEpatents

Chang, Shih-Ger [El Cerrito, CA; Liu, Shou-Heng [Kaohsiung, TW; Liu, Zhao-Rong [Beijing, CN; Yan, Naiqiang [Berkeley, CA

2011-08-30

Disclosed herein is a method for removing mercury from a gas stream comprising contacting the gas stream with a getter composition comprising bromine, bromochloride, sulphur bromide, sulphur dichloride or sulphur monochloride and mixtures thereof. In one preferred embodiment the getter composition is adsorbed onto a sorbent. The sorbent may be selected from the group consisting of flyash, limestone, lime, calcium sulphate, calcium sulfite, activated carbon, charcoal, silicate, alumina and mixtures thereof. Preferred is flyash, activated carbon and silica.

Method for scavenging mercury

DOEpatents

Chang, Shih-ger; Liu, Shou-heng; Liu, Zhao-rong; Yan, Naiqiang

2010-07-13

Disclosed herein is a method for removing mercury from a gas stream comprising contacting the gas stream with a getter composition comprising bromine, bromochloride, sulphur bromide, sulphur dichloride or sulphur monochloride and mixtures thereof. In one preferred embodiment the getter composition is adsorbed onto a sorbent. The sorbent may be selected from the group consisting flyash, limestone, lime, calcium sulphate, calcium sulfite, activated carbon, charcoal, silicate, alumina and mixtures thereof. Preferred is flyash, activated carbon and silica.

Concept Study for Military Port Design Using Natural Processes.

DTIC Science & Technology

1982-06-15

exchange methods are so good in this ocean heat sink with its diffused materials because it uses its chemicals to attach the ions and then to make acids...H.L., "Saturation State of Calcium Carbonate in Seawater and its Possible Significance for Scale Formation on OTEC Heat Exchanger ," Abstract...Which Harvest Calcium and Magnesium as Structural Materials E. Forming Structures from Silicates After Ion Exchanging , Using Hot and Cold Forming

Optical characteristics of novel bulk and nanoengineered laser host materials

NASA Astrophysics Data System (ADS)

Prasad, Narasimha S.; Sova, Stacey; Kelly, Lisa; Bevan, Talon; Arnold, Bradley; Cooper, Christopher; Choa, Fow-Sen; Singh, N. B.

2018-02-01

The hexagonal apatite single crystals have been investigated for their applications as laser host materials. Czochralksi and flux growth methods have been utilized to obtain single crystals. For low temperature processing (<100 0C), several techniques for crystal growth have been developed. The hexagonal apatite structure (space group P63/m) is characteristic of several compounds, some of which have extremely interesting and useful properties as laser hosts and bone materials. Calcium lanthanum silicate (Nd-doped) and lanthanum aluminate material systems were studied in detail. Nanoengineered calcium and lanthanum based silicates were synthesized by a solution method and their optical and morphological characteristics were compared with Czochralski grown bulk hydroxyapatite single crystals. Materials were evaluated by absorbance, fluorescence and Raman characteristics. Neodymium, iron and chromium doped crystals grown by a solution method showed weak but similar optical properties to that of Czochralski grown single crystals.

Calcium silicate-based cements: composition, properties, and clinical applications.

PubMed

Dawood, Alaa E; Parashos, Peter; Wong, Rebecca H K; Reynolds, Eric C; Manton, David J

2017-05-01

Mineral trioxide aggregate (MTA) is a calcium silicate-based cement (CSC) commonly used in endodontic procedures involving pulpal regeneration and hard tissue repair, such as pulp capping, pulpotomy, apexogenesis, apexification, perforation repair, and root-end filling. Despite the superior laboratory and clinical performance of MTA in comparison with previous endodontic repair cements, such as Ca(OH) 2 , MTA has poor handling properties and a long setting time. New CSC have been commercially launched and marketed to overcome the limitations of MTA. The aim of the present review was to explore the available literature on new CSC products, and to give evidence-based recommendations for the clinical use of these materials. Within the limitations of the available data in the literature regarding the properties and performance of the new CSC, the newer products could be promising alternatives to MTA; however, further research is required to support this assumption. © 2015 Wiley Publishing Asia Pty Ltd.

Docking 90Sr radionuclide in cement: An atomistic modeling study

NASA Astrophysics Data System (ADS)

Youssef, Mostafa; Pellenq, Roland J.-M.; Yildiz, Bilge

Cementitious materials are considered to be a waste form for the ultimate disposal of radioactive materials in geological repositories. We investigated by means of atomistic simulations the encapsulation of strontium-90, an important radionuclide, in calcium-silicate-hydrate (C-S-H) and its crystalline analog, the 9 Å-tobermorite. C-S-H is the major binding phase of cement. Strontium was shown to energetically favor substituting calcium in the interlayer sites in C-S-H and 9 Å-tobermorite with the trend more pronounced in the latter. The integrity of the silicate chains in both cementitious waste forms were not affected by strontium substitution within the time span of molecular dynamics simulation. Finally, we observed a limited degradation of the mechanical properties in the strontium-containing cementitious waste form with the increasing strontium concentration. These results suggest the cement hydrate as a good candidate for immobilizing radioactive strontium.

Obtaining and Characterization of Polyolefin-Filled Calcium Carbonate Composites Modified with Stearic Acid

NASA Astrophysics Data System (ADS)

Croitoru, C.; Pascu, A.; Roata, I. C.; Stanciu, E. M.

2017-06-01

In order to obtain high performance calcium carbonate-reinforced HDPE and PP composites, the dispersibility and compatibility of the inorganic phase in the polymer has been achieved through surface treatment of the amorphous calcium carbonate filler with stearic acid. The surface coating of the inorganic phase has been proved by XRD and FTIR spectroscopy, through forming of an intermediate layer of calcium stearate which acts as a surfactant, efficient in providing an optimum compatibility with the dominatingly hydrophobic polymer matrix, as determined from the structural information obtained through samples cross-sections analysing.

Biodentine™ material characteristics and clinical applications: a 3 year literature review and update.

PubMed

Rajasekharan, S; Martens, L C; Cauwels, R G E C; Anthonappa, R P; Verbeeck, R M H

2018-02-01

Biodentine™ has frequently been acknowledged in the literature as a promising material and serves as an important representative of tricalcium silicate based cements used in dentistry. To provide an update on the physical and biological properties of Biodentine™ and to compare these properties with those of other tricalcium silicate cements namely, different variants of mineral trioxide aggregate (MTA) such as ProRoot MTA, MTA Angelus, Micro Mega MTA (MM-MTA), Retro MTA, Ortho MTA, MTA Plus, GCMTA, MTA HP and calcium enriched mixture (CEM), Endosequence and Bioaggregate™. A comprehensive literature search for publications from November 20, 2013 to November 20, 2016 was performed by two independent reviewers on Medline (PubMed), Embase, Web of Science, CENTRAL (Cochrane), SIGLE, SciELO, Scopus, Lilacs and clinicaltrials.gov. Electronic and hand search was carried out to identify randomised control trials (RCTs), case control studies, case series, case reports, as well as in vitro and animal studies published in the English language. The enhanced physical and biologic properties of Biodentine™ could be attributed to the presence of finer particle size, use of zirconium oxide as radiopacifier, purity of tricalcium silicate, absence of dicalcium silicate, and the addition of calcium chloride and hydrosoluble polymer. Furthermore, as Biodentine™ overcomes the major drawbacks of MTA it has great potential to revolutionise the different treatment modalities in paediatric dentistry and endodontics especially after traumatic injuries. Nevertheless, high quality long-term clinical studies are required to facilitate definitive conclusions.

Source apportionment of aerosol particles near a steel plant by electron microscopy.

PubMed

Ebert, Martin; Müller-Ebert, Dörthe; Benker, Nathalie; Weinbruch, Stephan

2012-12-01

The size, morphology and chemical composition of 37,715 individual particles collected over 22 sampling days in the vicinity of a large integrated steel production were studied by scanning and transmission electron microscopy. Based on the morphology, chemistry and beam stability the particles were classified into the following fourteen groups: silicates, sea salt, calcium sulfates, calcium carbonates, carbonate-silicate mixtures, sulfate-silicate mixtures, iron oxides, iron mixtures, metal oxide-metals, complex secondary particles, soot, Cl-rich particles, P-rich particles, and other particles. The majority of iron oxide (≈85%) and metal oxide-metal (≈70%) particles as well as ≈20% of the silicate particles are fly ashes from high temperature processes. The emissions from the steel work are dominated by iron oxide particles. For source apportionment, seven source categories and two sectors of local wind direction (industrial and urban background) were distinguished. In both sectors PM₁₀ consists of four major source categories: 35% secondary, 20% industrial, 17% soil and 16% soot in the urban background sector compared to 45% industrial, 20% secondary, 13% soil, and 9% soot in the industrial sector. As the secondary and the soot components are higher in the urban background sector than in the industrial sector, it is concluded that both components predominantly originate from urban background sources (traffic, coal burning, and domestic heating). Abatement measures should not only focus on the steel work but should also include the urban background aerosol.

Effects of dietary supplementation of arginine-silicate-inositol complex on absorption and metabolism of calcium of laying hens

PubMed Central

Orhan, Cemal; Tuzcu, Mehmet; Hayirli, Armagan; Komorowski, James R.; Sahin, Nurhan

2018-01-01

The effects of supplementation of arginine-silicate-inositol complex (ASI; 49.5–8.2–25 g/kg, respectively) to laying hens were investigated with respect to eggshell quality, calcium (Ca) balance, and expression of duodenal proteins related to Ca metabolism (calbindin and tight junction proteins). A total of 360 laying hens, 25 weeks old, were divided into 3 groups consisting of 6 replicate of cages, 20 birds per cage. The groups were fed a basal diet and the basal diet supplemented with 500 or 1000 mg ASI complex per kilogram for 90 days. Data were analyzed by ANCOVA using data during the first week of the adaptation period as covariates. As the ASI complex supplementation level increased, there were increases in feed intake (P < 0.0001), egg production (P < 0.001), egg weight (P < 0.0001) and eggshell weight (P < 0.001) weight, and shell thickness (P < 0.001) and decreases in feed conversion ratio and cracked egg percentage (P < 0.0001 for both). Concentrations of serum osteocalcin (P < 0.0001), vitamin D (P < 0.0001), calcium (P < 0.001), phosphorus (P < 0.001), and alkaline phosphatase (P < 0.008) as well as amounts of calcium retention (P < 0.0001) and eggshell calcium deposition (P < 0.001), and Ca balance (P < 0.0001) increased, whereas amount of calcium excretion (P < 0.001) decreased linearly in a dose-dependent manner. The ASI complex supplementation increased expressions of calcium transporters (calbindin-D28k, N sodium-calcium exchanger, plasma membrane calcium ATPase, and vitamin D receptor) and tight junction proteins (zonula occludens-1 and occludin) in the duodenum in a linear fashion (P < 0.0001 for all). In conclusion, provision of dietary ASI complex to laying hens during the peak laying period improved eggshell quality through improving calcium utilization as reflected by upregulation of genes related to the calcium metabolism. Further studies are needed to elucidate the contribution of each of the ASI complex ingredients. PMID:29360830

The effect of crystal structure of TiO2 nanotubes on the formation of calcium phosphate coatings during biomimetic deposition

NASA Astrophysics Data System (ADS)

Liu, Yi; Kim, Sun; McLeod, John A.; Li, Jun; Guo, Xiaoxuan; Sham, Tsun-Kong; Liu, Lijia

2017-02-01

The crystallization process of bioactive calcium phosphate (CaP) species via biomimetic deposition onto anodic TiO2 nanotubes is investigated. The porous surface of nanostructured TiO2 provides an ideal substrate for CaP crystallization. The compositions of CaP coatings are studied using X-ray absorption near-edge structures (XANES) at the Ca K-edge. Using detection modes with different probing depths, both the surface of the CaP coating and the CaP-TiO2 interface are simultaneously analyzed. Calcium phosphate (CaP) species, such as hydroxyapatite (HAp), octacalcium phosphate (Ca8(HPO4)2(PO4)4·5H2O, OCP), brushite (CaHPO4·2H2O, DCPD), and amorphous calcium phosphate (ACP), are found in the CaP coatings. TiO2 nanotubes of amorphous and anatase phases are comparatively studied to determine their effect on the efficiency of CaP formation and the phase transformation among CaP species in prolonged deposition time. It is found the composition of CaP coating has a strong dependency on the crystal structure of TiO2 substrate and the kinetics (deposition time).

Effects of amorphous calcium phosphate stabilized by casein phosphopeptides on enamel de- and remineralization in primary teeth: an in vitro study.

PubMed

Bar-Hillel, Rita; Feuerstein, Osnat; Tickotsky, Nili; Shapira, Joseph; Moskovitz, Moti

2012-01-01

Amorphous calcium phosphate, stabilized by casein phosphopeptides, has been found to enhance remineralization of subsurface lesions in permanent teeth. The purpose of the present in vitro study was to evaluate the potential of GC Tooth Mousse to enhance remineralization of initial demineralized enamel sites in primary teeth. Forty-four demineralization sites were created in 22 extracted primary teeth. Samples were randomly assigned to 6 treatment groups (GC Tooth Mousse covering, GC Tooth Mousse covering and demineralization, and control groups). The mineral content of each sample was evaluated using energy dispersive X-ray analysis, performed from the enamel surface of each lesion inwards. The results were analyzed using analysis of variance, with a significance level P<.05. Samples treated with GC Tooth Mousse demonstrated an increase in the calcium-phosphate ratio by approximately 2% near the surface, a minimal increase of 1% at a depth over 60 μm, and no change at a depth from 40 to 60 μm, with no statistically significant differences (P>.05). This study demonstrates a minimal increase in the subsurface calcium-phosphate ratio following GC Tooth Mousse treatment, especially in demineralized enamel tissue.

Material transport in laser-heated diamond anvil cell melting experiments

NASA Technical Reports Server (NTRS)

Campbell, Andrew J.; Heinz, Dion L.; Davis, Andrew M.

1992-01-01

A previously undocumented effect in the laser-heated diamond anvil cell, namely, the transport of molten species through the sample chamber, over distances large compared to the laser beam diameter, is presented. This effect is exploited to determine the melting behavior of high-pressure silicate assemblages of olivine composition. At pressures where beta-spinel is the phase melted, relative strengths of partitioning can be estimated for the incompatible elements studied. Iron was found to partition into the melt from beta-spinel less strongly than calcium, and slightly more strongly than manganese. At higher pressures, where a silicate perovskite/magnesiowuestite assemblage is melted, it is determined that silicate perovskite is the liquidus phase, with iron-rich magnesiowuestite accumulating at the end of the laser-melted stripe.

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

Feng, Pei; Wei, Pingpin; Li, Pengjian

Calcium silicate possessed excellent biocompatibility, bioactivity and degradability, while the high brittleness limited its application in load-bearing sites. Hydroxyapatite whiskers ranging from 0 to 30 wt.% were incorporated into the calcium silicate matrix to improve the strength and fracture resistance. Porous scaffolds were fabricated by selective laser sintering. The effects of hydroxyapatite whiskers on the mechanical properties and toughening mechanisms were investigated. The results showed that the scaffolds had a uniform and continuous inner network with the pore size ranging between 0.5 mm and 0.8 mm. The mechanical properties were enhanced with increasing hydroxyapatite whiskers, reached a maximum at 20more » wt.% (compressive strength: 27.28 MPa, compressive Young's modulus: 156.2 MPa, flexural strength: 15.64 MPa and fracture toughness: 1.43 MPa·m{sup 1/2}) and then decreased by addition of more hydroxyapatite whiskers. The improvement of mechanical properties was due to whisker pull-out, crack deflection and crack bridging. Moreover, the degradation rate decreased with the increase of hydroxyapatite whisker content. A layer of bone-like apatite was formed on the scaffold surfaces after being soaked in simulated body fluid. Human osteoblast-like MG-63 cells spread well on the scaffolds and proliferated with increasing culture time. These findings suggested that the calcium silicate scaffolds reinforced with hydroxyapatite whiskers showed great potential for bone regeneration and tissue engineering applications. - Highlights: • HA whiskers were incorporated into CS to improve the properties. • The scaffolds were successfully fabricated by SLS. • Toughening mechanisms was whisker pull-out, crack deflection and bridging. • The scaffolds showed excellent apatite forming ability.« less

In vitro effects of two silicate-based materials, Biodentine and BioRoot RCS, on dental pulp stem cells in models of reactionary and reparative dentinogenesis

PubMed Central

Loison-Robert, Ludwig Stanislas; Berbar, Tsouria; Isaac, Juliane; Berdal, Ariane; Simon, Stéphane

2018-01-01

Background Calcium silicate-based cements are biomaterials with calcium oxide and carbonate filler additives. Their properties are close to those of dentin, making them useful in restorative dentistry and endodontics. The aim of this study was to evaluate the in vitro biological effects of two such calcium silicate cements, Biodentine (BD) and Bioroot (BR), on dental stem cells in both direct and indirect contact models. The two models used aimed to mimic reparative dentin formation (direct contact) and reactionary dentin formation (indirect contact). An original aspect of this study is the use of an interposed thin agarose gel layer to assess the effects of diffusible components from the materials. Results The two biomaterials were compared and did not modify dental pulp stem cell (DPSC) proliferation. BD and BR showed no significant cytotoxicity, although some cell death occurred in direct contact. No apoptosis or inflammation induction was detected. A striking increase of mineralization induction was observed in the presence of BD and BR, and this effect was greater in direct contact. Surprisingly, biomineralization occurred even in the absence of mineralization medium. This differentiation was accompanied by expression of odontoblast-associated genes. Exposure by indirect contact did not stimulate the induction to such a level. Conclusion These two biomaterials both seem to be bioactive and biocompatible, preserving DPSC proliferation, migration and adhesion. The observed strong mineralization induction through direct contact highlights the potential of these biomaterials for clinical application in dentin-pulp complex regeneration. PMID:29370163

Effect of the calcium silicate-based sealer removal protocols and time-point of acid etching on the dentin adhesive interface.

