Morphological control of CaCO3 films with large area: effect of additives and self-organization under atmospheric conditions

Hierarchically structured CaCO(3) films were synthesized at atmospheric conditions (room temperature and 1 atm) without the use of templates or amphiphilic molecules in this process. The resulting CaCO(3) film was formed by self-organization between Ca(OH)(2) and aqueous CO(2). The building blocks of the CaCO(3) film were thought to be CaCO(3) primary nanoparticles that aligned to build higher level structures with greater size, called mesocrystals, depending on the additives. The soluble additives played a key role in the control of the morphology, crystallinity, and polymorphism of the CaCO(3) film, and the effects strongly depended on the type of additive and their concentrations. The additives used in this study decreased the crystallinity of CaCO(3) (calcite) film in the order of glucose > aspartic acid > serine in a manner inversely proportional to the concentration of the additives. In addition, Mg(2+), K(+), and Na(+) ion additives led to the formation of an aragonite phase, the proportion of which increased with the concentration of ions. The threshold concentrations of these ions for the formation of the aragonite phase in CaCO(3) film were found to be in the order of Na(+) > K(+) > Mg(2+).     

Synthesis of nanosized BaSO4 and CaCO3 particles with a membrane reactor: effects of additives on particles

Nanosized BaSO(4) particles, about 15 nm in size, were synthesized successfully by a membrane reactor at the aids of additives, in which Na(2)SO(4) solutions were added into BaCl(2) solutions gradually through the micropores of ultrafiltration membranes to control the saturation ratio, subsequently the nucleation and growth rates. The effects of additives species, additives concentrations, and membranes molecular weight cut-off (MWCO) on the particle morphology, along with the formation processes of particles, were investigated. CaCO(3) nanoparticles of 30-60 nm in size were also prepared by the reactor. The results revealed that the addition of methyl alcohol, ethanol etc. favor the synthesis of nanoparticles with small size. The particles size decreases with the increase in ethanol concentrations. With the increase in membrane MWCO, the products tend from nanoparticles towards aggregates.     

Crystallization of CaCO3 in the presence of sulfate and additives: experimental and molecular dynamics simulation studies

The effects of sulfate and BHTPMP (Bis (hexamethylene) triaminepentakis (methylene phosphonic acid)) on the crystallization rate, phase composition and morphology of calcium carbonate have been studied. It was observed that sulfate reduces the nucleation rate and favors the formation of aragonite form in the calcium carbonate precipitate. Moreover, in the presence of sulfate the rhombohedral morphology of the calcite crystals is modified, and during the formation of calcite, the development of {104} faces are more significantly prohibited than {110} faces. In the presence of sulfate together with BHTPMP, the crystallization process is inhibited and the modified morphology and the dominant calcite form are observed in the solid. The results from molecular dynamics simulations show the more strong combination of sulfate with calcite surface, in particular the {104} face, in comparison with the aragonite surface. The strong interaction of BHTPMP with sulfate and the aragonite surface favors the formation of the dominant calcite phase in the precipitate.     

Hydration of C3a in the presence of CaCO3

The hydration of C₃A with and without CaCO₃ was studied. The techniques used were X-ray diffraction, thermogravimetry, differential thermogravimetry and calorimetry.In the presence of CaCO₃, the hydration of C₃A is accelerated. The hexagonal hydrates are formed first. They react with CaCO₃ to form calcium carboaluminate hydrate. This reaction blocks formation of the cubic hydrate. The latter appears when CaCO₃ is completely consumed.     

