Cold Sintering of Calcium Carbonate for Construction Material Applications.
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ABSTRACT:
SUBMITTER: Zahabi M
PROVIDER: S-EPMC7859949 | biostudies-literature |
REPOSITORIES: biostudies-literature
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Project description:The formation mechanism of calcium carbonate (CC) skeletal tissues in biomineralization has remained poorly understood for a long time. Here, we propose an artificial CC biomineralization system equivalent to the natural one in terms of the primary physicochemical mechanism. Our system is constructed of a polymer gel and a CC solution unsaturated by a dissociated anionic polymer. The gel network consists of proton donor and proton acceptor polymers, which are analogues of polymers in the natural biomineralization system and have affinity for each other through hydrogen bonding interaction. Artificial biomineralization takes place within the polymer gel to produce a monolithic composite of the network and CC, whose powder X-ray diffraction pattern indicates calcite or calcite/vaterite. Scanning electron microscopy and energy-dispersive X-ray spectroscopy observation of the composite during the mineralization process revealed a two-phase structure (network/CC solid solution phase and CC hypercomplex gel phase). As artificial biomineralization proceeds, the solid phase grows in size at the cost of the gel phase as if the latter is substituted with the former, until the solid phase occupies the whole depth of the composite. These results suggest that the hypercomplex gel is the precursor of the resultant network/CC solid solution, and its discontinuous change is a phase transition to the solid solution. Despite minute differences in higher-order structures between our model system and the natural system, the fundamental structure of CC skeletal tissues in the latter can be interpreted as a network/CC solid solution, whereas that of CC cartilaginous tissues as a CC hypercomplex gel. Then, it can be deduced that, in biomineralization, the CC skeletal tissue is in principle formed via a phase transition of the CC cartilaginous tissue.
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Project description:The incorporation of ceramic additives is the most commonly used strategy to improve the biofunctionality of polymer-based scaffolds intended for bone regeneration. By embedding ceramic particles as a coating, the functionality improvement in the polymeric scaffolds can be concentrated on the cell-surface interface, thus creating a more favourable environment for the adhesion and proliferation of osteoblastic cells. In this work, a pressure-assisted and heat-induced method to coat polylactic acid (PLA) scaffolds with calcium carbonate (CaCO3) particles is presented for the first time. The coated scaffolds were evaluated by optical microscopy observations, a scanning electron microscopy analysis, water contact angle measurements, compression testing, and an enzymatic degradation study. The ceramic particles were evenly distributed, covered more than 60% of the surface, and represented around 7% of the coated scaffold weight. A strong bonding interface was achieved, and the thin layer of CaCO3 (~20 µm) provided a significant increase in the mechanical properties (with a compression modulus improvement up to 14%) while also enhancing the surface roughness and hydrophilicity. The results of the degradation study confirmed that the coated scaffolds were able to maintain the pH of the media during the test (~7.6 ± 0.1), in contrast to the pure PLA scaffolds, for which a value of 5.07 ± 0.1 was obtained. The ceramic-coated scaffolds developed showed potential for further evaluations in bone tissue engineering applications.
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Project description:Aqueous cold sintering of two lithium-based compounds, the electrolyte Li6.25La3Zr2Al0.25O12 (LLZAO) and cathode material LiCoO2 (LCO), is reported. For LLZAO, a relative density of ∼87% was achieved, whereas LCO was sintered to ∼95% with 20 wt % LLZAO as a flux/binder. As-cold sintered LLZAO exhibited a low total conductivity (10-8 S/cm) attributed to an insulating grain boundary blocking layer of Li2CO3. The blocking layer was reduced with a post-annealing process or, more effectively, by replacing deionized water with 5 M LiCl during cold sintering to achieve a total conductivity of ∼3 × 10-5 S/cm (similar to the bulk conductivity). For LCO-LLZAO composites, scanning electron microscopy and X-ray computer tomography indicated a continuous LCO matrix with the LLZAO phase evenly distributed but isolated throughout the ceramics. [001] texturing during cold sintering resulted in an order of magnitude difference in electronic conductivity between directions perpendicular and parallel to the c-axis at room temperature. The electronic conductivity (∼10-2 S/cm) of cold sintered LCO-LLZAO ceramics at room temperature was comparable to that of single crystals and higher than those synthesized via either conventional sintering or hot pressing.