PubMed

Morais, Jéssika Mayhara Pereira; Victorino, Keli Regina; Escalante-Otárola, Wilfredo Gustavo; Jordão-Basso, Keren Cristina Fagundes; Palma-Dibb, Regina Guenka; Kuga, Milton Carlos

2018-06-15

The aim of the study was to evaluate the effects when acid etching on the dentin surface was immediately performed (I) or 7 days (D) after calcium silicate-based sealer (MTA Fillapex) removal, using 95% ethanol (E) or xylol (X). First study, 60 bovine incisor dentin specimens were impregnated with sealer and divided into six groups (n = 10): (EI), E + I; (XI), X + I; (ED), E + D; (XD), X + D, (UN), untreated and (MR), mechanical removal of sealer. Scanning electron microscopy (SEM) images (500×) were obtained from each specimen and scores assessed the sealer residues persistence. Second study, 60 specimens were similarly treated; however, the specimens were restored with composite resin after the removal protocols. Hybrid layer formation was evaluated using confocal laser microscopy (1,024×). Third study, 60 specimens were similarly obtained and subjected to micro-shear test to evaluate the effects of removal protocols on the bond strength of etch-and- rinse adhesive system to dentin. XI showed the highest persistence of sealer residues (p < .05), similar to MR (p > .05). EI showed the greatest hybrid layer extension, except in relation to UN (p < .05). XI and MR presented the lowest bond strength adhesive system to dentin (p < .05). Acid etching immediately after calcium silicate-based endodontic sealer removal using xylol presented the highest residues persistence and negatively affected the adhesive interface between dentin and etch-and-rinse adhesive system. © 2018 Wiley Periodicals, Inc.

Thermodynamics and Kinetics of Boron Removal from Metallurgical Grade Silicon by Addition of High Basic Potassium Carbonate to Calcium Silicate Slag

NASA Astrophysics Data System (ADS)

Wu, Jijun; Wang, Fanmao; Ma, Wenhui; Lei, Yun; Yang, Bin

2016-06-01

In this study, we investigated the thermodynamics and kinetics of boron removal from metallurgical grade silicon (MG-Si) using a calcium silicate slag containing a high basic potassium carbonate. The distribution of boron between slag and silicon was theoretically derived and the distribution coefficients ( L B) of boron with different compositions of CaO, SiO2, and K2CO3 in slag reagents were determined. The maximal value of L B reached 2.08 with a high basicity slag of 40 pctCaO-40 pctSiO2-20 pctK2CO3 (Λ = 0.73). The boron removal rates from MG-Si using CaO-SiO2 and CaO-SiO2-K2CO3 slags at 1823 K (1550 °C) were investigated in an electromagnetic induction furnace. The results showed that the boron concentration in MG-Si can be reduced from 22 to 1.8 ppmw at 1823 K (1550 °C) with 20 pct K2CO3 addition to calcium silicate slag, where the removal efficiency of boron reached 91.8 pct. The mass transfer coefficient ( β S) of boron in binary 50 pctCaO-50 pctSiO2 slag was 3.16 × 10-6 m s-1 at 1823 K (1550 °C) and was 2.43 × 10-5 m s-1 in ternary 40 pctCaO-40 pctSiO2-20 pctK2CO3 slag.

Hydration behaviors of calcium silicate-based biomaterials.

PubMed

Lee, Yuan-Ling; Wang, Wen-Hsi; Lin, Feng-Huie; Lin, Chun-Pin

2017-06-01

Calcium silicate (CS)-based biomaterials, such as mineral trioxide aggregate (MTA), have become the most popular and convincing material used in restorative endodontic treatments. However, the commercially available CS-based biomaterials all contain different minor additives, which may affect their hydration behaviors and material properties. The purpose of this study was to evaluate the hydration behavior of CS-based biomaterials with/without minor additives. A novel CS-based biomaterial with a simplified composition, without mineral oxides as minor additives, was produced. The characteristics of this biomaterial during hydration were investigated using scanning electron microscopy (SEM), X-ray diffraction (XRD), and Fourier transform infrared (FTIR) spectrometry. The hydration behaviors of commercially available gray and white MTAs with mineral oxide as minor additives were also evaluated for reference. For all three test materials, the XRD analysis revealed similar diffraction patterns after hydration, but MTAs presented a significant decrease in the intensities of Bi 2 O 3 -related peaks. SEM results demonstrated similar porous microstructures with some hexagonal and facetted crystals on the outer surfaces. In addition, compared to CS with a simplified composition, the FTIR plot indicated that hydrated MTAs with mineral oxides were better for the polymerization of calcium silicate hydrate (CSH), presenting Si-O band shifting to higher wave numbers, and contained more water crystals within CSH, presenting sharper bands for O-H bending. Mineral oxides might not result in significant changes in the crystal phases or microstructures during the hydration of CS-based biomaterials, but these compounds affected the hydration behavior at the molecular level. Copyright © 2016. Published by Elsevier B.V.

New high-capacity, calcium-based sorbents, calcium silicate sorbents. Final report, 1993--August 31, 1994

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

Kenney, M.C.; Chiang, R.K.; Fillgrove, K.L.

1995-02-01

A search is being carried out for new calcium-based S0{sub 2} sorbents for induct injection. More specifically, a search is being carried out for induct injection calcium silicate sorbents that are highly cost effective. The objectives for the current year include the study of sorbents made from Ca(OH){sub 2}, from mixtures of Ca(OH){sub 2} and SiO{sub 2}, and from portland cement. They also include the study of sorbents made from model compounds. During this year, sorbents prepared from Ca(OH){sub 2} and from mixtures of Ca(OH){sub 2} and fumed SiO{sub 2} were investigated. The results show that very good SiO{sub 2}-modifiedmore » Ca(OH){sub 2} sorbents in which the Si-to-Ca reactant ratio is low can be prepared from Ca(OH){sub 2} and fumed SiO{sub 2}. Sorbents prepared from Ca(OH){sub 2} and natural SiO{sub 2} or natural SiO{sub 2} sources were also studied. The results obtained show that very good SiO{sub 2}-modified Ca(OH){sub 2} sorbents and calcium silicate hydrate sorbents, C-S-H sorbents, can be prepared from Ca(OH){sub 2} and diatomite, pumice or perlite, minerals that are readily available. In addition. sorbents prepared from Ca{sub 3}SiO{sub 5} and {beta}-Ca{sub 2}SiO{sub 4} and from mixtures of these compounds and SiO{sub 2} were studied. The results secured demonstrate that very good C-S-H rich sorbents can be prepared from these compounds and from mixtures of them with SiO{sub 2}. They also provide information useful for interpreting the cement sorbent results. Sorbents prepared from cement and from mixtures of cement and natural SiO{sub 2} or SiO{sub 2} sources were investigated as well. The results secured show that cement and mixtures of it with diatomite, pumice or perlite rapidly yield excellent sorbents with the proper reaction conditions.« less

Enhanced removal of humic acid from aqueous solution by novel stabilized nano-amorphous calcium phosphate: Behaviors and mechanisms

NASA Astrophysics Data System (ADS)

Jiang, Ling; Li, Yiming; Shao, Yi; Zhang, Yong; Han, Ruiming; Li, Shiyin; Wei, Wei

2018-01-01

Stabilized nano-amorphous calcium phosphate (nACP) was prepared using polyethylene glycol as stabilizer to obtain a nanosized amorphous adsorbent. The produced nACP was evaluated by using XRD, FTIR, SEM and X-ray photoelectron spectroscopy (XPS). The sedimentation test demonstrated that nACP exhibited better stability than crystallized hydroxyapatite. The adsorption efficiency of the nACP material for aqueous humic acid (HA) was evaluated from the point of view of medium pH, adsorption time, temperature, and ionic strength, as well as the presences of metal ions. The results of the study showed very good adsorption performance towards aqueous HA. The Sips modeling results revealed that the stabilized nACP adsorbent had a considerably high adsorption capacity (248.3 mg/g) for HA at 298 K. The adsorption data fitted well into pseudo-second order and Elovich kinetic models. XPS analyses indicated that HA retention on nACP material might be due to the surface complexation reaction between oxygen-containing group and calcium of HA and nACP, respectively. Moreover, the HA adsorption capacity of nACP could still keep more than 86% after four adsorption-desorption cycles. By taking into account all results it was concluded that the nACP adsorbent leveraged its stability in combination with its high uptake capacity to offer a great promise for HA adsorption from water.

Modeling of Amorphous Calcium Carbonate

NASA Astrophysics Data System (ADS)

Sinha, Sourabh; Rez, Peter

2011-10-01

Many species (e.g. sea urchin) form amorphous calcium carbonate (ACC) precursor phases that subsequently transform into crystalline CaCO3. It is certainly possible that ACC might have up to 10 wt% Mg and ˜3 wt% of water. The structure of ACC and mechanisms by which it transforms to crystalline phase are still unknown. Our goal here is to determine an atomic structure model that is consistent with diffraction and IR measurements of ACC. For this purpose a calcite supercell with 24 formula units (120 atoms) was constructed. Various configurations with 6 Mg atoms substituting for Ca (6 wt%) and 3-5 H2O molecules (2.25- 3.75 wt%) inserted in the spaces between Ca atoms, were relaxed using VASP. Most noticeable effects were the tilts of CO3 groups and distortion of Ca sub-lattice, especially in the case of water. The distributions of nearest Ca-Ca distance and CO3 tilts were extracted from those configurations. We also performed the same analysis starting with aragonite. Sampling from above distributions we built models for amorphous calcite/aragonite of size ˜1700 nm^3. We found that the induced distortions were not enough to generate a diffraction pattern typical of an amorphous material. Next we studied diffraction pattern of several nano-crystallites as recent studies suggest that amorphous calcite might be composed of nano- crystallites. We could then generate a diffraction pattern that appeared similar to that from ACC, for a nano-crystallite of size ˜2 nm^3.

Synthesis and characterization of nanosized calcium phosphates by flame spray pyrolysis, and their effect on osteogenic differentiation of stem cells

NASA Astrophysics Data System (ADS)

Ataol, Sibel; Tezcaner, Ayşen; Duygulu, Ozgur; Keskin, Dilek; Machin, Nesrin E.

2015-02-01

The present study evaluates the synthesis of biocompatible osteoconductive and osteoinductive nano calcium phosphate (CaP) particles by industrially applied, aerosol-derived flame spray pyrolysis method for biomedical field. Calcium phosphate nanoparticles were produced in a range of calcium-to-phosphorus ratio, (1.20-2.19) in order to analyze the morphology and crystallinity changes, and to test the bioactivity of particles. The characterization results confirmed that nanometer-sized, spherical calcium phosphate particles were produced. The average primary particle size was determined as 23 nm by counting more than 500 particles in TEM pictures. XRD patterns, HRTEM, SAED, and SEM analyses revealed the amorphous nature of the as-prepared nano calcium phosphate particles at low Ca/P ratios. Increases in the specific surface area and crystallinity were observed with the increasing Ca/P ratio. TGA-DTA analysis showed that the thermally stable crystal phases formed after 700 °C. Cell culture studies were conducted with urine-derived stem cells that possess the characteristics of mesenchymal stem cells. Synthesized amorphous nanoparticles did not have cytotoxic effect at 5-50 μg/ml concentration range. Cells treated with the as-prepared nanoparticles had higher alkaline phosphatase (ALP) enzyme activity than control cells, indicating osteogenic differentiation of cells. A slight decrease in ALP activity of cells treated with two highest Ca:P ratios at 50 μg/ml concentration was observed at day 7. The findings suggest that calcium phosphate nanoparticles produced in this work have a potential to be used as biomaterials in biomedical applications.

Mode of action studies on the formation of enamel minerals from a novel toothpaste containing calcium silicate and sodium phosphate salts.

PubMed

Sun, Yuekui; Li, Xiaoke; Deng, Yan; Sun, Jianing N; Tao, DanYing; Chen, Hui; Hu, Qinghong; Liu, Renjiang; Liu, Weining; Feng, Xiping; Wang, Jinfang; Carvell, Mel; Joiner, Andrew

2014-06-01

To investigate in vitro and in situ the deposition and formation of hydroxyapatite (HAP) on enamel surfaces following brushing with a novel toothpaste containing calcium silicate (CaSi), sodium phosphate salts and fluoride. Polished enamel blocks were brushed in vitro with a slurry of the CaSi toothpaste. After one brush and four weeks simulated brushing the enamel surfaces were analysed. In an in situ protocol, enamel blocks were attached to first or second molar teeth of healthy subjects, exposed to 4 weeks twice per day brushing with the CaSi toothpaste and then analysed. The surface deposits were analysed using scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM) and selected area electron diffraction (SAED). In addition, the CaSi toothpaste was slurried in simulated oral fluid (SOF) over a 3 hour period and the solids were isolated and analysed by Fourier transform infrared spectroscopy (FTIR). The FTIR study demonstrated that calcium phosphate phases had formed and these became increasingly crystalline over 3 hours. CaSi was deposited onto enamel surfaces following one brushing with the toothpaste in vitro.The deposited particles showed evidence of HAP crystalline phases associated with the CaSi. Following 4 weeks brushing in vitro, the deposition increased and analyses showed that the deposited material was HAP. These results were confirmed by the in situ study. Calcium silicate can be deposited onto enamel surfaces from a novel toothpaste formulation where it can form the enamel mineral HAP. A novel toothpaste formulation containing CaSi can form HAP on enamel surfaces. The potential of this technology is for a novel approach to the repair of demineralised enamel and the protection of enamel during acid exposure. © 2014 Elsevier Ltd. All rights reserved.

Influence of bioactive particles on the chemical-mechanical properties of experimental enamel resin infiltrants.

PubMed

Sfalcin, Ravana Angelini; Correr, Américo Bortolazzo; Morbidelli, Lucas Rafael; Araújo, Tatiany Gabrielle Freire; Feitosa, Victor Pinheiro; Correr-Sobrinho, Lourenço; Watson, Timothy Frederick; Sauro, Salvatore

2017-07-01

This study aimed at evaluating the chemophysical properties of experimental resin infiltrants (ERIs) doped with different bioactive particles. A control resin infiltrant (CR) was formulated using triethylene glycol dimethacrylate (TEGDMA) and ethoxylated bisphenol A dimethacrylate (BisEMA). Moreover, five experimental ERIs were also created by incorporating the following bioactive fillers (10 wt%) into the CR: hydroxyapatite (Hap), amorphous calcium phosphate (ACP), zinc-polycarboxylated bioactive glass (BAG-Zn), bioactive glass 45S5 (BAG 45S5), and calcium silicate modified with beta tricalcium phosphate (β-TCP). ICON® resin infiltrant was also used as control. All the ERIs used in this study were assessed for degree of conversion (DC), Knoop microhardness (KHN), softening ratio (SR), tensile cohesive strength (TCS), modulus of elasticity (E-modulus), water sorption (WS), and solubility (SL). Data were subjected to ANOVA and Tukey's test (α = 5%). ICON® presented the lowest DC, KHN, TCS, E-modulus, and SR. Incorporation of bioactive fillers into CR caused significant increase in the KHN. Conversely, no significant effect was observed on DC, TCS, and E-modulus. The resin infiltrant containing Hap showed a significant increase in softening ratio, while, ICON® presented the highest WS and SL. The WS of ACP-doped resin infiltrant was significantly higher than that of the Hap-doped infiltrant. The SL of the ACP-doped infiltrant was higher than CR BAG-Zn or BAG 45S5. The incorporation of bioactive particles into experimental resin infiltrants can improve the chemomechanical properties and reduce water sorption and solubility. Resin infiltrants doped with bioactive particles may improve the long-term performance of the treatment of white-spot lesions.