Production of CaCO3/hyperbranched polyglycidol hybrid films using spray-coating technique

Biomineralizing organisms employ macromolecules and cellular processing strategies in order to produce highly complex composite materials such as nacre. Bionic approaches translating this knowledge into viable technical production schemes for a large-scale production of biomimetic hybrid materials have met with limited success so far. Investigations presented here thus focus on the production of CaCO(3)/polymer hybrid coatings that can be applied to huge surface areas via reactive spray-coating. Technical requirements for simplicity and cost efficiency include a straightforward one-pot synthesis of low molecular weight hyperbranched polyglycidols (polyethers of 2,3-epoxy-1-propanol) as a simple mimic of biological macromolecules. Polymers functionalized with phosphate monoester, sulfate or carboxylate groups provide a means of controlling CaCO(3) particle density and morphology in the final coatings. We employ reactive spray-coating techniques to generate CaCO(3)/hybrid coatings among which vaterite composites can be prepared in the presence of sulfate-containing hyperbranched polyglycidol. These coatings show high stability and remained unchanged for periods longer than 9 months. By employing carboxylate-based hyperbranched polyglycidol, it is possible to deposit vaterite-calcite composites, whereas phosphate-ester-based hyperbranched polyglycidol leads to calcite composites. Nanoindentation was used to study mechanical properties, showing that coatings thus obtained are slightly harder than pure calcite.     

Exploring the feasibility of bioaerosol analysis as a novel fingerprinting technique

The purpose of this review is to investigate the feasibility of bioaerosol fingerprinting based on current understanding of cellular debris (with emphasis on human-emitted particulates) in aerosols and arguments regarding sampling, sensitivity, separations, and detection schemes. Target aerosol particles include cellular material and proteins emitted by humans, animals, and plants and can be regarded as information-rich packets that carry biochemical information specific to the living organisms present where the sample is collected. In this work we discuss sampling and analysis techniques that can be integrated with molecular (e.g. protein)-detection procedures to properly assess the aerosolized cellular material of interest. Developing a detailed understanding of bioaerosol molecular profiles in different environments suggests exciting possibilities of bioaerosol analysis with applications ranging from military defense to medical diagnosis and wildlife identification     

Studies on characterization of nano CaCO3 prepared by the in situ deposition technique and its application in PP‐nano CaCO3 composites

The elegant approach of in situ deposition technique was used for the synthesis of nano CaCO₃. the nanosize of particles was confirmed by the X‐ray diffraction (XRD) technique. Differential scanning calorimetry (DSC) was used for determination of the enthalpy. The nano CaCO₃ polypropylene (PP) composites were prepared by taking 2 and 10 wt % of different nanosizes (21–39 nm) of CaCO₃. Conversion of the α phase to β was observed in the case of 2 wt % of a 30‐nm sized amount of CaCO₃ in a PP composite. The decrement in ΔH and percent crystallinity, as well as the increment in melt temperature were recorded for 6 wt % nano CaCO₃ with a decrease in nanosize from 39 to 21 nm. The increment in tensile strength with an increase in the amount of nano CaCO₃ was observed, and the lower particle size showed greater improvement. The improvement in thermal and mechanical properties is because of the formation of a greater number of small spherulites uniformly present in the PP matrix. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 107–113, 2004     

Hybrids of dihydrophylic ionic-nonionic block copolymers and CaCO3. Determination of the number of CaCO3 molecules attached to the ionic groups

Polymer mediated crystallization of CaCO₃, in the presence of dihydrophilic ionic-nonionic block copolymer (DHBC), gave hybrid crystalline particles in the form of partially open empty spheres. The DHBC used were composed of a poly(ethylene oxide) block and a block of phosphorylated glycidol. The outer skin of the empty spheres (hybrid particles) is formed of a double layer of small spherical particles of diameter equal to 20 nm. NMR measurements enabled determination of the DHBC content in the hybrids. The calculations on this basis gave a number of macromolecules of DHBC attached to one small sphere (approx. equal to 50). Finally, it was estimated that every fourth CaCO3 molecule on the surface of the small sphere is attached to one phosphate unit of DHBC.     

