碳酸钙在聚合物胶束控制下的仿生合成

合成了温敏性的聚(N-异丙基丙烯酰胺)-b-聚(L-谷氨酸)(PNIPAM-b-PLGA)嵌段共聚物,在较高温度下制备了以PNIPAM为核、以PLGA为壳的自组装胶束,研究了胶束对碳酸钙晶体生长的控制作用.使用扫描电镜和X射线衍射表征了碳酸钙晶体的形貌和晶型.当聚合物胶束浓度较高时,得到纤维状的文石;当胶束浓度较低时,...     

Crystallization and aggregation behaviors of calcium carbonate in the presence of poly(vinylpyrrolidone) and sodium dodecyl sulfate

An anionic surfactant interacts strongly with a polymer molecule to form a self-assembled structure, due to the attractive force of the hydrophobic association and electrostatic repulsion. In this crystallization medium, the surfactant-stabilized inorganic particles adsorbed on the polymer chains, as well as the bridging effect of polymer molecules, controlled the aggregation behavior of colloidal particles. In this presentation, the spontaneous precipitation of calcium carbonate (CaCO3) was conducted from the aqueous systems containing a water-soluble polymer (poly(vinylpyrrolidone), PVP) and an anionic surfactant (sodium dodecyl sulfate, SDS). When the SDS concentrations were lower than the onset of interaction between PVP and SDS, the precipitated CaCO3 crystals were typically hexahedron-shaped calcite; the increasing SDS concentration caused the morphologies of CaCO3 aggregates to change from the flower-shaped calcite to hollow spherical calcite, then to solid spherical vaterite. These results indicate that the self-organized configurations of the polymer/surfactant supramolecules dominate the morphologies of CaCO3 aggregates, implying that this simple and versatile method expands the morphological investigation of the mineralization process.     

Formation of stable vaterite with poly(acrylic acid) by the delayed addition method

The crystallization of CaCO3 was examined by changing the addition time of poly(acrylic acid) (PAA) to an aqueous solution of calcium carbonate by selectively interacting with the crystal at different stages during the crystal-forming process. The precipitation of CaCO3 was carried out by a double jet method to prevent heterogeneous nucleation on glass walls, and the sodium salt of PAA was added by a delayed addition method. In the initial presence of PAA in an aqueous solution of calcium carbonate, PAA acted as an inhibitor for the nucleation and growth of crystallization. However, it was found that stable vaterite particles were successfully obtained by delaying the addition of PAA from 1 to 60 min. The vaterite particles were stable in the aqueous solution for more than 30 days, and the CaCO3 particles were formed by a spherulitic growth mechanism. It is suggested that PAA strongly binds with the Ca2+ ion on the surface of CaCO3 particles to stabilize the unstable vaterite form effectively. Upon changing the addition time of PAA, we found that CaCO3 particles were formed through different formation mechanisms in selectively controlled crystallization at different stages during the crystallization process.     

Preparation of core-shell CaCO3 capsules via Pickering emulsion templates

Micron size and food grade pristine CaCO(3) particles were used to stabilize an oil in water Pickering emulsion. The particles also acted as nucleation sites for the subsequent crystallization of CaCO(3) with the addition of CaCl(2) and CO(2) gas as precursors. After the controllable crystallization process, a dense CaCO(3) shell with a few microns in thickness was formed. The CaCO(3) shell was proven to be calcite without the presence of crystallization modifiers. The crystallization speed and the shell integrity were controlled by manipulating the addition of CaCl(2) amount during the different crystallization stages; therefore, the homogeneous nucleation in the bulk was almost inhibited, and the heterogeneous nucleation at the oil-water interface on pristine CaCO(3) particles was the main contribution to the growth of the shell. The encapsulated limonene flavor in CaCO(3) capsules showed a prolonged release in neutral water at 85°C, while a burst release at pH 2 water as expected. The method is a simple and scalable process for creating inorganic core-shell capsules and can be used for producing food grade capsules for controlling the flavor release or masking undesirable taste in mouth.     