Effects of solution chemistry on arsenic(V) removal by low-cost adsorbents.

PubMed

Wang, Yuru; Tsang, Daniel C W

2013-11-01

Natural and anthropogenic arsenic (As) contamination of water sources pose serious health concerns, especially for small communities in rural areas. This study assessed the applicability of three industrial byproducts (coal fly ash, lignite, and green waste compost) as the low-cost adsorbents for As(V) removal under various field-relevant conditions (dissolved oxygen, As(V)/Fe ratio, solution pH, and presence of competing species). The physico-chemical properties of the adsorbents were characterized by XRD, XRF, FT-IR, and NMR analysis. Batch experiments demonstrated that coal fly ash could provide effective As(V) removal (82.1%-95%) because it contained high content of amorphous iron/aluminium hydroxides for As(V) adsorption and dissolvable calcium minerals for calcium arsenate precipitation. However, the addition of lignite and green waste compost was found unfavourable since they hindered the As(V) removal by 10%-42% possibly due to dissolution of organic matter and ternary arsenate-iron-organic matter complexes. On the other hand, higher concentrations of dissolved iron (comparing As(V)/Fe ratios of 1:1 and 1:10) and dissolved oxygen (comparing 0.2 and 6 mg/L) only marginally enhanced the As(V) removal at pH 6 and 8. Thus, addition of dissolved iron, water aeration, or pH adjustment became unnecessary because coal fly ash was able to provide effective As(V) removal under the natural range of geochemical conditions. Moreover, the presence of low levels of background competing (0.8 or 8 mg/L of humic acid, phosphate, and silicate) imposed little influence on As(V) removal, possibly because the high adsorption capacity of coal fly ash was far from exhaustion. These results suggested that coal fly ash was a potentially promising adsorbent that warranted further investigation.

Intrinsic differences in atomic ordering of calcium (alumino)silicate hydrates in conventional and alkali-activated cements

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

White, Claire E., E-mail: whitece@princeton.edu; Andlinger Center for Energy and the Environment, Princeton University, Princeton; Lujan Neutron Scattering Center, Los Alamos National Laboratory, Los Alamos

2015-01-15

The atomic structures of calcium silicate hydrate (C–S–H) and calcium (–sodium) aluminosilicate hydrate (C–(N)–A–S–H) gels, and their presence in conventional and blended cement systems, have been the topic of significant debate over recent decades. Previous investigations have revealed that synthetic C–S–H gel is nanocrystalline and due to the chemical similarities between ordinary Portland cement (OPC)-based systems and low-CO{sub 2} alkali-activated slags, researchers have inferred that the atomic ordering in alkali-activated slag is the same as in OPC–slag cements. Here, X-ray total scattering is used to determine the local bonding environment and nanostructure of C(–A)–S–H gels present in hydrated tricalcium silicatemore » (C{sub 3}S), blended C{sub 3}S–slag and alkali-activated slag, revealing the large intrinsic differences in the extent of nanoscale ordering between C–S–H derived from C{sub 3}S and alkali-activated slag systems, which may have a significant influence on thermodynamic stability, and material properties at higher length scales, including long term durability of alkali-activated cements.« less

ILLUMINATING THE ROLE OF AGGLOMERATES ON CRITICAL PHYSICOCHEMICAL PROPERTIES OF AMORPHOUS CALCIUM PHOSPHATE COMPOSITES

PubMed Central

O’Donnell, J.N.R.; Antonucci, J.M.; Skrtic, D.

2009-01-01

Water sorption (WS), mechanical strength, and ion release of polymeric composites formulated with 40 % as-made or milled amorphous calcium phosphate (ACP) are compared after 1, 2 and 3 months of aqueous exposure. Ethoxylated bisphenol A dimethacrylate, triethylene glycol dimethacrylate, 2-hydroxyethyl methacrylate and methacryloxyethyl phthalate comprised the resin. The WS (mass %) peaked at 3 months. WS of as-made ACP composites was significantly higher than WS of milled ACP composites and copolymers. Both composite groups experienced decreases in biaxial flexural strength (BFS) with water aging, with milled ACP composites retaining a significantly higher BFS throughout immersion. Ion release was moderately reduced in milled ACP composites, though they remained superior to as-made ACP composites due to significantly lower WS and higher BFS after prolonged aqueous exposure. PMID:19774100

Probing the 9.7 μm Interstellar Silicate Extinction Profile through the Spitzer/IRS Spectroscopy of OB Stars

NASA Astrophysics Data System (ADS)

Shao, Zhenzhen; Jiang, B. W.; Li, Aigen; Gao, Jian; Lv, Zhangpan; Yao, Jiawen

2018-05-01

The 9.7 μm interstellar spectral feature, arising from the Si-O stretch of amorphous silicate dust, is the strongest extinction feature in the infrared (IR). In principle, the spectral profile of this feature could allow one to diagnose the mineralogical composition of interstellar silicate material. However, observationally, the 9.7 μm interstellar silicate extinction profile is not well determined. Here we utilize the Spitzer/IRS spectra of five early-type (one O- and four B-type) stars and compare them with that of unreddened stars of the same spectral type to probe the interstellar extinction of silicate dust around 9.7 μm. We find that, while the silicate extinction profiles all peak at ˜ 9.7 μm, two stars exhibit a narrow feature of FWHM ˜ 2.0 μm and three stars display a broad feature of FWHM ˜ 3.0 μm. We also find that the width of the 9.7 μm extinction feature does not show any environmental dependence. With a FWHM of ˜ 2.2 μm, the mean 9.7 μm extinction profile, obtained by averaging over our five stars, closely resembles that of the prototypical diffuse interstellar medium along the lines of sight toward Cyg OB2 No. 12 and WR 98a. Finally, an analytical formula is presented to parameterize the interstellar extinction in the IR at 0.9 μm ≲ λ ≲ 15 μm.

Properties of calcium silicate-monobasic calcium phosphate materials for endodontics containing tantalum pentoxide and zirconium oxide.

PubMed

Zamparini, Fausto; Siboni, Francesco; Prati, Carlo; Taddei, Paola; Gandolfi, Maria Giovanna

2018-05-08

The aim of the study was to evaluate chemical-physical properties and apatite-forming ability of three premixed calcium silicate materials containing monobasic calcium phosphate (CaH 4 P 2 O 8 ) bioceramic, tantalum pentoxide and zirconium oxide, recently marketed for endodontics (TotalFill BC-Sealer, BC-RRM-Paste, BC-RRM-Putty). Microchemical and micromorphological analyses, radiopacity, initial and final setting times, calcium release and alkalising activity were tested. The nucleation of calcium phosphates (CaPs) and/or apatite after 28 days ageing was evaluated by ESEM-EDX and micro-Raman spectroscopy. BC-Sealer and BC-RRM-Paste showed similar initial (23 h), prolonged final (52 h) setting times and good radiopacity (> 7 mm Al); BC-RRM-Putty showed fast initial (2 h) and final setting times (27 h) and excellent radiopacity (> 9 mm Al). All materials induced a marked alkalisation (pH 11-12) up to 28 days and showed the release of calcium ions throughout the entire test period (cumulative calcium release 641-806 ppm). After 28 days ageing, a well-distributed mineral layer was present on all samples surface; EDX demonstrated relevant calcium and phosphorous peaks. B-type carbonated apatite and calcite deposits were identified by micro-Raman spectroscopy on all the 28-day-aged samples; the deposit thickness was higher on BC-RRM-Paste and BC-RRM-Putty, in agreement with calcium release data. These materials met the required chemical and physical standards and released biologically relevant ions. The CaSi-CaH 4 P 2 O 8 system present in the materials provided Ca and OH ions release with marked abilities to nucleate a layer of B-type carbonated apatite favoured/accelerated by the bioceramic presence. The ability to nucleate apatite may lead many clinical advantages: In orthograde endodontics, it may improve the sealing ability by the deposition of CaPs at the material-root dentine interface, and in endodontic surgery, it could promote bone and periodontal tissue regeneration. As premixed materials, their application in endodontics may result easier in several complex endodontic situations (apicoectomy, root perforation, presence of wide/wet apices).

REM-containing silicate concentrates

NASA Astrophysics Data System (ADS)

Pavlov, V. F.; Shabanova, O. V.; Pavlov, I. V.; Pavlov, M. V.; Shabanov, A. V.

2016-01-01

A new method of advanced complex processing of ores containing rare-earth elements (REE) is proposed to obtain porous X-ray amorphous aluminosilicate material with a stable chemical composition which concentrates oxides of rare-earth metals (REM). The ferromanganese oxide ores of Chuktukon deposit (Krasnoyarsk Region, RF) were used for the experiment. The obtained aluminosilicate material is appropriate for treatment with 5 - 15% solutions of mineral acids to leach REM.

Possible Gems and Ultra-Fine Grained Polyphase Units in Comet Wild 2.

NASA Technical Reports Server (NTRS)

Gainsforth, Z.; Butterworth, A. L.; Jilly-Rehak, C. E.; Westphal, A. J.; Brownlee, D. E.; Joswiak, D.; Ogliore, R. C.; Zolensky, M. E.; Bechtel, H. A.; Ebel, D. S.;

Greener durable concretes through geopolymerisation of blast furnace slag

NASA Astrophysics Data System (ADS)

Rajamane, N. P.; Nataraja, M. C.; Jeyalakshmi, R.; Nithiyanantham, S.

2015-05-01

The eco-friendliness of concrete is quantified by parameters such as ‘embodied energy’ (EE) and ‘embodied CO2 emission’ (ECO2e), besides duration of designed ‘service life’. It may be noted that ECO2e is also referred as carbon footprint (CF) in the literature. Geopolymer (GP) is an inorganic polymeric gel, a type of amorphous alumino-silicate product, which can be synthesised by polycondensation reactions. The concrete reported in this paper was prepared using industrial wastes in the form of blast furnace slag, fly ash as geopolymeric source materials and sodium silicate and sodium hydroxide as activators. Many mechanical properties such as compressive strength, chloride diffusion, steel corrosion, rapid chloride permeability test and rapid migration test are compared with Portland cement.

Nanoscale zinc silicate from phytoliths

NASA Astrophysics Data System (ADS)

Qadri, S. B.; Gorzkowski, E. P.; Rath, B. B.; Feng, C. R.; Amarasinghe, R.; Freitas, J. A.; Culbertson, J. C.; Wollmershauser, J. A.

2017-10-01

We report a faster, less expensive method of producing zinc silicate nanoparticles. Such particles are used in high volume to make phosphors and anti-corrosion coatings. The approach makes use of phytoliths (plant rocks), which are microscopic, amorphous, and largely silicate particles embedded in plants, that lend themselves to being easily broken down into nanoparticles. Nanoparticles of Zn2SiO4 were produced in a two stage process. In the refinement stage, plant residue, mixed with an appropriate amount of ZnO, was heated in an argon atmosphere to a temperature exceeding 1400 °C for four to six hours and then heated in air at 650 °C to remove excess carbon. TEM shows 50-100 nm nanoparticles. Raman scattering indicates that only the -Zn2SiO4 crystalline phase was present. X-ray analysis indicated pure rhombohedral R 3 bar phase results from using rice/wheat husks. Both samples luminesced predominantly at 523 nm when illuminated with X-rays or UV laser light.

Reflectance spectra of 'featureless' materials and the surface mineralogies of M- and E-class asteroids

NASA Technical Reports Server (NTRS)

Cloutis, Edward A.; Smith, Dorian G.; Lambert, Richard St. J.; Gaffey, Michael J.

1990-01-01

In a search for diagnostic spectral parameters which can be used to distinguish different materials on the surface of asteroids and to provide information on the detection limits for mafic silicates, the 0.3- to 2.6-micron reflectance spectra of meteoritic enstatite (nearly pure MgSiO3), iron meteorite metal, magnetite, and amorphous carbon as well as various mixtures of these materials with mafic silicates were examined. Results are presented on the dependence of the spectral detectability of mafic silicates associated with metal, carbon, and magnetite on the particle sizes of the phases, their chemistries, crystal structures, and abundances. It is shown that the observational data for a representative M-class asteroid, (16) Psyche, are largely consistent with a fine-grained metal-rich surface assemblage, whereas data for the E-class asteroid (44) Nysa indicate that its surface is composed of fine-grained material similar to enstatite achondrites, with a small amount of material comparable to the chondritic inclusions found in the Cumberland Falls aubrite.

Laboratory simulation of infrared astrophysical features. [Terrestrial silicate, meteoritic and lunar soil 10-micron spectral comparisons with comets Bennet and Kohoutek

NASA Technical Reports Server (NTRS)

Rose, L. A.

1979-01-01

Laboratory infrared emission and absorption spectra have been taken of terrestrial silicates, meteorites, and lunar soils in the form of micrometer and submicrometer grains. The emission spectra were taken in a way that imitates telescopic observations. The purpose was to see which materials best simulate the 10-micron astrophysical feature. The emission spectra of dunite, fayalite, and Allende give a good fit to the 10-micron broadband emission feature of comets Bennett and Kohoutek. A study of the effect of grain size on the presence of the 10-micron emission feature of dunite shows that for particles larger than 37 microns no feature is seen. The emission spectrum of the Murray meteorite, a Type 2 carbonaceous chrondrite, is quite similar to the intermediate-resolution spectrum of comet Kohoutek in the 10-micron region. Hydrous silicates or amorphous magnesium silicates in combination with high-temperature condensates, such as olivine or anorthite, would yield spectra that match the intermediate-resolution spectrum of comet Kohoutek in the 10-micron region. Glassy olivine and glassy anorthite in approximately equal proportions would also give a spectrum that is a good fit to the cometary 10-micron feature.

Constraints on interstellar dust models from extinction and spectro-polarimetry

NASA Astrophysics Data System (ADS)

Siebenmorgen, R.; Voshchinnikov, N. V.; Bagnulo, S.; Cox, N. L. J.

2017-12-01

We present polarisation spectra of seven stars in the lines-of-sight towards the Sco OB1 association. Our spectra were obtained within the framework of the Large Interstellar Polarization Survey carried out with the FORS instrument of the ESO VLT. We have modelled the wavelength-dependence of extinction and linear polarisation with a dust model for the diffuse interstellar medium which consists of a mixture of particles with size ranging from the molecular domain of 0.5 nm up to 350 nm. We have included stochastically heated small dust grains with radii between 0.5 and 6 nm made of graphite and silicate, as well as polycyclic aromatic hydrocarbon molecules (PAHs), and we have assumed that larger particles are prolate spheroids made of amorphous carbon and silicate. Overall, a dust model with eight free parameters best reproduces the observations, and is in agreement with cosmic abundance constraints. Reducing the number of free parameters leads to results that are inconsistent with the cosmic abundances of silicate and carbon. We found that aligned silicates are the dominant contributor to the observed polarisation, and that the polarisation spectra are best-fit by a lower limit of the equivolume sphere radius of aligned grains of 70-200 nm.

TEM study of a silicate-carbonate-microbe interface prepared by focused ion beam milling

NASA Astrophysics Data System (ADS)

Benzerara, Karim; Menguy, Nicolas; Guyot, François; Vanni, Christian; Gillet, Philippe

2005-03-01

The biogeochemical alteration of an Mg-Fe orthopyroxene, reacted for 70 yr under arid conditions in a desert environment, was studied by transmission electron microscopy. For this purpose, an electron transparent cross-section of the interface between a single microorganism, an orthopyroxene and nanometer-sized calcite crystals, was prepared with a focused ion beam system. X-ray energy dispersive spectrometry and electron energy loss spectroscopy allowed one to clearly distinguish the microorganism en route to fossilization from the nanometer-sized calcite crystals, showing the usefulness of such a protocol for identifying unambiguously traces of life in rocks. A 100-nm-deep depression was observed in the orthopyroxene close to the microorganism, suggesting an enhanced dissolution mediated by the microbe. However, an Al- and Si-rich amorphous altered layer restricted to the area just below the microorganism could be associated with decreased silicate dissolution rates at this location, suggesting complex effects of the microorganism on the silicate dissolution process. The close association observed between silicate dissolution and carbonate formation at the micrometer scale suggests that Urey-type CO 2 sequestration reactions could be mediated by microorganisms under arid conditions.