Fluxional additives: a second generation control in enantioselective catalysis

The concept of "fluxional additives", additives that can adopt enantiomeric conformations depending on the chiral information in the ligand, is demonstrated in enantioselective Diels-Alder and nitrone cycloaddition reactions. The additive design is modular, and diverse structures are accessible in three steps. Chiral Lewis acids from main group and transition metals show enhancements in enantioselectivity in the presence of these additives.     

Superstructures of temporarily stabilized nanocrystalline CaCO3 particles: morphological control via water surface tension variation

In this paper, the formation of different complex morphologies of nanocrystalline CaCO3 under the control of double hydrophilic block copolymers (DHBCs) carrying phosphate groups is described. The DHBCs consist of a poly(ethylene glycol) (PEG) block and a pendant poly[2-(2-hydroxy ethyl)ethylene] block with different degrees of phosphorylation up to 40%, some of which show surface activity. The polymers furthermore temporarily stabilize CaCO3 nanocrystals, which are formed by slow CO2 evaporation from a supersaturated Ca(HCO3)2 solution (Kitano method). The polymers are active down to concentrations of 10(-4) g/L. In dependence of the nature and concentration of the DHBC, tunable complex shuttlecock flowerlike and other superstructures are formed, which are aggregates of CaCO3 vaterite nanoparticles with an enhanced stability of at least 2 months. It is shown that the aggregation starts around template CO2 gas bubbles at the air/water interface. The size and morphology of the growing aggregates depends on the polymer concentration, phosphorylation degree, and water surface tension. The latter determines when the aggregate sinks to the bottom, interrupting the further growth process. Variation of the water surface tension by addition of the nonionic surfactant Antharox CO880 also allows a variation of the aggregate morphology, thus implying the described method as simple and versatile for the generation of complex CaCO3 morphologies.     

A bio-inspired approach to the synthesis of CaCO3 spherical assemblies in a soluble ternary-additive system

Two different soluble polymers, poly(ethylene glycol) (PEG) and poly(methacrylic acid) (PMAA), with individual functions were successfully employed in combination with a third additive, sodium dodecyl sulfate (SDS), in one system, and spherical assemblies (e.g., hollow spheres) with multiscale constructs of CaCO3 were obtained. The variation of polymer concentration drastically changed both the morphology and polymorph of the produced CaCO3 crystals due to the corresponding transformation of the micelle structure. This study suggests that noncovalent interaction and cooperation between soluble macromolecules play key roles in controlling the growth of biominerals. The results also suggest a novel and facile route toward biomimetic inorganic synthesis.     

Multiple chromatographic fingerprinting and its application to the quality control of herbal medicines

Recently, chromatographic fingerprinting has become one of the most powerful approaches to quality control of herbal medicines. However, the performance of reported chromatographic fingerprinting constructed by single chromatogram sometimes turns out to be inadequate for complex herbal medicines, such as multi-herb botanical drug products. In this study, multiple chromatographic fingerprinting, which consists of more than one chromatographic fingerprint and represents the whole characteristics of chemical constitutions of the complex medicine, is proposed as a potential strategy in this complicated case. As a typical example, a binary chromatographic fingerprinting of “Danshen Dropping Pill” (DSDP), the best-sold traditional Chinese medicine in China, was developed. First, two HPLC fingerprints that, respectively, represent chemical characteristics of depsides and saponins of DSDP were developed, which were used to construct binary chromatographic fingerprints of DSDP. Moreover, the authentication and validation of the binary fingerprints were performed. Then, a data-level information fusion method was employed to capture the chemical information encoded in two chromatographic fingerprints. Based on the fusion results, the lot-to-lot consistency and frauds can be determined either using similarity measure or by chemometrics approach. The application of binary chromatographic fingerprinting to consistency assessment and frauds detection of DSDP clearly demonstrated that the proposed method was a powerful approach to quality control of complex herbal medicines.     

How will additives shape the future of plastics?