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Project description:The design of new birefringent materials is very significant owing to their indispensable role in modulating the polarization of light and is vital in laser technology. Herein, by applying a large optical anisotropy-oriented construction induced by a synergy effect of multiple anionic groups, a promising carbonate-nitrate chloride, Na3Rb6(CO3)3(NO3)2Cl·(H2O)6, has been designed and synthesized successfully by the solvent evaporation method and single crystals of centimeter size were obtained by the recrystallization method in aqueous solution. It crystallizes in the hexagonal P63/mcm space group, the RbO9Cl polyhedra and the NaO7 polyhedra construct a three-dimensional (3D) framework by sharing O or Cl atoms and trigonal plane units (CO3 and NO3). The transmittance spectrum based on a 1 mm thick single-crystal plate shows that its short UV cut-off edge is about 231 nm. And the refractive index differences (0.14 @ 546 nm) measured by using a polarizing microscope on the (101) crystal plane, proves that Na3Rb6(CO3)3(NO3)2Cl·(H2O)6 has a large birefringence, which has potential application in the solar blind ultraviolet region. The theoretical calculations reveal that the π-conjugated CO3 and NO3 groups are the main cause of the birefringence. It demonstrates that combining π-conjugated CO3 and NO3 groups in one structure is an extremely effective strategy to explore new UV birefringent crystals.
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Project description:RationaleThe stable carbon isotopic (δ13 C) reference material (RM) LSVEC Li2 CO3 has been found to be unsuitable for δ13 C standardization work because its δ13 C value increases with exposure to atmospheric CO2 . A new CaCO3 RM, USGS44, has been prepared to alleviate this situation.MethodsUSGS44 was prepared from 8 kg of Merck high-purity CaCO3 . Two sets of δ13 C values of USGS44 were determined. The first set of values was determined by online combustion, continuous-flow (CF) isotope-ratio mass spectrometry (IRMS) of NBS 19 CaCO3 (δ13 CVPDB = +1.95 milliurey (mUr) exactly, where mUr = 0.001 = 1‰), and LSVEC Li2 CO3 (δ13 CVPDB = -46.6 mUr exactly), and normalized to the two-anchor δ13 CVPDB-LSVEC isotope-delta scale. The second set of values was obtained by dual-inlet (DI)-IRMS of CO2 evolved by reaction of H3 PO4 with carbonates, corrected for cross contamination, and normalized to the single-anchor δ13 CVPDB scale.ResultsUSGS44 is stable and isotopically homogeneous to within 0.02 mUr in 100-μg amounts. It has a δ13 CVPDB-LSVEC value of -42.21 ± 0.05 mUr. Single-anchor δ13 CVPDB values of -42.08 ± 0.01 and -41.99 ± 0.02 mUr were determined by DI-IRMS with corrections for cross contamination.ConclusionsThe new high-purity, well-homogenized calcium carbonate isotopic reference material USGS44 is stable and has a δ13 CVPDB-LSVEC value of -42.21 ± 0.05 mUr for both EA/IRMS and DI-IRMS measurements. As a carbonate relatively depleted in 13 C, it is intended for daily use as a secondary isotopic reference material to normalize stable carbon isotope delta measurements to the δ13 CVPDB-LSVEC scale. It is useful in quantifying drift with time, determining mass-dependent isotopic fractionation (linearity correction), and adjusting isotope-ratio-scale contraction. Due to its fine grain size (smaller than 63 μm), it is not suitable as a δ18 O reference material. A δ13 CVPDB-LSVEC value of -29.99 ± 0.05 mUr was determined for NBS 22 oil.
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Project description:Patterned calcium carbonate materials with controlled morphologies have broad applications in both environmental and engineering fields. However, how to fabricate such materials through environmental-friendly methods under ambient conditions is still challenging. Here, we report a green approach for fabricating patterned calcium carbonate materials. This eco-friendly approach is based on template-assisted microbially induced calcium carbonate precipitation. As a proof of concept, by varying the templates and optimizing fabrication parameters, different patterned calcium carbonate materials were obtained. The optimized parameters include C Ca2+ = 80 mM, T i = 15 °C, and templates made of small-sized CaCO3 particles with a concentration of 1.5 mg mL-1, under which better and more sharp patterns were obtained. Materials with periodic patterns were also fabricated through a periodic template, showing good scalability of this approach. The results of this study could mean great potential in applications where spatially controlled calcium carbonate depositions with user-designed patterns are needed.
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