The development of electrical treeing in LDPE and its nanocomposites with spherical silica and fibrous and laminar silicates

NASA Astrophysics Data System (ADS)

Tiemblo, Pilar; Hoyos, Mario; Gómez-Elvira, Jose Manuel; Guzmán, Julio; García, Nuria; Dardano, Andrea; Guastavino, Francesco

2008-06-01

Electrical treeing in LDPE and three LDPE nanocomposites, with spherical silica and fibrous and laminar phyllosilicates, has been studied. Electrical tests were performed at a 50 Hz frequency and voltages between 8 and 29 kV, and the time to inception of the first electrical partial discharges (TTI) of the electrical trees and the time to breakdown (TBD), related to the electrical stability of the insulator, were determined. Above 15 kV all the nanocomposites show longer inception times and shorter tree growth times than LDPE. It is proposed that both observations are caused by the modification of the polymer crystalline morphology induced by the presence of the fillers and by the development of a large number of interfacial structures, both organo-inorganic and amorphous-crystalline. Below 15 kV the TBD is increased in the nanocomposites with the laminar silicate because of tortuosity and the TTI is increased in the fibrous silicate containing a nanocomposite because of the LDPE crystalline morphology in the presence of the silicate. The nanosilica particles decrease the electrical stability in the whole voltage range by decreasing both TTI and TBD.

The fate of silicon during glass corrosion under alkaline conditions: A mechanistic and kinetic study with the International Simple Glass

NASA Astrophysics Data System (ADS)

Gin, Stéphane; Jollivet, Patrick; Fournier, Maxime; Berthon, Claude; Wang, Zhaoying; Mitroshkov, Alexandre; Zhu, Zihua; Ryan, Joseph V.

2015-02-01

International Simple Glass - a six oxide borosilicate glass selected by the international nuclear glass community to improve the understanding of glass corrosion mechanisms and kinetics - was altered at 90 °C in a solution initially saturated with respect to amorphous 29SiO2. The pH90°C, was fixed at 9 at the start of the experiment and raised to 11.5 after 209 d by the addition of KOH. Isotope sensitive analytical techniques were used to analyze the solution and altered glass samples, helping to understand the driving forces and rate limiting processes controlling long-term glass alteration. At pH 9, the corrosion rate continuously drops and the glass slowly transforms into a uniform, homogeneous amorphous alteration layer. The mechanisms responsible for this transformation are water penetration through the growing alteration layer and ion exchange. We demonstrate that this amorphous alteration layer is not a precipitate resulting from the hydrolysis of the silicate network; it is mostly inherited from the glass structure from which the most weakly bonded cations (Na, Ca and B) have been released. At pH 11.5, the alteration process is very different: the high solubility of glass network formers (Si, Al, Zr) triggers the rapid and complete dissolution of the glass (dissolution becomes congruent) and precipitation of amorphous and crystalline phases. Unlike at pH 9 where glass corrosion rate decreased by 3 orders of magnitude likely due to the retroaction of the alteration layer on water dynamics/reactivity at the reaction front, the rate at pH 11.5 is maintained at a value close to the forward rate due to both the hydrolysis of the silicate network promoted by OH- and the precipitation of CSH and zeolites. This study provides key information for a unified model for glass dissolution.

Silicic volcanism on Mars evidenced by tridymite in high-SiO2 sedimentary rock at Gale crater

NASA Astrophysics Data System (ADS)

Morris, Richard V.; Vaniman, David T.; Blake, David F.; Gellert, Ralf; Chipera, Steve J.; Rampe, Elizabeth B.; Ming, Douglas W.; Morrison, Shaunna M.; Downs, Robert T.; Treiman, Allan H.; Yen, Albert S.; Grotzinger, John P.; Achilles, Cherie N.; Bristow, Thomas F.; Crisp, Joy A.; Des Marais, David J.; Farmer, Jack D.; Fendrich, Kim V.; Frydenvang, Jens; Graff, Trevor G.; Morookian, John-Michael; Stolper, Edward M.; Schwenzer, Susanne P.

2016-06-01

Tridymite, a low-pressure, high-temperature (>870 °C) SiO2 polymorph, was detected in a drill sample of laminated mudstone (Buckskin) at Marias Pass in Gale crater, Mars, by the Chemistry and Mineralogy X-ray diffraction instrument onboard the Mars Science Laboratory rover Curiosity. The tridymitic mudstone has ˜40 wt.% crystalline and ˜60 wt.% X-ray amorphous material and a bulk composition with ˜74 wt.% SiO2 (Alpha Particle X-Ray Spectrometer analysis). Plagioclase (˜17 wt.% of bulk sample), tridymite (˜14 wt.%), sanidine (˜3 wt.%), cation-deficient magnetite (˜3 wt.%), cristobalite (˜2 wt.%), and anhydrite (˜1 wt.%) are the mudstone crystalline minerals. Amorphous material is silica-rich (˜39 wt.% opal-A and/or high-SiO2 glass and opal-CT), volatile-bearing (16 wt.% mixed cation sulfates, phosphates, and chlorides-perchlorates-chlorates), and has minor TiO2 and Fe2O3T oxides (˜5 wt.%). Rietveld refinement yielded a monoclinic structural model for a well-crystalline tridymite, consistent with high formation temperatures. Terrestrial tridymite is commonly associated with silicic volcanism, and detritus from such volcanism in a “Lake Gale” catchment environment can account for Buckskin's tridymite, cristobalite, feldspar, and any residual high-SiO2 glass. These cogenetic detrital phases are possibly sourced from the Gale crater wall/rim/central peak. Opaline silica could form during diagenesis from high-SiO2 glass, as amorphous precipitated silica, or as a residue of acidic leaching in the sediment source region or at Marias Pass. The amorphous mixed-cation salts and oxides and possibly the crystalline magnetite (otherwise detrital) are primary precipitates and/or their diagenesis products derived from multiple infiltrations of aqueous solutions having variable compositions, temperatures, and acidities. Anhydrite is post lithification fracture/vein fill.

Silicic volcanism on Mars evidenced by tridymite in high-SiO2 sedimentary rock at Gale crater

PubMed Central

Morris, Richard V.; Vaniman, David T.; Blake, David F.; Gellert, Ralf; Chipera, Steve J.; Rampe, Elizabeth B.; Ming, Douglas W.; Morrison, Shaunna M.; Downs, Robert T.; Treiman, Allan H.; Yen, Albert S.; Grotzinger, John P.; Achilles, Cherie N.; Bristow, Thomas F.; Crisp, Joy A.; Des Marais, David J.; Farmer, Jack D.; Fendrich, Kim V.; Graff, Trevor G.; Morookian, John-Michael; Stolper, Edward M.; Schwenzer, Susanne P.

2016-01-01

Tridymite, a low-pressure, high-temperature (>870 °C) SiO2 polymorph, was detected in a drill sample of laminated mudstone (Buckskin) at Marias Pass in Gale crater, Mars, by the Chemistry and Mineralogy X-ray diffraction instrument onboard the Mars Science Laboratory rover Curiosity. The tridymitic mudstone has ∼40 wt.% crystalline and ∼60 wt.% X-ray amorphous material and a bulk composition with ∼74 wt.% SiO2 (Alpha Particle X-Ray Spectrometer analysis). Plagioclase (∼17 wt.% of bulk sample), tridymite (∼14 wt.%), sanidine (∼3 wt.%), cation-deficient magnetite (∼3 wt.%), cristobalite (∼2 wt.%), and anhydrite (∼1 wt.%) are the mudstone crystalline minerals. Amorphous material is silica-rich (∼39 wt.% opal-A and/or high-SiO2 glass and opal-CT), volatile-bearing (16 wt.% mixed cation sulfates, phosphates, and chlorides−perchlorates−chlorates), and has minor TiO2 and Fe2O3T oxides (∼5 wt.%). Rietveld refinement yielded a monoclinic structural model for a well-crystalline tridymite, consistent with high formation temperatures. Terrestrial tridymite is commonly associated with silicic volcanism, and detritus from such volcanism in a “Lake Gale” catchment environment can account for Buckskin’s tridymite, cristobalite, feldspar, and any residual high-SiO2 glass. These cogenetic detrital phases are possibly sourced from the Gale crater wall/rim/central peak. Opaline silica could form during diagenesis from high-SiO2 glass, as amorphous precipitated silica, or as a residue of acidic leaching in the sediment source region or at Marias Pass. The amorphous mixed-cation salts and oxides and possibly the crystalline magnetite (otherwise detrital) are primary precipitates and/or their diagenesis products derived from multiple infiltrations of aqueous solutions having variable compositions, temperatures, and acidities. Anhydrite is post lithification fracture/vein fill. PMID:27298370

Molecular dynamics simulations of Li transport between cathode crystals

NASA Astrophysics Data System (ADS)

Garofalini, S. H.

The molecular dynamics (MD) computer simulation technique has been used to study the effect of an amorphous intergranular film (IGF) present in a polycrystalline cathode on Li transport. The solid electrolyte is a model lithium silicate glass while the cathode is a nanocrystalline vanadia with an amorphous V 2O 5 IGF separating the crystals. Thin (˜1 to a few nanometer thick) IGFs are known to be present in most polycrystalline oxide materials. However, the role of such a film on Li transport in oxide cathodes has not been addressed. Current scanning probe microscopy (SPM) studies have shown that the orientation of the layered nanocrystalline vanadia crystals near the cathode/solid electrolyte interface is not optimized for Li ion transport. While the precise structure of the material between the crystals has not been identified, initially it can be initially considered as likely to be a thin non-crystalline (amorphous) film. This is based on the ubiquitous presence of such a structure in other polycrystalline oxides. Also, and with more relevance to the materials used in thin film batteries, an amorphous film can be expected to form between nanocrystals that crystallized from an amorphous matrix, as would be the case in a deposited thin film cathode. Consistent with simulations of Li transport in amorphous vanadia, the current simulations show that Li ions diffuse more rapidly into the amorphous intergranular thin film than into the layered vanadia with the (0 0 1) planes parallel to the cathode/electrolyte interface.

[Preventive and remineralization effect over incipient lesions of caries decay by phosphopeptide-amorphous calcium phosphate].

PubMed

Juárez-López, María Lilia Adriana; Hernández-Palacios, Rosa Diana; Hernández-Guerrero, Juan Carlos; Jiménez-Farfán, Dolores; Molina-Frechero, Nelly

2014-01-01

INTRODUCTION. Dental caries continues to affect a large percentage of Mexican children and currently advises that if diagnosed at an early stage can be reversed with minimally invasive treatments. The casein phosphopeptide amorphous calcium phosphate known as CPP-ACP is a phosphoprotein capable of releasing calcium and phosphate ions in the oral environment promoting remineralization. OBJECTIVE. To evaluate the effect of CPP-ACP with fluoride added in a scholar preventive program. MATERIAL AND METHODS. A cuasi- experimental study was conducted in 104 schools of six years old. The children were classified into three groups and received six months biweekly applications of different treatments: casein phosphopeptide amorphous calcium phosphate added fluoride (CPP-ACPF), sodium fluoride (NaF) and a control group. Clinical evaluation was performed with the laser fluorescence technique (Diagnodent model 2095). 1340 teeth were included: 294 teeth with incipient lesions and 1,046 healthy teeth. Statistical tests of χ2 y Mc Nemar were used. RESULTS. In the group that received the application of CPP-ACPF, 38% of incipient carious lesions were remineralizing compared with 21% in the group receiving the NaF (p < 0.001) and 15% in the control group (p < 0.0001) The percentage of teeth free of caries were preserved in the therapy group phosphoprotein was the biggest. This group also showed the lower proportion of deep carious lesion development (p < 0.0001). CONCLUSION. The application biweekly for six months of CPP-ACPF showed a protective and remineralizing effect on incipient carious lesions. His action was better than the application of NaF. However, to reduce the impact from dental caries in schoolchildren is important to have a comprehensive preventive approach that includes promoting self-care, as well as the application of sealants.

Mechanisms of scale formation and carbon dioxide partial pressure influence. Part I. Elaboration of an experimental method and a scaling model.

PubMed

Gal, Jean-Yves; Fovet, Yannick; Gache, Nathalie

2002-02-01

Scale formation in industrial or domestic installations is still an important economic problem. The existence of a metastable domain for calcium carbonate supersaturated solutions and its breakdown are observed under conditions rarely well defined. In most cases it is the pH rise caused by the carbon dioxide loss that involves calcium carbonate precipitation. Before studying this problem, we suggest in this first part, a new model for the evolution of the calcocarbonic system that takes into account the hydrated forms of CaCO3: CaCO3 amorphous, CaCO3 x 6H2O (ikaite) and CaCO3 x H2O (monohydrate). According to this model, the precipitation of any one of these hydrated forms could be responsible for the breakdown of the metastable state. After this first step, the solids evolve into dehydrated forms. At first, the metastable domain spread of the calcium carbonate supersaturated solutions was studied by the elaboration of computer programs in which the formation of CaCO3(0)(aq) ion pairs was taken into account. These ion pairs are supposed to evolve through dehydration to form the various calcium carbonate solid form precursors. This thermodynamic study was then compared to the experimental methods of the critical pH. Here the pH rise was caused by adding sodium hydroxide under different conditions for sodium hydroxide addition speed, agitation mode and ageing of solutions. For the highest speed of sodium hydroxide addition, the CaCO3 ionic product reached the value of the amorphous calcium carbonate solubility product, and the reaction of the amorphous calcium carbonate precipitation was of the homogenous type. Decreasing the reagent's addition speed caused an extension of the titration time. Then, the breakdown of the metastable state was obtained with the CaCO3 x H2O heterogeneous precipitation. This clearly illustrates the probable ageing of the precursors of the solid states that are considered in this model.

Releasing effects in flame photometry: Determination of calcium

USGS Publications Warehouse

Dinnin, J.I.

1960-01-01

Strontium, lanthanum, neodymium, samarium, and yttrium completely release the flame emission of calcium from the depressive effects of sulfate, phosphate, and aluminate. Magnesium, beryllium, barium, and scandium release most of the calcium emission. These cations, when present in high concentration, preferentially form compounds with the depressing anions when the solution is evaporated rapidly in the flame. The mechanism of the interference and releasing effects is explained on the basis of the chemical equilibria in the evaporating droplets of solution and is shown to depend upon the nature of the compounds present in the aqueous phase of the solution. The need for background correction techniques is stressed. The releasing effect is used in the determination of calcium in silicate rocks without the need for separations.

Effect of carbonic anhydrase on silicate weathering and carbonate formation at present day CO2 concentrations compared to primordial values

PubMed Central

Xiao, Leilei; Lian, Bin; Hao, Jianchao; Liu, Congqiang; Wang, Shijie

2015-01-01

It is widely recognized that carbonic anhydrase (CA) participates in silicate weathering and carbonate formation. Nevertheless, it is still not known if the magnitude of the effect produced by CA on surface rock evolution changes or not. In this work, CA gene expression from Bacillus mucilaginosus and the effects of recombination protein on wollastonite dissolution and carbonate formation under different conditions are explored. Real-time fluorescent quantitative PCR was used to explore the correlation between CA gene expression and sufficiency or deficiency in calcium and CO2 concentration. The results show that the expression of CA genes is negatively correlated with both CO2 concentration and ease of obtaining soluble calcium. A pure form of the protein of interest (CA) is obtained by cloning, heterologous expression, and purification. The results from tests of the recombination protein on wollastonite dissolution and carbonate formation at different levels of CO2 concentration show that the magnitudes of the effects of CA and CO2 concentration are negatively correlated. These results suggest that the effects of microbial CA in relation to silicate weathering and carbonate formation may have increased importance at the modern atmospheric CO2 concentration compared to 3 billion years ago. PMID:25583135

Influence of solution conditions on deposition of calcium phosphate on titanium by NaOH-treatment

NASA Astrophysics Data System (ADS)

Feng, Q. L.; Cui, F. Z.; Wang, H.; Kim, T. N.; Kim, J. O.

2000-03-01

The present paper demonstrated a biomimetic method to coat calcium phosphate (Ca-P) on the surface of titanium induced by NaOH-treatment from a simple supersaturated hydroxyapatite solution (SHS). The influence of pH value and calcium ions concentration on the precipitation process was investigated. It is necessary for the solution to be supersaturated than the critical concentration of octacalcium phosphate (OCP) to get Ca-P coatings on titanium surface. In the precipitating process, it seems that amorphous calcium phosphate (ACP) precipitated first, then OCP, and finally hydroxyapatite (HA). The system was in continuous evolution and the phase transitions occurred in sequence.

3-D-Observation of Matrix of MIL 090657 Meteorite by Absorption-Phase Tomography

NASA Technical Reports Server (NTRS)

Miyama, Sugimoto; Tsuchiyama, Akira; Matsuno, Junya; Miyake, Akira; Nakano, Tsukasa; Uesugi, Kentaro; Takeuchi, Akihisa; Takigawa, Aki; Takayama, Akiko; Nakamura-Messenger, Keiko;

Bioactive nanocomposite for chest-wall replacement: Cellular response in a murine model.