Additives are essential components of plastic formulations providing maintenance and/or modification of polymer properties, performance and long-term use. The extension of polymer properties by additives has played a substantial role in the growth of plastics. At the beginning of the plastics age additives were used mainly to maintain polymer properties and to help plastics to survive heat treatment during transforming processes. The next generation of additives provided extension of service life as well as modification of mechanical and physical properties. These well-established additives - antioxidants, heat stabilizers, light stabilizers and others - cover the requirements of standard plastics and today's mass applications. The more recent developments of high-performance additives address more stringent or new requirements, more severe processing and use conditions and/or environmental concerns, but still with the main target of maintaining plastic properties. The future will introduce more and more new effects and functionalities through additives in plastic applications tailoring the properties of polymers and offering a vast potential of innovation in the plastics area. Recent examples of emerging technologies show that additives will not only modify the polymer itself and add new properties, but can also, when incorporated into the plastic, beneficially impact properties, which are of high value for the user. The paper shows the role of additives used in plastics from the past to the present with the focus on stabilization and performance of additives incorporated during melt processing, and outlines future trends.     

Water as the Key to Proto‐Aragonite Amorphous CaCO3

Temperature and pH value can affect the short‐range order of proto‐structured and additive‐free amorphous calcium carbonates (ACCs). Whereas a distinct change occurs in proto‐vaterite (pv) ACC above 45 °C at pH 9.80, proto‐calcite (pc) ACC (pH 8.75) is unaffected within the investigated range of temperatures (7–65 °C). IR and NMR spectroscopic studies together with EXAFS analysis showed that the temperature‐induced change is related to the formation of proto‐aragonite (pa) ACC. The data strongly suggest that the binding of water molecules induces dipole moments across the carbonate ions in pa‐ACC as in aragonite, where the dipole moments are due to the symmetry of the crystal structure. Altogether, a (pseudo‐)phase diagram of the CaCO₃ polyamorphism in which water plays a key role can be formulated based on variables of state, such as the temperature, and solution parameters, such as the pH value.     

Unsaturated hyperbranched polyester as a surface modifier of CaCO3 and enhanced effect on mechanical properties of HDPE/CaCO3 composites

The unsaturated hyperbranched polyester (UH20) based on Boltorn™ H20 (H20) end‐capped with methacrylate groups and carboxylic acid groups was introduced to treat calcium carbonate (CaCO₃) as a new type of surface modifier by a wet‐coating technique. The interaction between CaCO₃ and modifier was proven to be due to the ionic character by FT‐IR after the extraction with acetone. The maximum amount of tightly bonded UH20 modifier was determined to be around 9% by thermogravimetric analysis (TGA). The incorporation of CaCO₃ coated with UH20 into high‐density polyethylene (HDPE) decreased the mechanical performance of HDPE/CaCO₃ composite in comparison with CaCO₃ coated with stearic acid. In the presence of a small amount of dicumyl peroxide (DCP), a greatly improvement of the notched impact strength as well the tensile strength of HDPE/CaCO₃ coated with UH20 composite was obtained. An enhanced effect in the mechanical performance of the composite between CaCO₃ coated with UH20 and HDPE matrix in the existence of DCP was suggested. Moreover, the morphological structures of impact fracture surface of the HDPE/CaCO₃ composites were studied by scanning electron microscopy (SEM) to confirm the possible mechanism for explaining the improvement of mechanical properties of the composite. Copyright © 2005 John Wiley & Sons, Ltd.     

investigation of the thermal stability of CaCO3-SrCO3 solid solutions

The decomposition of solid solutions of CaCO₃-SrCO₃, covering the whole range of composition, has been studied by simultaneous TG-DTA. In all cases a two-stage decomposition occurs and the presence of strontium stabilizes CaCO₃.The effect of the different amounts of calcium and strontium ions present in the samples has been separately evaluated by comparison with the results obtained by decomposing mechanical mixtures of CaCO₃ and SrCO₃ of the same composition.     

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