PubMed

Jungraithmayr, Wolfgang; Laube, Isabelle; Hild, Nora; Stark, Wendelin J; Mihic-Probst, Daniela; Weder, Walter; Buschmann, Johanna

2014-07-01

Chest-wall invading malignancies usually necessitate the resection of the respective part of the thoracic wall. Gore-Tex® is the material of choice that is traditionally used to repair thoracic defects. This material is well accepted by the recipient; however, though not rejected, it is an inert material and behaves like a 'foreign body' within the thoracic wall. By contrast, there are materials that have the potential to physiologically integrate into the host, and these materials are currently under in vitro and also in vivo investigation. These materials offer a gradual but complete biodegradation over time, and severe adverse inflammatory responses can be avoided. Here, we present a novel material that is a biodegradable nanocomposite based on poly-lactic-co-glycolic acid and amorphous calcium phosphate nanoparticles in comparison to the traditionally employed Gore-Tex® being the standard for chest-wall replacement. On a mouse model of thoracic wall resection, that resembles the technique and localization applied in humans, poly-lactic-co-glycolic acid and amorphous calcium phosphate nanoparticles and Gore-Tex® were implanted subcutaneously and additionally tested in a separate series as a chest-wall graft. After 1, 2, 4 and 8 weeks cell infiltration into the respective materials, inflammatory reactions as well as neo-vascularization (endothelial cells) were determined in six different zones. While Gore-Tex® allowed for cell infiltration only at the outer surface, electrospun poly-lactic-co-glycolic acid and amorphous calcium phosphate nanoparticles were completely penetrated by infiltrating cells. These cells were composed mainly by macrophages, with only 4% of giant cells and lymphocytes. Total macrophage count increased by time while the number of IL1-β-expressing macrophages decreased, indicating a protective state towards the graft. As such, poly-lactic-co-glycolic acid and amorphous calcium phosphate nanoparticles seem to develop ideal characteristics as a material for chest-wall replacement by (a) having the advantage of full biodegradation, (b) displaying stable chest-wall structures and (c) adapting a physiological and integrating graft compared to Gore-Tex®. © The Author(s) 2013 Reprints and permissions: sagepub.co.uk/journalsPermissions.nav.

Chemical-garden formation, morphology, and composition. II. Chemical gardens in microgravity.

PubMed

Cartwright, Julyan H E; Escribano, Bruno; Sainz-Díaz, C Ignacio; Stodieck, Louis S

2011-04-05

We studied the growth of metal-ion silicate chemical gardens under Earth gravity (1 g) and microgravity (μg) conditions. Identical sets of reaction chambers from an automated system (the Silicate Garden Habitat or SGHab) were used in both cases. The μg experiment was performed on board the International Space Station (ISS) within a temperature-controlled setup that provided still and video images of the experiment downlinked to the ground. Calcium chloride, manganese chloride, cobalt chloride, and nickel sulfate were used as seed salts in sodium silicate solutions of several concentrations. The formation and growth of osmotic envelopes and microtubes was much slower under μg conditions. In 1 g, buoyancy forces caused tubes to grow upward, whereas a random orientation for tube growth was found under μg conditions.

Sealing of cracks in cement using microencapsulated sodium silicate

NASA Astrophysics Data System (ADS)

Giannaros, P.; Kanellopoulos, A.; Al-Tabbaa, A.

2016-08-01

Cement-based materials possess an inherent autogenous self-healing capability allowing them to seal, and potentially heal, microcracks. This can be improved through the addition of microencapsulated healing agents for autonomic self-healing. The fundamental principle of this self-healing mechanism is that when cracks propagate in the cementitious matrix, they rupture the dispersed capsules and their content (cargo material) is released into the crack volume. Various healing agents have been explored in the literature for their efficacy to recover mechanical and durability properties in cementitious materials. In these materials, the healing agents are most commonly encapsulated in macrocontainers (e.g. glass tubes or capsules) and placed into the material. In this work, microencapsulated sodium silicate in both liquid and solid form was added to cement specimens. Sodium silicate reacts with the calcium hydroxide in hydrated cement paste to form calcium-silicate-hydrate gel that fills cracks. The effect of microcapsule addition on rheological and mechanical properties of cement is reported. It is observed that the microcapsule addition inhibits compressive strength development in cement and this is observed through a plateau in strength between 28 and 56 days. The improvement in crack-sealing for microcapsule-containing specimens is quantified through sorptivity measurements over a 28 day healing period. After just seven days, the addition of 4% microcapsules resulted in a reduction in sorptivity of up to 45% when compared to specimens without any microcapsule addition. A qualitative description of the reaction between the cargo material and the cementitious matrix is also provided using x-ray diffraction analysis.

Cement and concrete

NASA Technical Reports Server (NTRS)

Corley, Gene; Haskin, Larry A.

1992-01-01

To produce lunar cement, high-temperature processing will be required. It may be possible to make calcium-rich silicate and aluminate for cement by solar heating of lunar pyroxene and feldspar, or chemical treatment may be required to enrich the calcium and aluminum in lunar soil. The effects of magnesium and ferrous iron present in the starting materials and products would need to be evaluated. So would the problems of grinding to produce cement, mixing, forming in vacuo and low gravity, and minimizing water loss.

Phosphorylation of serine residues is fundamental for the calcium-binding ability of Orchestin, a soluble matrix protein from crustacean calcium storage structures.

PubMed

Hecker, Arnaud; Testenière, Olivier; Marin, Frédéric; Luquet, Gilles

2003-01-30

Orchestia cavimana is a terrestrial crustacean, which cyclically stores calcium in diverticula of the midgut, in the form of calcified amorphous concretions. These concretions are associated with a proteinaceous matrix, the main constituent of the soluble matrix is Orchestin, an acidic calcium-binding protein [Testenière et al., Biochem. J. 361 (2002) 327-335]. In the present paper, we clearly demonstrate that Orchestin is phosphorylated on serine and tyrosine residues, but that calcium binding only occurs via the phosphoserine residues. To our knowledge, this is the first example of an invertebrate mineralization for which a post-translational modification is clearly related to an important function of a calcifying protein.

Defining the flexibility window in ordered aluminosilicate zeolites

PubMed Central

Wells, Stephen A.; Leung, Ka Ming; Edwards, Peter P.; Tucker, Matt G.

2017-01-01

The flexibility window in zeolites was originally identified using geometric simulation as a hypothetical property of SiO2 systems. The existence of the flexibility window in hypothetical structures may help us to identify those we might be able to synthesize in the future. We have previously found that the flexibility window in silicates is connected to phase transitions under pressure, structure amorphization and other physical behaviours and phenomena. We here extend the concept to ordered aluminosilicate systems using softer ‘bar’ constraints that permit additional flexibility around aluminium centres. Our experimental investigation of pressure-induced amorphization in sodalites is consistent with the results of our modelling. The softer constraints allow us to identify a flexibility window in the anomalous case of goosecreekite. PMID:28989777

Strontium-doped calcium silicate bioceramic with enhanced in vitro osteogenic properties.

PubMed

No, Young Jung; Roohaniesfahani, Seyediman; Lu, Zufu; Shi, Jeffrey; Zreiqat, Hala

2017-06-05

Gehlenite (GLN, Ca 2 SiAl 2 O 7 ) is a bioceramic that has been recently shown to possess excellent mechanical strength and in vitro osteogenic properties for bone regeneration. Substitutional incorporation of strontium in place of calcium is an effective way to further enhance biological properties of calcium-based bioceramics and glasses. However, such strategy has the potential to affect other important physicochemical parameters such as strength and degradation due to differences in the ionic radius of strontium and calcium. This study is the first to investigate the effect of a range of concentrations of strontium substitution of calcium at 1, 2, 5, 10 mol% (S1-GLN, S2-GLN, S5-GLN and S10-GLN) on the physicochemical and biological properties of GLN. We showed that up to 2 mol% strontium ion substitution retains the monophasic GLN structure when sintered at 1450 °C, whereas higher concentrations resulted in presence of calcium silicate impurities. Increased strontium incorporation resulted in changes in grain morphology and reduced densification when the ceramics were sintered at 1450 °C. Porous GLN, S1-GLN and S2-GLN scaffolds (∼80% porosity) showed compressive strengths of 2.05 ± 0.46 MPa, 1.76 ± 0.79 MPa and 1.57 ± 0.52 MPa respectively. S1-GLN and S2-GLN immersed in simulated body fluid showed increased strontium ion release but reduced calcium and silicon ion release compared to GLN without affecting overall weight loss and pH over a 21 d period. The bioactivity of the S2-GLN ceramics was significantly improved as reflected in the significant upregulation of HOB proliferation and differentiation compared to GLN. Overall, these results suggest that increased incorporation of strontium presents a trade-off between bioactivity and mechanical strength for GLN bioceramics. This is an important consideration in the development of strontium-doped bioceramics.

In vitro cytotoxicity of calcium silicate-containing endodontic sealers.

PubMed

Zhou, Hui-min; Du, Tian-feng; Shen, Ya; Wang, Zhe-jun; Zheng, Yu-feng; Haapasalo, Markus

2015-01-01

The cytotoxicity of 2 novel calcium silicate-containing endodontic sealers to human gingival fibroblasts was studied. EndoSequence BC (Brasseler, Savannah, GA), MTA Fillapex (Angelus Indústria de Produtos Odontológicos S/A, Londrina, PR, Brazil) and a control sealer (AH Plus; Dentsply DeTrey GmbH, Konstanz, Germany) were evaluated. Human gingival fibroblasts were incubated for 3 days both with the extracts from fresh and set materials in culture medium and cultured on the surface of the set materials in Dulbecco-modified Eagle medium. Fibroblasts cultured in Dulbecco-modified Eagle medium were used as a control group. Cytotoxicity was evaluated by flow cytometry, and the adhesion of the fibroblasts to the surface of the set materials was assessed using scanning electron microscopy. The data of cell cytotoxicity were analyzed statistically using a 1-way analysis of variance test at a significance level of P < .05. Cells incubated with extracts from BC Sealer showed higher viabilities at all extract concentrations than cells incubated with extracts from freshly mixed AH Plus and fresh and set MTA Fillapex, esspecially for the high extract concentrations (1:2 and 1:8 dilutions). Extracts from set MTA Fillapex of 2 weeks and older were more cytotoxic than extracts from freshly mixed and 1-week-old cement. With extract concentrations of 1:32 and lower, MTA Fillapex was no longer cytotoxic. After setting, AH Plus was no longer cytotoxic, and the fibroblast cells grew on set AH Plus equally as well as on BC Sealer. BC Sealer and MTA Fillapex, the 2 calcium silicate-containing endodontic sealers, exhibited different cytotoxicity to human gingival fibroblasts. Copyright © 2015 American Association of Endodontists. Published by Elsevier Inc. All rights reserved.

Dehydration-induced amorphous phases of calcium carbonate.

PubMed

Saharay, Moumita; Yazaydin, A Ozgur; Kirkpatrick, R James

2013-03-28

Amorphous calcium carbonate (ACC) is a critical transient phase in the inorganic precipitation of CaCO3 and in biomineralization. The calcium carbonate crystallization pathway is thought to involve dehydration of more hydrated ACC to less hydrated ACC followed by the formation of anhydrous ACC. We present here computational studies of the transition of a hydrated ACC with a H2O/CaCO3 ratio of 1.0 to anhydrous ACC. During dehydration, ACC undergoes reorganization to a more ordered structure with a significant increase in density. The computed density of anhydrous ACC is similar to that of calcite, the stable crystalline phase. Compared to the crystalline CaCO3 phases, calcite, vaterite, and aragonite, the computed local structure of anhydrous ACC is most-similar to those of calcite and vaterite, but the overall structure is not well described by either. The strong hydrogen bond interaction between the carbonate ions and water molecules plays a crucial role in stabilizing the less hydrated ACC compositions compared to the more hydrated ones, leading to a progressively increasing hydration energy with decreasing water content.

Protein adsorption on thin films of carbon and carbon nitride monitored with in situ ellipsometry.

PubMed

Berlind, T; Tengvall, P; Hultman, L; Arwin, H

2011-03-01

Thin films of amorphous carbon and amorphous, graphitic and fullerene-like carbon nitride were deposited by reactive magnetron sputtering and optically characterized with spectroscopic ellipsometry. Complementary studies using scanning electron microscopy and atomic force microscopy were performed. The films were exposed to human serum albumin (HSA) and the adsorption was monitored in situ using dynamic ellipsometry. From the ellipsometric data the adsorbed amount of proteins was quantified in terms of surface mass density using de Feijter's model. The results indicate larger adsorption of proteins onto the amorphous films compared to the films with a more textured structure. Complementary studies with 125I-labeled HSA showed an apparent protein adsorption up to six times larger compared to the ellipsometry measurement. In addition, the four types of films were incubated in blood plasma followed by exposure to anti-fibrinogen, anti-HMWK or anti-C3c, revealing the materials' response to complement and contact activation. The amorphous and graphitic carbon nitride exhibit rather high immune activity compared to a titanium reference, whereas the amorphous carbon and the fullerene-like CNx show less immune complement deposition. Compared to the reference, all films exhibit indications of a stronger ability to initiate the intrinsic pathway of coagulation. Finally, the surfaces' bone-bonding ability was investigated by examination of their ability to form calcium phosphate crystals in a simulated body fluid, with a-CNx depositing most calcium phosphate after 21 days of incubation. Copyright © 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Zinc-Containing Restorations Create Amorphous Biogenic Apatite at the Carious Dentin Interface: A X-Ray Diffraction (XRD) Crystal Lattice Analysis.

PubMed

Toledano, Manuel; Aguilera, Fátima S; López-López, Modesto T; Osorio, Estrella; Toledano-Osorio, Manuel; Osorio, Raquel

2016-10-01

The aim of this research was to assess the ability of amalgam restorations to induce amorphous mineral precipitation at the caries-affected dentin substrate. Sound and caries-affected dentin surfaces were subjected to both Zn-free and Zn-containing dental amalgam restorations. Specimens were submitted to thermocycling (100,000 cycles/5°C-55°C, 3 months). Dentin surfaces were studied by atomic force microscopy (nanoroughness), X-ray diffraction, field emission scanning electron microscopy, and energy-dispersive analysis, for physical and morphological surface characterization. Zn-containing amalgam placement reduced crystallinity, crystallite size, and grain size of calcium phosphate crystallites at the dentin surface. Both microstrain and nanoroughness were augmented in caries-affected dentin restored with Zn-containing amalgams. Caries-affected dentin showed the shortest mineral crystallites (11.04 nm), when Zn-containing amalgams were used for restorations, probably leading to a decrease of mechanical properties which might favor crack propagation and deformation. Sound dentin restored with Zn-free amalgams exhibited a substantial increase in length of grain particles (12.44 nm) embedded into dentin crystallites. Zn-containing amalgam placement creates dentin mineralization and the resultant mineral was amorphous in nature. Amorphous calcium phosphate provides a local ion-rich environment, which is considered favorable for in situ generation of prenucleation clusters, promotong further dentin remineralization.

Microstructure of amorphous aluminum hydroxide in belite-calcium sulfoaluminate cement

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

Song, Fei; Yu, Zhenglei; Yang, Fengling

Belite-calcium sulfoaluminate (BCSA) cement is a promising low-CO{sub 2} alternative to ordinary Portland cement. Herein, aluminum hydroxide (AH{sub 3}), the main amorphous hydration product of BCSA cement, was investigated in detail. The microstructure of AH{sub 3} with various quantities of gypsum was investigated via scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS). The AH{sub 3} with various morphologies were observed and confirmed in the resulting pastes. Particular attention was paid to the fact that AH{sub 3} always contained a small amount of Ca according to the results of EDS analysis. The AH{sub 3} was then characterized via highmore » resolution transmission electron microscopy (HRTEM). The results of HRTEM indicated that Ca arose from nanosized tricalcium aluminate hexahydrate which existed in the AH{sub 3}.« less

Evaluation of the remineralization potential of amorphous calcium phosphate and fluoride containing pit and fissure sealants using scanning electron microscopy.

PubMed

Choudhary, Prashant; Tandon, Shobha; Ganesh, M; Mehra, Anshul

2012-01-01

To evaluate the remineralization potential of Amorphous Calcium Phosphate (ACP) and Fluoride containing pit and Fissure Sealants using Scanning Electron Microscopy. Thirty maxillary first premolars were divided into three groups of ten each and were randomly selected for ACP containing (Aegis- Opaque White, Bosworth Co. Ltd.), Fluoride containing (Teethmate F1 Natural Clear, Kuraray Co. Ltd.), resin based (Concise- Opaque White, 3M ESPE Co. Ltd.) pit and fissure sealant applications. The Concise group served as a control. The teeth weresubjected to the pH-cycling regimen for a period of two weeks. After two weeks, the teeth were sectioned bucco-lingually into 4mm sections and were observed under Scanning Electron Microscope at 50X, 250X, 500X, 1000X and 1500X magnifications. The qualitative changes at the tooth surface and sealant interface were examined and presence of white zone at the interface was considered positive for remineralization. Both ACP containing (Aegis) and Fluoride containing (Teethmate F1) group showed white zone at the tooth surface-sealant interface. The resin based group (Concise) showed regular interface between the sealant and the tooth structure, but no clear cut white zone was observed. Both, Aegis and Teethmate F1 have the potential to remineralize. Release of Amorphous Calcium Phosphate molecules in Aegis group and formation of Fluoroapetite in Teethmate F1 group, were probably responsible for the remineralization.

The comparison of phosphate-titanate-silicate layers on the titanium and Ti6Al4V alloy base.

PubMed

Rokita, M

2011-08-15

The studied layers were composed of two parts: titanate-silicate underlayer for better adhesion and titanate-phosphate-silicate layers for potential bioparameters. The layers with different amounts of hydroxyapatite were deposited on titanium and Ti6Al4V alloy substrates using dipping sol-gel method and electrophoresis. The selection of sol/suspension composition, deposition time and heat treatment conditions have the decisive influence on the layers parameters. The obtained layers should be very thin and almost amorphous. The specific nature of ceramic layers on the metal substrates excludes the use of some measurements methods or makes it difficult to interpret the measurement results. All the obtained samples were compared using XRD analysis data (GID technique), SEM with EDX measurements and FTIR spectroscopy (transmission and reflection techniques) before and after soaking in simulated body fluid. FTIR spectroscopy with mathematical treatment of the spectra (BIO-RAD Win-IR program, Arithmetic-subtract function) was used to detect the increase or decrease of any phosphate phases during SBF soaking. Based on the FTIR results the processes of hydroxyapatite (HAp) growth or layer dissolution were estimated. The layers deposited on titanium substrate are more crystalline then the ones deposited on Ti6Al4V. During SBF soaking process the growth of small amount of microcrystalline carbonate hydroxyapatite was observed on titanium substrate. The layer on Ti6Al4V base contained amorphous carbonate apatite. During heating treatment above about 870-920 K this apatite transforms into carbonate hydroxyapatite. The Ti6Al4V substrate seems to be more advantageous in context of potentially bioactive materials obtaining. Copyright © 2010 Elsevier B.V. All rights reserved.

Rare-earth gate oxides for GaAs MOSFET application

NASA Astrophysics Data System (ADS)

Kwon, Kwang-Ho; Yang, Jun-Kyu; Park, Hyung-Ho; Kim, Jongdae; Roh, Tae Moon

2006-08-01

Rare-earth oxide films for gate dielectric on n-GaAs have been investigated. The oxide films were e-beam evaporated on S-passivated GaAs, considering interfacial chemical bonding state and energy band structure. Rare-earth oxides such as Gd 2O 3, (Gd xLa 1- x) 2O 3, and Gd-silicate were employed due to high resistivity and no chemical reaction with GaAs. Structural and bonding properties were characterized by X-ray photoemission, absorption, and diffraction. The electrical characteristics of metal-oxide-semiconductor (MOS) diodes were correlated with material properties and energy band structures to guarantee the feasibility for MOS field effect transistor (FET) application. Gd 2O 3 films were grown epitaxially on S-passivated GaAs (0 0 1) at 400 °C. The passivation induced a lowering of crystallization temperature with an epitaxial relationship of Gd 2O 3 (4 4 0) and GaAs (0 0 1). A better lattice matching relation between Gd 2O 3 and GaAs substrate was accomplished by the substitution of Gd with La, which has larger ionic radius. The in-plane relationship of (Gd xLa 1- x) 2O 3 (4 4 0) with GaAs (0 0 1) was found and the epitaxial films showed an improved crystalline quality. Amorphous Gd-silicate film was synthesized by the incorporation of SiO 2 into Gd 2O 3. These amorphous Gd-silicate films excluded defect traps or current flow path due to grain boundaries and showed a relatively larger energy band gap dependent on the contents of SiO 2. Energy band parameters such as Δ EC, Δ EV, and Eg were effectively controlled by the film composition.

Numerical modeling of mineral dissolution - precipitation kinetics integrating interfacial processes

NASA Astrophysics Data System (ADS)

Azaroual, M. M.

2016-12-01

The mechanisms of mineral dissolution/precipitation are complex and interdependent. Within a same rock, the geochemical modelling may have to manage kinetic reactions with high ratios between the most reactive minerals (i.e., carbonates, sulfate salts, etc.) and less reactive minerals (i.e., silica, alumino-silicates, etc.). These ratios (higher than 10+6) induce numerical instabilities for calculating mass and energy transfers between minerals and aqueous phases at the appropriate scales of time and space. The current scientific debate includes: i) changes (or not) of the mineral reactive surface with the progress of the dissolution/precipitation reactions; ii) energy jumps (discontinuity) in the thermodynamic affinity function of some dissolution/precipitation reactions and iii) integration of processes at the "mineral - aqueous solution" interfaces for alumino-silicates, silica and carbonates. In recent works dealing with the specific case of amorphous silica, measurements were performed on nano-metric cross-sections indicating the presence of surface layer between the bulk solution and the mineral. This thin layer is composed by amorphous silica and hydrated silica "permeable" to the transfer of water and ionic chemical constituents. The boundary/interface between the initial mineral and the silica layer is characterized by a high concentration jump of chemical products at the nanoscale and some specific interfacial dissolution/precipitation processes.In this study, the results of numerical simulations dealing with different mechanisms of silicate and carbonate dissolution/precipitation reactions and integrating interfacial processes will be discussed. The application of this approach to silica precipitation is based on laboratory experiments and it highlights the significant role of the "titration" surface induced by surface complexation reactions in the determination of the kinetics of precipitation.

The comparison of phosphate-titanate-silicate layers on the titanium and Ti6Al4V alloy base

NASA Astrophysics Data System (ADS)

Rokita, M.

2011-08-01

The studied layers were composed of two parts: titanate-silicate underlayer for better adhesion and titanate-phosphate-silicate layers for potential bioparameters. The layers with different amounts of hydroxyapatite were deposited on titanium and Ti6Al4V alloy substrates using dipping sol-gel method and electrophoresis. The selection of sol/suspension composition, deposition time and heat treatment conditions have the decisive influence on the layers parameters. The obtained layers should be very thin and almost amorphous. The specific nature of ceramic layers on the metal substrates excludes the use of some measurements methods or makes it difficult to interpret the measurement results. All the obtained samples were compared using XRD analysis data (GID technique), SEM with EDX measurements and FTIR spectroscopy (transmission and reflection techniques) before and after soaking in simulated body fluid. FTIR spectroscopy with mathematical treatment of the spectra (BIO-RAD Win-IR program, Arithmetic-subtract function) was used to detect the increase or decrease of any phosphate phases during SBF soaking. Based on the FTIR results the processes of hydroxyapatite (HAp) growth or layer dissolution were estimated. The layers deposited on titanium substrate are more crystalline then the ones deposited on Ti6Al4V. During SBF soaking process the growth of small amount of microcrystalline carbonate hydroxyapatite was observed on titanium substrate. The layer on Ti6Al4V base contained amorphous carbonate apatite. During heating treatment above about 870-920 K this apatite transforms into carbonate hydroxyapatite. The Ti6Al4V substrate seems to be more advantageous in context of potentially bioactive materials obtaining.

Composition, structure and chemistry of interstellar dust

NASA Technical Reports Server (NTRS)

Tielens, Alexander G. G. M.; Allamandola, Louis J.

1986-01-01

The observational constraints on the composition of the interstellar dust are analyzed. The dust in the diffuse interstellar medium consists of a mixture of stardust (amorphous silicates, amorphous carbon, polycyclic aromatic hydrocarbons, and graphite) and interstellar medium dust (organic refractory material). Stardust seems to dominate in the local diffuse interstellar medium. Inside molecular clouds, however, icy grain mantles are also important. The structural differences between crystalline and amorphous materials, which lead to differences in the optical properties, are discussed. The astrophysical consequences are briefly examined. The physical principles of grain surface chemistry are discussed and applied to the formation of molecular hydrogen and icy grain mantles inside dense molecular clouds. Transformation of these icy grain mantles into the organic refractory dust component observed in the diffuse interstellar medium requires ultraviolet sources inside molecular clouds as well as radical diffusion promoted by transient heating of the mantle. The latter process also returns a considerable fraction of the molecules in the grain mantle to the gas phase.

Phase analysis of ZrO2-SiO2 systems synthesized through Ball milling mechanical activations

NASA Astrophysics Data System (ADS)

Nurlaila, Rizka; Musyarofah, Muwwaqor, Nibras Fuadi; Triwikantoro, Kuswoyo, Anton; Pratapa, Suminar

2017-01-01

Zircon powders have been produced from raw materials of amorphous zirconia and amorphous silica powders obtained from natural zircon sand of Kalimantan Tengah, Indonesia. Synthesis process was started with the extraction of zircon powder to produce sodium silicate solution and pure zircon powder. The amorphous zirconia and silica powders were prepared by alkali fusion and co-precipitation techniques. The powders were mixed using a planetary ball mill, followed by a calcination of various holding time of 3, 10, and 15 h. Phase characterization was done using X-Ray Diffraction (XRD) technique and analysis of the diffraction data was carried out using Rietica and MAUD software. The identified phases after the calcination were zircon, tetragonal zirconia, and cristobalite. The highest zircon content was obtained in the sample calcinated for15 hours - reaching 99.66 %wt. Crystallite size analysis revealed that the samples calcinated for 3, 10, and 15 h exhibited zircon crystal size of 176 (1) nm, 191 (1) nm and 233 (1) nm respectively.

METHOD OF PURIFYING RADIOACTIVE WATER

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

Acfi, D.; Schmitt, M.; Neveu, M.

The utilization of lithothamnium calcareum as an ion exchanger for the decontamination of radioactive water is described. In order to retain cobalt and strontium the ion exchanger is mixed with calcium silicate or borate; alternatively sodium phosphate is added to the water prior to the purification process. (NPO)

Double cross-polarization MAS NMR in the assignment of abundant-spin resonances: ¹⁹F-{²⁹Si}-¹⁹F FBCP/MAS NMR of fluoride ions incorporated in calcium silicate hydrate (C-S-H) phases.

PubMed

Tran, Thuan T; Bildsøe, Henrik; Jakobsen, Hans J; Skibsted, Jørgen

2012-08-01

A new version of the double cross-polarization MAS NMR experiment, which transfers polarization Forth and Back (FBCP) between high- and low-γ spin nuclei, is presented. The pulse sequence is demonstrated by ¹⁹F-{²⁹Si}-¹⁹F and ¹⁹F-{¹³C}-¹⁹F FBCP NMR spectra of a mixture of cuspidine (Ca₄Si₂O₇F₂) and Teflon (-CF₂-)(n). The experiment is useful for assignment of the high-γ spin resonances, as demonstrated by ¹⁹F-{²⁹Si}-¹⁹F FBCP NMR of a fluoride-containing calcium-silicate-hydrate (C-S-H) phase, where the ¹⁹F resonance from fluoride ions incorporated in the interlayer structure of the C-S-H phase is identified. Copyright © 2012 Elsevier Inc. All rights reserved.

Solubility of a new calcium silicate-based root-end filling material

PubMed Central

Singh, Shishir; Podar, Rajesh; Dadu, Shifali; Kulkarni, Gaurav; Purba, Rucheet

2015-01-01

Introduction: The purpose of this study was to compare solubility of a new calcium silicate-based cement, Biodentine with three commonly used root-end filling materials viz. glass-ionomer cement (GIC), intermediate restorative material (IRM), and mineral trioxide aggregate (MTA). Materials and Methods: Twenty stainless steel ring molds were filled with cements corresponding to four groups (n = 5). The weight of 20 dried glass bottles was recorded. Samples were transferred to bottles containing 5 ml of distilled water and stored for 24 h. The bottles were dried at 105΀C and weighed. This procedure was repeated for 3, 10, 30, and 60 days. Data was analyzed with one-way analysis of variance (ANOVA) test (P < 0.05). Results: Biodentine demonstrated significantly higher solubility than MTA for 30- and 60-day immersion periods. Statistical difference was noted between the solubility values of Biodentine samples amongst each of the five time intervals. Conclusions: Biodentine exhibited higher solubility in comparison with all other cements. PMID:25829696

Mesocrystalline calcium silicate hydrate: A bioinspired route toward elastic concrete materials

PubMed Central

Picker, Andreas; Nicoleau, Luc; Burghard, Zaklina; Bill, Joachim; Zlotnikov, Igor; Labbez, Christophe; Nonat, André; Cölfen, Helmut

2017-01-01

Calcium silicate hydrate (C-S-H) is the binder in concrete, the most used synthetic material in the world. The main weakness of concrete is the lack of elasticity and poor flexural strength considerably limiting its potential, making reinforcing steel constructions necessary. Although the properties of C-S-H could be significantly improved in organic hybrids, the full potential of this approach could not be reached because of the random C-S-H nanoplatelet structure. Taking inspiration from a sea urchin spine with highly ordered nanoparticles in the biomineral mesocrystal, we report a bioinspired route toward a C-S-H mesocrystal with highly aligned C-S-H nanoplatelets interspaced with a polymeric binder. A material with a bending strength similar to nacre is obtained, outperforming all C-S-H–based materials known to date. This strategy could greatly benefit future construction processes because fracture toughness and elasticity of brittle cementitious materials can be largely enhanced on the nanoscale. PMID:29209660

First investigations on the quaternary system Na2O-K2O-CaO-SiO2: synthesis and crystal structure of the mixed alkali calcium silicate K1.08Na0.92Ca6Si4O15

NASA Astrophysics Data System (ADS)

Kahlenberg, Volker; Mayerl, Michael Jean-Philippe; Schmidmair, Daniela; Krüger, Hannes; Tribus, Martina

2018-04-01

In the course of an exploratory study on the quaternary system Na2O-K2O-CaO-SiO2 single crystals of the first anhydrous sodium potassium calcium silicate have been obtained from slow cooling of a melt in the range between 1250 and 1050 °C. Electron probe micro analysis suggested the following idealized molar ratios of the oxides for the novel compound: K2O:Na2O:CaO:SiO2 = 1:1:12:8 (or KNaCa6Si4O15). Single-crystal diffraction measurements on a crystal with chemical composition K1.08Na0.92Ca6Si4O15 resulted in the following basic crystallographic data: monoclinic symmetry, space group P 21/ c, a = 8.9618(9) Å, b = 7.3594(6) Å, c = 11.2453(11) Å, β= 107.54(1)°, V = 707.2(1) Å3, Z = 2. Structure solution was performed using direct methods. The final least-squares refinement converged at a residual of R(|F|) = 0.0346 for 1288 independent reflections and 125 parameters. From a structural point of view, K1.08Na0.92Ca6Si4O15 belongs to the group of mixed-anion silicates containing [Si2O7]- and [SiO4]-units in the ratio 1:2. The mono- and divalent cations occupy a total of four crystallographically independent positions located in voids between the tetrahedra. Three of these sites are exclusively occupied by calcium. The fourth site is occupied by 54(1)% K and 46%(1) Na, respectively. Alternatively, the structure can be described as a heteropolyhedral framework based on corner-sharing silicate tetrahedra and [CaO6]-octahedra. The network can build up from kröhnkite-like [Ca(SiO4)2O2]-chains running along [001]. A detailed comparison with other A2B6Si4O15-compounds including topological and group-theoretical aspects is presented.

Interstellar Silicon Depletion and the Ultraviolet Extinction

NASA Astrophysics Data System (ADS)

Mishra, Ajay; Li, Aigen

2018-01-01

Spinning small silicate grains were recently invoked to account for the Galactic foreground anomalous microwave emission. These grains, if present, will absorb starlight in the far ultraviolet (UV). There is also renewed interest in attributing the enigmatic 2175 Å interstellar extinction bump to small silicates. To probe the role of silicon in the UV extinction, we explore the relations between the amount of silicon required to be locked up in silicates [Si/H]dust and the 2175 Å bump or the far-UV extinction rise, based on an analysis of the extinction curves along 46 Galactic sightlines for which the gas-phase silicon abundance [Si/H]gas is known. We derive [Si/H]dust either from [Si/H]ISM - [Si/H]gas or from the Kramers- Kronig relation which relates the wavelength-integrated extinction to the total dust volume, where [Si/H]ISM is the interstellar silicon reference abundance and taken to be that of proto-Sun or B stars. We also derive [Si/H]dust from fi�tting the observed extinction curves with a mixture of amorphous silicates and graphitic grains. We fi�nd that in all three cases [Si/H]dust shows no correlation with the 2175 Å bump, while the carbon depletion [C/H]dust tends to correlate with the 2175 Å bump. This supports carbon grains instead of silicates as the possible carrier of the 2175 Å bump. We also �find that neither [Si/H]dust nor [C/H]dust alone correlates with the far-UV extinction, suggesting that the far-UV extinction is a combined effect of small carbon grains and silicates.

Interstellar Silicon Depletion and the Ultraviolet Extinction

NASA Astrophysics Data System (ADS)

Mishra, Ajay; Li, Aigen

2017-12-01

Spinning small silicate grains were recently invoked to account for the Galactic foreground anomalous microwave emission. These grains, if present, will absorb starlight in the far-ultraviolet (UV). There is also renewed interest in attributing the enigmatic 2175 \\mathringA interstellar extinction bump to small silicates. To probe the role of silicon in the UV extinction, we explore the relations between the amount of silicon required to be locked up in silicates {[{Si}/{{H}}]}{dust} and the 2175 \\mathringA bump or the far-UV extinction rise, based on an analysis of the extinction curves along 46 Galactic sightlines for which the gas-phase silicon abundance {[{Si}/{{H}}]}{gas} is known. We derive {[{Si}/{{H}}]}{dust} either from {[{Si}/{{H}}]}{ISM}‑{[{Si}/{{H}}]}{gas} or from the Kramers–Kronig relation, which relates the wavelength-integrated extinction to the total dust volume, where {[{Si}/{{H}}]}{ISM} is the interstellar silicon reference abundance and taken to be that of proto-Sun or B stars. We also derive {[{Si}/{{H}}]}{dust} from fitting the observed extinction curves with a mixture of amorphous silicates and graphitic grains. We find that in all three cases {[{Si}/{{H}}]}{dust} shows no correlation with the 2175 \\mathringA bump, while the carbon depletion {[{{C}}/{{H}}]}{dust} tends to correlate with the 2175 \\mathringA bump. This supports carbon grains instead of silicates as the possible carriers of the 2175 \\mathringA bump. We also find that neither {[{Si}/{{H}}]}{dust} nor {[{{C}}/{{H}}]}{dust} alone correlates with the far-UV extinction, suggesting that the far-UV extinction is a combined effect of small carbon grains and silicates.

Insights into the interfacial strengthening mechanisms of calcium-silicate-hydrate/polymer nanocomposites.

PubMed

Zhou, Yang; Hou, Dongshuai; Geng, Guoqing; Feng, Pan; Yu, Jiao; Jiang, Jinyang

2018-03-28

The mechanical properties of organic/inorganic composites can be highly dependent on the interfacial interactions. In this work, with organic polymers intercalated into the interlayer of inorganic calcium silicate hydrate (C-S-H), the primary binding phase of Portland cement, great ductility improvement is obtained for the nanocomposites. Employing reactive molecular dynamics, the simulation results indicate that strong interfacial interactions between the polymers and the substrate contribute greatly to strengthening the materials, when C-S-H/poly ethylene glycol (PEG), C-S-H/poly acrylic acid (PAA), and C-S-H/poly vinyl alcohol (PVA) were subject to uniaxial tension along different lattice directions. In the x and z direction tensile processes, the Si-OCa bonds of the C-S-H gel, which were elongated and broken to form Si-OH and Ca-OH, play a critical role in loading resistance, while the incorporation of polymers bridged the neighboring silicate sheets, and activated more the hydrolytic reactions at the interfaces to avoid strain localization, thus increasing the tensile strength and postponing the fracture. On the other hand, Si-O-Si bonds of C-S-H mainly take the load when tension was applied along the y direction. During the post-yield stage, rearrangements of silicate tetrahedra occurred to prevent rapid damage. The polymer intercalation further elongates this post-yield period by forming interfacial Si-O-C bonds, which promote rearrangements and improve the connectivity of the defective silicate morphology, significantly improving the ductility. Among the polymers, PEG exhibits the strongest interaction with C-S-H, and thus C-S-H/PEG possesses the highest ductility. We expect that the molecular-scale mechanisms interpreted here will shed new light on the stress-activated chemical interactions at the organic/inorganic interfaces, and help eliminate the brittleness of cement-based materials on a genetic level.

Initial stages of calcium uptake and mineral deposition in sea urchin embryos

PubMed Central

Vidavsky, Netta; Addadi, Sefi; Mahamid, Julia; Shimoni, Eyal; Ben-Ezra, David; Shpigel, Muki; Weiner, Steve; Addadi, Lia

2014-01-01

Sea urchin larvae have an endoskeleton consisting of two calcitic spicules. We reconstructed various stages of the formation pathway of calcium carbonate from calcium ions in sea water to mineral deposition and integration into the forming spicules. Monitoring calcium uptake with the fluorescent dye calcein shows that calcium ions first penetrate the embryo and later are deposited intracellularly. Surprisingly, calcium carbonate deposits are distributed widely all over the embryo, including in the primary mesenchyme cells and in the surface epithelial cells. Using cryo-SEM, we show that the intracellular calcium carbonate deposits are contained in vesicles of diameter 0.5–1.5 μm. Using the newly developed airSEM, which allows direct correlation between fluorescence and energy dispersive spectroscopy, we confirmed the presence of solid calcium carbonate in the vesicles. This mineral phase appears as aggregates of 20–30-nm nanospheres, consistent with amorphous calcium carbonate. The aggregates finally are introduced into the spicule compartment, where they integrate into the growing spicule. PMID:24344263

Initial stages of calcium uptake and mineral deposition in sea urchin embryos.

PubMed

Vidavsky, Netta; Addadi, Sefi; Mahamid, Julia; Shimoni, Eyal; Ben-Ezra, David; Shpigel, Muki; Weiner, Steve; Addadi, Lia

2014-01-07

Sea urchin larvae have an endoskeleton consisting of two calcitic spicules. We reconstructed various stages of the formation pathway of calcium carbonate from calcium ions in sea water to mineral deposition and integration into the forming spicules. Monitoring calcium uptake with the fluorescent dye calcein shows that calcium ions first penetrate the embryo and later are deposited intracellularly. Surprisingly, calcium carbonate deposits are distributed widely all over the embryo, including in the primary mesenchyme cells and in the surface epithelial cells. Using cryo-SEM, we show that the intracellular calcium carbonate deposits are contained in vesicles of diameter 0.5-1.5 μm. Using the newly developed airSEM, which allows direct correlation between fluorescence and energy dispersive spectroscopy, we confirmed the presence of solid calcium carbonate in the vesicles. This mineral phase appears as aggregates of 20-30-nm nanospheres, consistent with amorphous calcium carbonate. The aggregates finally are introduced into the spicule compartment, where they integrate into the growing spicule.

High-compactness coating grown by plasma electrolytic oxidation on AZ31 magnesium alloy in the solution of silicate-borax

NASA Astrophysics Data System (ADS)

Shen, M. J.; Wang, X. J.; Zhang, M. F.

2012-10-01

A ceramic coating was formed on the surface of AZ31 magnesium alloy by plasma electrolytic oxidation (PEO) in the silicate solution with and without borax doped. The composition, morphology, elements and roughness as well as mechanical property of the coating were investigated by X-ray diffraction (XRD), scanning electron microscope (SEM), energy dispersive X-ray spectrometry (EDS), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and reciprocal-sliding tribometer. The results show that the PEO coating is mainly composed of magnesia. When using borax dope, boron element is permeating into the coating and the boron containing phase exist in the form of amorphous. In addition, the microhardness and compactness of the PEO coating are improved significantly due to doped borax.

Hyperactivity and Dust Composition of Comet 103P/Hartley 2 During the EPOXI Encounter

NASA Astrophysics Data System (ADS)

Harker, David E.; Woodward, Charles E.; Kelley, Michael S. P.; Wooden, Diane H.

2018-05-01

Short-period comet 103P/Hartley 2 (103P) was the flyby target of the Deep Impact eXtended Investigation on 2010 November 4 UT. This comet has a small hyperactive nucleus, i.e., it has a high water production rate for its surface area. The underlying cause of the hyperactivity is unknown; the relative abundances of volatiles in the coma of 103P are not unusual. However, the dust properties of this comet have not been fully explored. We present four epochs of mid-infrared spectra and images of comet 103P observed from Gemini-South +T-ReCS on 2010 November 5, 7, 21 and December 13 UT, near and after the spacecraft encounter. Comet 103P exhibited a weak 10 μm emission feature ≃1.14 ± 0.01 above the underlying local 10 μm continuum. Thermal dust grain modeling of the spectra shows the grain composition (mineralogy) was dominated by amorphous carbon and amorphous pyroxene with evidence for Mg-rich crystalline olivine. The grain size has a peak grain radius range of a peak ∼ 0.5–0.9 μm. On average, the crystalline silicate mass fraction is ≃0.24, fairly typical of other short-period comets. In contrast, the silicate-to-carbon ratio of ≃0.48–0.64 is lower compared to other short-period comets, which indicates that the flux measured in the 10 μm region of 103P was dominated by amorphous carbon grains. We conclude that the hyperactivity in comet 103P is not revealing dust properties similar to the small grains seen with the Deep Impact experiment on comet 9P/Tempel 1 or from comet C/1995 O1 (Hale–Bopp).

Conventional Radiology in Crystal Arthritis: Gout, Calcium Pyrophosphate Deposition, and Basic Calcium Phosphate Crystals.

PubMed

Jacques, Thibaut; Michelin, Paul; Badr, Sammy; Nasuto, Michelangelo; Lefebvre, Guillaume; Larkman, Neal; Cotten, Anne

2017-09-01

This article reviews the main radiographic features of crystal deposition diseases. Gout is linked to monosodium urate crystals. Classic radiographic features include subcutaneous tophi, large and well-circumscribed paraarticular bone erosions, and exuberant bone hyperostosis. Calcium pyrophosphate deposition (CPPD) can involve numerous structures, such as hyaline cartilages, fibrocartilages, or tendons. CPPD arthropathy involves joints usually spared by osteoarthritis. Basic calcium phosphate deposits are periarticular or intraarticular. Periarticular calcifications are amorphous, dense, and round or oval with well-limited borders, and most are asymptomatic. When resorbing, they become cloudy and less dense with an ill-defined shape and can migrate into adjacent structures. Copyright © 2017 Elsevier Inc. All rights reserved.

Effects of ionizing radiation and temperature on uranyl silicates: soddyite (UO2)2(SiO4)(H2O)2 and Uranophane Ca(UO2)2(SiO3OH)2·5H2O.

PubMed

Sureda, R; Casas, I; Giménez, J; de Pablo, J; Quiñones, J; Zhang, J; Ewing, R C

2011-03-15

The stability of soddyite under electron irradiation has been studied over the temperature range of 25-300 °C. At room temperature, soddyite undergoes a crystalline-to-amorphous transformation (amorphization) at a total dose of 6.38 × 10(8) Gy. The electron beam irradiation results suggest that the soddyite structure is susceptible to radiation-induced nanocrystallization of UO(2). The temperature dependence of amorphization dose increases linearly up to 300 °C. A thermogravimetric and calorimetric analysis (TGA-DSC) combined with X-ray diffraction (XRD) indicates that soddyite retains its water groups up to 400 °C, followed by the collapse of the structure. Based on thermal analysis of uranophane, the removal of some water groups at relatively low temperatures provokes the collapse of the uranophane structure. This structural change appears to be the reason for the increase of amorphization dose at 140 °C. According to the results obtained, radiation field of a nuclear waste repository, rather than temperature effects, may cause changes in the crystallinity of soddyite and affect its stability during long-term storage.

Antagonist effects of calcium on borosilicate glass alteration

NASA Astrophysics Data System (ADS)

Mercado-Depierre, S.; Angeli, F.; Frizon, F.; Gin, S.

2013-10-01

Numerous studies have been conducted on glass and cement durability in contact with water, but very little work to date has focused directly on interactions between the two materials. These interactions are mostly controlled by silicon-calcium reactivity. However, the physical and chemical processes involved remain insufficiently understood to predict the evolution of coupled glass-cement systems used in several industrial applications. Results are reported from borosilicate glass alteration in calcium-rich solutions. Our data show that four distinct behaviors can be expected according to the relative importance of three key parameters: the pH, the reaction progress (short- or long-term alteration) and the calcium concentration. Glass alteration is thus controlled by specific mechanisms depending on the solution chemistry: calcium complexation at the glass surface, precipitation of calcium silicate hydrates (C-S-H) or calcium incorporation in the altered layer. These findings highlight the impact of silicon-calcium interactions on glass durability and open the way for a better understanding of glass-cement mixing in civil engineering applications as well as in nuclear waste storage.

A review of the bioactivity of hydraulic calcium silicate cements

PubMed Central

Niu, Li-na; Jiao, Kai; Wang, Tian-da; Zhang, Wei; Camilleri, Josette; Bergeron, Brian E.; Feng, Hai-lan; Mao, Jing; Chen, Ji-hua; Pashley, David H.; Tay, Franklin R.

2014-01-01

Objectives In tissue regeneration research, the term “bioactivity” was initially used to describe the resistance to removal of a biomaterial from host tissues after intraosseous implantation. Hydraulic calcium silicate cements (HCSCs) are putatively accepted as bioactive materials, as exemplified by the increasing number of publications reporting that these cements produce an apatite-rich surface layer after they contact simulated body fluids. Methods In this review, the same definitions employed for establishing in vitro and in vivo bioactivity in glass–ceramics, and the proposed mechanisms involved in these phenomena are used as blueprints for investigating whether HCSCs are bioactive. Results The literature abounds with evidence that HCSCs exhibit in vitro bioactivity; however, there is a general lack of stringent methodologies for characterizing the calcium phosphate phases precipitated on HCSCs. Although in vivo bioactivity has been demonstrated for some HCSCs, a fibrous connective tissue layer is frequently identified along the bone–cement interface that is reminiscent of the responses observed in bioinert materials, without accompanying clarifications to account for such observations. Conclusions As bone-bonding is not predictably achieved, there is insufficient scientific evidence to substantiate that HCSCs are indeed bioactive. Objective appraisal criteria should be developed for more accurately defining the bioactivity profiles of HCSCs designed for clinical use. PMID:24440449

Cell adhesion to borate glasses by colloidal probe microscopy.

PubMed

Wiederhorn, Sheldon M; Chae, Young-Hun; Simon, Carl G; Cahn, Jackson; Deng, Yan; Day, Delbert

2011-05-01

The adhesion of osteoblast-like cells to silicate and borate glasses was measured in cell growth medium using colloidal probe microscopy. The probes consisted of silicate and borate glass spheres, 25-50 μm in diameter, attached to atomic force microscope cantilevers. Variables of the study included glass composition and time of contact of the cell to the glasses. Increasing the time of contact from 15 to 900 s increased the force of adhesion. The data could be plotted linearly on a log-log plot of adhesive force versus time. Of the seven glasses tested, five had slopes close to 0.5, suggesting a square root dependence of the adhesive force on the contact time. Such behavior can be interpreted as a diffusion limited process occurring during the early stages of cell attachment. We suggest that the rate limiting step in the adhesion process is the diffusion of integrins resident in the cell membrane to the area of cell attachment. Data presented in this paper support the hypothesis of Hench et al. that strong adhesion depends on the formation of a calcium phosphate reaction layer on the surfaces of the glass. Glasses that did not form a calcium phosphate layer exhibited a weaker adhesive force relative to those glasses that did form a calcium phosphate layer. Published by Elsevier Ltd.

Clinical Effects of a Dietary Antioxidant Silicate Supplement, Microhydrin((R)), on Cardiovascular Responses to Exercise.

PubMed

Purdy Lloyd, Kimberly L.; Wasmund, Wendy; Smith, Leonard; Raven, Peter B.

2001-01-01

Amorphous silicate minerals, often described as rock flour, were once common in natural water sources and abundant in glacial stream waters. Not only do the silica mineral particles bond water and other elements for transport; they also can be adsorbed with reduced hydrogen, which releases electrons, providing antioxidant or reducing potential to surrounding fluids. The purpose of this investigation was to examine the cardiovascular responses during exercise after consumption of a dietary silicate mineral antioxidant supplement, Microhydrin((R)) (Royal BodyCare, Inc., Irving, TX). A clinical trial incorporating a double-blind, placebo-controlled, crossover experimental design was employed. Subjects received either active agent or placebo, four capsules per day, for 7 days before the trial. The trial evaluated six exercise bicycle-trained subjects performing a 40-km bicycling time trial. Ratings of perceived exertion and measurements of oxygen uptake, heart rate, performance workload, and preexercise and postexercise blood lactate concentrations were obtained. Although there were no differences (P >/=.05) in work performed, heart rate, oxygen uptake, and ratings of perceived exertion during the time trial, the postexercise blood lactate concentrations were significantly lower (P

Silicification in Grasses: Variation between Different Cell Types

PubMed Central

Kumar, Santosh; Soukup, Milan; Elbaum, Rivka

2017-01-01

Plants take up silicon as mono-silicic acid, which is released to soil by the weathering of silicate minerals. Silicic acid can be taken up by plant roots passively or actively, and later it is deposited in its polymerized form as amorphous hydrated silica. Major silica depositions in grasses occur in root endodermis, leaf epidermal cells, and outer epidermal cells of inflorescence bracts. Debates are rife about the mechanism of silica deposition, and two contrasting scenarios are often proposed to explain it. According to the passive mode of silicification, silica deposition is a result of silicic acid condensation due to dehydration, such as during transpirational loss of water from the aboveground organs. In general, silicification and transpiration are positively correlated, and continued silicification is sometimes observed after cell and tissue maturity. The other mode of silicification proposes the involvement of some biological factors, and is based on observations that silicification is not necessarily coupled with transpiration. Here, we review evidence for both mechanisms of silicification, and propose that the deposition mechanism is specific to the cell type. Considering all the cell types together, our conclusion is that grass silica deposition can be divided into three modes: spontaneous cell wall silicification, directed cell wall silicification, and directed paramural silicification in silica cells. PMID:28400787

FORCAST Observations of Galactic Evolved Stars: Measurements of Carbonaceous Dust, Crystalline Silicates, and Fullerenes from SOFIA

NASA Astrophysics Data System (ADS)

Kraemer, Kathleen; Sloan, G. C.; Keller, L. D.; Groenewegen, M. A. T.

2018-01-01

We present preliminary results from two projects to observe the mid-infrared spectra of evolved stars in the Milky Way using the FORCAST instrument on SOFIA. In the first project, we observed a set of 31 carbon stars over the course of three cycles (government shutdowns contributed to the delays in the program execution), covering a wavelength range of 5-13.7 μm, which includes prominent dust and gas diagnostics. The sources were selected to sample portions of period and flux phase space which were not covered in existing samples from older telescopes such as the Infrared Space Observatory (ISO) or Infrared Astronomical Satellite (IRAS). In the second project, we searched for fullerene emission (C60) at 18.9 μm in Galactic sources with crystalline silicate emission. Although most evolved stars are either carbon-rich or oxygen- (silicate-) rich, fullerenes, a carbon-rich molecule, have been observed in several oxygen-rich evolved stars whose silicate emission features are crystalline rather than the more usual amorphous types. None of our targets show clear signatures of fullerene emission.Support for this work was provided by NASA through awards SOF 03-0079, SOF 03-0104, and SOF 04-0129 issued by USRA.

Oxalate secretion by ectomycorrhizal Paxillus involutus is mineral-specific and controls calcium weathering from minerals

PubMed Central

Schmalenberger, A.; Duran, A. L.; Bray, A. W.; Bridge, J.; Bonneville, S.; Benning, L. G.; Romero-Gonzalez, M. E.; Leake, J. R.; Banwart, S. A.

2015-01-01

Trees and their associated rhizosphere organisms play a major role in mineral weathering driving calcium fluxes from the continents to the oceans that ultimately control long-term atmospheric CO2 and climate through the geochemical carbon cycle. Photosynthate allocation to tree roots and their mycorrhizal fungi is hypothesized to fuel the active secretion of protons and organic chelators that enhance calcium dissolution at fungal-mineral interfaces. This was tested using 14CO2 supplied to shoots of Pinus sylvestris ectomycorrhizal with the widespread fungus Paxillus involutus in monoxenic microcosms, revealing preferential allocation by the fungus of plant photoassimilate to weather grains of limestone and silicates each with a combined calcium and magnesium content of over 10 wt.%. Hyphae had acidic surfaces and linear accumulation of weathered calcium with secreted oxalate, increasing significantly in sequence: quartz, granite < basalt, olivine, limestone < gabbro. These findings confirmed the role of mineral-specific oxalate exudation in ectomycorrhizal weathering to dissolve calcium bearing minerals, thus contributing to the geochemical carbon cycle. PMID:26197714

Oxalate secretion by ectomycorrhizal Paxillus involutus is mineral-specific and controls calcium weathering from minerals

NASA Astrophysics Data System (ADS)

Schmalenberger, A.; Duran, A. L.; Bray, A. W.; Bridge, J.; Bonneville, S.; Benning, L. G.; Romero-Gonzalez, M. E.; Leake, J. R.; Banwart, S. A.

2015-07-01

Trees and their associated rhizosphere organisms play a major role in mineral weathering driving calcium fluxes from the continents to the oceans that ultimately control long-term atmospheric CO2 and climate through the geochemical carbon cycle. Photosynthate allocation to tree roots and their mycorrhizal fungi is hypothesized to fuel the active secretion of protons and organic chelators that enhance calcium dissolution at fungal-mineral interfaces. This was tested using 14CO2 supplied to shoots of Pinus sylvestris ectomycorrhizal with the widespread fungus Paxillus involutus in monoxenic microcosms, revealing preferential allocation by the fungus of plant photoassimilate to weather grains of limestone and silicates each with a combined calcium and magnesium content of over 10 wt.%. Hyphae had acidic surfaces and linear accumulation of weathered calcium with secreted oxalate, increasing significantly in sequence: quartz, granite < basalt, olivine, limestone < gabbro. These findings confirmed the role of mineral-specific oxalate exudation in ectomycorrhizal weathering to dissolve calcium bearing minerals, thus contributing to the geochemical carbon cycle.

Generation of composites for bone tissue-engineering applications consisting of gellan gum hydrogels mineralized with calcium and magnesium phosphate phases by enzymatic means.

PubMed

Douglas, Timothy E L; Krawczyk, Grzegorz; Pamula, Elzbieta; Declercq, Heidi A; Schaubroeck, David; Bucko, Miroslaw M; Balcaen, Lieve; Van Der Voort, Pascal; Bliznuk, Vitaliy; van den Vreken, Natasja M F; Dash, Mamoni; Detsch, Rainer; Boccaccini, Aldo R; Vanhaecke, Frank; Cornelissen, Maria; Dubruel, Peter

2016-11-01

Mineralization of hydrogels, desirable for bone regeneration applications, may be achieved enzymatically by incorporation of alkaline phosphatase (ALP). ALP-loaded gellan gum (GG) hydrogels were mineralized by incubation in mineralization media containing calcium and/or magnesium glycerophosphate (CaGP, MgGP). Mineralization media with CaGP:MgGP concentrations 0.1:0, 0.075:0.025, 0.05:0.05, 0.025:0.075 and 0:0.1 (all values mol/dm 3 , denoted A, B, C, D and E, respectively) were compared. Mineral formation was confirmed by IR and Raman, SEM, ICP-OES, XRD, TEM, SAED, TGA and increases in the the mass fraction of the hydrogel not consisting of water. Ca was incorporated into mineral to a greater extent than Mg in samples mineralized in media A-D. Mg content and amorphicity of mineral formed increased in the order A < B < C < D. Mineral formed in media A and B was calcium-deficient hydroxyapatite (CDHA). Mineral formed in medium C was a combination of CDHA and an amorphous phase. Mineral formed in medium D was an amorphous phase. Mineral formed in medium E was a combination of crystalline and amorphous MgP. Young's moduli and storage moduli decreased in dependence of mineralization medium in the order A > B > C > D, but were significantly higher for samples mineralized in medium E. The attachment and vitality of osteoblastic MC3T3-E1 cells were higher on samples mineralized in media B-E (containing Mg) than in those mineralized in medium A (not containing Mg). All samples underwent degradation and supported the adhesion of RAW 264.7 monocytic cells, and samples mineralized in media A and B supported osteoclast-like cell formation. Copyright © 2014 John Wiley & Sons, Ltd. Copyright © 2014 John Wiley & Sons, Ltd.

In vitro evaluation of different heat-treated radio frequency magnetron sputtered calcium phosphate coatings.

PubMed

Yonggang, Yan; Wolke, Joop G C; Yubao, Li; Jansen, John A

2007-06-01

Surface chemical compositions, such as calcium/phosphorus ratio and phase content, have a strong influence on the bioactivity and biocompatibility of calcium phosphate (CaP) coatings as applied on orthopedic and dental implants. Hydroxylapatite (HA) and dicalcium pyrophosphate (DCPP) coatings were prepared on titanium substrates by RF magnetron sputter deposition. The surfaces were left as-prepared (amorphous HA coating; A-HA, amorphous DCPP coating; A-DCPP) or heat treated with: infrared (IR) at 550 degrees C (I-HA) or at 650 degrees C (I-DCPP), and a water steam at 140 degrees C (S-HA and S-DCPP). The surface changes of these coatings were determined after incubation in simulated body fluid (SBF). Also, the growth of rat bone marrow cells (RBM) was studied with scanning electron microscopy (SEM). Both IR and water steam heat treatment changed the sputter-deposited coatings from the amorphous into the crystalline phase. As-prepared amorphous coatings dissolved partially in SBF within 4 weeks of incubation, while heat-treated coatings supported the deposition of a precipitate, i.e., carbonated apatite on both I-HA and S-HA specimens, and tricalciumphosphate on the I-DCPP and S-DCPP specimens. The Ca/P ratio of the A-HA, I-HA, S-HA, A-DCPP, I-DCPP and S-DCPP coatings changed, respectively, from 1.98 to 1.12, 2.01 to 1.76, 1.91 to 1.68, 0.76 to 1.23, 0.76 to 1.26 and 1.62 to 1.55 after 4 weeks of incubation in SBF. Finally, the RBM cells grew well on all heat-treated coatings, but showed different mineralization morphology during cell culturing. The different heat-treatment procedures for the sputtered HA and DCPP coatings influenced the surface characteristics of these coatings, whereby a combination of crystallinity and specific phase composition (Ca/P ratio) strongly affected their in vitro bioactivity.

Drying-induced atomic structural rearrangements in sodium-based calcium-alumino-silicate-hydrate gel and the mitigating effects of ZrO2 nanoparticles

NASA Astrophysics Data System (ADS)

Yang, Kengran; Özçelik, V. Ongun; Garg, Nishant; Gong, Kai; White, Claire E.

Conventional drying of colloidal materials and gels (including cement) can lead to detrimental effects due to the buildup of internal stresses as water evaporates from the nano/microscopic pores. However, the underlying nanoscopic alterations in these gel materials that are, in part, responsible for macroscopically-measured strain values, especially at low relative humidity, remain a topic of open debate in the literature. In this study, sodium-based calcium-alumino-silicate-hydrate (C-(N)-A-S-H) gel, the major binding phase of silicate-activated blast furnace slag (one type of low-CO$_2$ cement), is investigated from a drying perspective, since it is known to suffer extensively from drying-induced microcracking. By employing in situ synchrotron X-ray total scattering measurements and pair distribution function (PDF) analysis we show that the significant contributing factor to the strain development in this material at extremely low relative humidity (0%) is the local atomic structural rearrangement of the C-(N)-A-S-H gel, including collapse of interlayer spacing and slight disintegration of the gel. Moreover, analysis of the medium range (1.0 - 2.2 nm) ordering in the PDF data reveals that the PDF-derived strain values are in much closer agreement (same order of magnitude) with the macroscopically measured strain data, compared to previous results based on reciprocal space X-ray diffraction data. From a mitigation standpoint, we show that small amounts of ZrO$_2$ nanoparticles are able to actively reinforce the structure of silicate-activated slag during drying, preventing atomic level strains from developing. Mechanistically, these nanoparticles induce growth of a silica-rich gel during drying, which, via density functional theory calculations, we show is attributed to the high surface reactivity of tetragonal ZrO$_2$.

Investigations on the crystal-structure and non-ambient behaviour of K2Ca2Si8O19 - a new potassium calcium silicate

NASA Astrophysics Data System (ADS)

Schmidmair, Daniela; Kahlenberg, Volker; Praxmarer, Alessandra; Perfler, Lukas; Mair, Philipp

2017-09-01

Within the context of a systematic re-investigation of phase relationships between compounds of the ternary system K2O-CaO-SiO2 a new potassium calcium silicate with the chemical formula K2Ca2Si8O19 was synthesized via solid state reactions as well as the flux method using KCl as a solvent. Its crystal structure was determined from single-crystal X-ray diffraction data by applying direct methods. The new compound crystallizes in the triclinic space group P 1 bar . Unit cell dimensions are a = 7.4231(7) Å, b = 10.7649(10) Å, c = 12.1252(10) Å, α = 70.193(8)°, β = 83.914(7)° and γ = 88.683(7)°. K2Ca2Si8O19 is built up of corner-connected, slightly distorted [SiO4]-tetrahedra forming double-sheets, which are linked by double-chains of edge-sharing [CaO6]-octahedra. Electroneutrality of the material is provided by additional potassium atoms that are located within the voids of the silicate layers and between adjacent [Ca2O6]-double-chains. Further characterization of the compound was performed by Raman spectroscopy and differential thermal analysis. The behaviour of K2Ca2Si8O19 under high-temperature and high-pressure was investigated by in-situ high-temperature powder X-ray diffraction up to a maximum temperature of 1125 °C and a piston cylinder experiment at 1.5 GPa and 1100 °C. Additionally an overview of known double-layer silicates is given as well as a comparison of K2Ca2Si8O19 to closely related structures.

Mapping the Mineral Resource Base for Mineral Carbon-Dioxide Sequestration in the Conterminous United States

USGS Publications Warehouse

Krevor, S.C.; Graves, C.R.; Van Gosen, B. S.; McCafferty, A.E.

2009-01-01

This database provides information on the occurrence of ultramafic rocks in the conterminous United States that are suitable for sequestering captured carbon dioxide in mineral form, also known as mineral carbon-dioxide sequestration. Mineral carbon-dioxide sequestration is a proposed greenhouse gas mitigation technology whereby carbon dioxide (CO2) is disposed of by reacting it with calcium or magnesium silicate minerals to form a solid magnesium or calcium carbonate product. The technology offers a large capacity to permanently store CO2 in an environmentally benign form via a process that takes little effort to verify or monitor after disposal. These characteristics are unique among its peers in greenhouse gas disposal technologies. The 2005 Intergovernmental Panel on Climate Change report on Carbon Dioxide Capture and Storage suggested that a major gap in mineral CO2 sequestration is locating the magnesium-silicate bedrock available to sequester the carbon dioxide. It is generally known that silicate minerals with high concentrations of magnesium are suitable for mineral carbonation. However, no assessment has been made in the United States that details their geographical distribution and extent, nor has anyone evaluated their potential for use in mineral carbonation. Researchers at Columbia University and the U.S. Geological Survey have developed a digital geologic database of ultramafic rocks in the conterminous United States. Data were compiled from varied-scale geologic maps of magnesium-silicate ultramafic rocks. The focus of our national-scale map is entirely on ultramafic rock types, which typically consist primarily of olivine- and serpentine-rich rocks. These rock types are potentially suitable as source material for mineral CO2 sequestration.

Coma in Comet C/2012 S1 (ISON) at ~4 au

NASA Astrophysics Data System (ADS)

Videen, Gorden; Zubko, Evgenij; Hines, Dean C.; Shkuratov, Yuriy; Kaydash, Vadym; Muinonen, Karri; Knight, Matthew W.; Sitko, Michael L.; Lisse, Carrey M.; Mutchler, Max; Wooden, Diane H.; Li, Jian-Yang; Kobayashi, Hiroshi

2015-11-01

We analyze HST observations of Comet ISON (C/2012 S1) at heliocentric distance ~4 au and phase angle ~12-14 degree. The inner coma (< 5000 km) reveals two polarimetric features, positive degree of linear polarization P = (2.48 ± 0.45)% at projected distances less than 236 km and negative polarization P = - (1.6 ± 0.45)% at 1000 - 5000 km [Hines et al. 2014: ApJL 780, L32]. At these projected distances, average color slope was found to be ~6% per 100 nm [Li et al. 2013: ApJL 779, L3]. When considered simultaneously, these two features place significant constraint on the physical and chemical properties of dust particles [Zubko et al. 2015: Planet. Space Sci., http://dx.doi.org/10.1016/j.pss.2015.08.002].We model this response with agglomerated debris particles, having highly irregular morphology and density of constituent material being consistent with in situ studies of comets. We consider particles of 28 different refractive indices that correspond to in situ studies of comets and plausible assumptions on chemical composition of cometary dust and ices. What emerges from our analysis is that the ISON coma was chemically heterogeneous at the epoch of observation. The positive polarization at small projected distances suggests a high spatial concentration of highly absorbing materials, such as amorphous carbon and/or organics highly irradiated with UV radiation. At larger distances, the negative polarization P = - (1.6 ± 0.45)% and color slope ~6% per 100 nm appear consistent with organics slightly processed with UV radiation, tholins, Mg-Fe silicates, and Mg-rich silicates contaminated with ~10% (by volume) amorphous carbon. A significant abundance of pure water-ice particles and/or pure Mg-rich silicates must be ruled out in this region. These materials have been found in situ in other comets and also detected with imaging polarimetry in the circumnucleus halo regions. Analyses of polarimetric images suggest that Mg-rich silicates could originate from a refractory surface layer on the surface of cometary nuclei [Zubko et al. 2012: A&A 544, L8]. A depletion of such particles in Comet ISON could imply an absence of such a layer on its nucleus.