Influence of conducting polymers based on carboxylated polyaniline on in vitro CaCO3 crystallization

Conducting polymers are interesting materials of technological applications, while the use of polymers as additives controlling crystal nucleation and growth is a fast growing research field. In the present article, we make a first step in combining both topics and report the effect of conducting polymer derivatives, which are based on carboxylated polyanilines (c-PANIs), on in vitro CaCO3 crystallization by the Kitano and gas diffusion method. This is the first example of the mineralization control of CaCO3 by a rigid carboxylated polymer. Both the concentration of c-PANI and the presence of carboxylate groups have a strong influence on the CaCO3 crystallization behavior and crystal morphology. X-ray diffraction (XRD) analysis shows crystalline calcite particles confirmed by FTIR spectra. pH and Ca2+ measurements during CaCO3 crystallization utilizing the Kitano and a constant-pH approach show a defined nucleation period of CaCO3 particles. The measurements allow for the calculation of the supersaturation time development, and the kinetic data can be combined with time-dependent light microscopy. The presence of c-PANIs delays the time of nucleation indicative of calcite nucleation inhibition. Microscopy illustrates the morphologies of CaCO3 crystals at all crystallization stages, from homogeneous spherical amorphous CaCO3 (ACC) particles corresponding to the first steps of crystallization to transition stage calcite crystals also involving a dissolution-recrystallization process in a late stage of crystallization. The data show that it is not possible to conclude the crystallization mechanism even for a very simple additive controlled crystallization process without time-resolved microscopic data supplemented by the analysis of the species present in the solution. Finally, fluorescence analysis indicates that conducting polymer derivatives can be incorporated into precipitated calcite particles. This gives rise to CaCO3 particles with novel and interesting optical properties.     

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.     

P(St-co-MAA)乳液体系对CaCO3结晶的调控

大量研究表明, 有机/无机界面上的相互作用[1]是控制无机结晶的晶型、形貌、粒径等特征的决定因素. 本文利用乳液聚合方法合成了在诱导无机矿化后依然保持较为刚性界面的、能与无机离子作用的微球, 并在乳液中进行碳酸钙结晶实验, 用XRD, FTIR和SEM等手段对结晶进行了表征.     

Mesocrystals: inorganic superstructures made by highly parallel crystallization and controlled alignment

Controlled self-organization of nanoparticles can lead to new materials. The colloidal crystallization of non-spherical nanocrystals is a reaction channel in many crystallization reactions. With additives, self-organization can be stopped at an intermediary step-a mesocrystal-in which the primary units can still be identified. Mesocrystals were observed for various systems as kinetically metastable species or as intermediates in a crystallization reaction leading to single crystals with typical defects and inclusions. The control forces and mechanism of mesocrystal formation are largely unknown, but several mesocrystal properties are known. Mesocrystals are exiting examples of nonclassical crystallization, which does not proceed through ion-by-ion attachment, but by a modular nanobuilding-block route. This path makes crystallization more independent of ion products or molecular solubility, it occurs without pH or osmotic pressure changes, and opens new strategies for crystal morphogenesis.     

Effects of Carboxylic Acids on the Crystallization of Calcium Carbonate

The effects of seven carboxylic acids, i.e., acrylic acid, maleic acid, tartaric acid, malic acid, succinic acid, and citric acid, on CaCO(3) crystallization were studied using the unseeded pH-drift method along with a light-scattering technique. Experiments were started by mixing solutions of CaCl(2) and NaHCO(3) in the presence or absence of additives. The crystallization was studied by recording the decrease in pH resulting from the reaction Ca(2+)+HCO(3)(-)-->CaCO(3)+H(+). A given amount of carboxylic acid was added to the solution of CaCl(2) or NaHCO(3) before mixing the reactants. The pH profiles obtained in the case of the CaCl(2) solution containing an additive were similar to those for the NaHCO(3) solution containing one, and when an additive was added after the onset of crystallization, the growth of CaCO(3) immediately stopped. The light-scattering observations, in all cases, indicated that CaCO(3) nucleation occurred at 10-20 s after mixing of the reactants. The results indicated that the nucleation of CaCO(3) was not influenced by the presence of carboxylic acids, but CaCO(3) crystal growth was reduced by their adsorption to the surface of the CaCO(3) crystals. These phenomena were explained by assuming a stronger affinity of the carboxylic acids for CaCO(3) particles than for the free Ca(2+) ions in solution. The crystallization of CaCO(3) in the presence of additives was divided into three stages: nucleation, growth incubation, and growth periods. Copyright 2001 Academic Press.     

Influence of ozonized kraft lignin on the crystallization of CaCO3

Results are reviewed from a study examining how structural modifications introduced by ozonization enhance the influence of kraft lignin on the crystallization of CaCO(3). Ozone treatment of kraft lignin in an aqueous environment is shown to increase its carboxylic acid and overall oxygen content and reduce its molecular weight. Calcium concentration and temperature were monitored in heated supersaturated solutions containing ozonized kraft lignins to gauge their influence on CaCO(3) crystallization processes. The presence of kraft lignin raises the temperature necessary to induce crystallization. This effect is shown to level off at relatively low lignin concentrations and be dependent on the extent of ozone treatment the kraft lignin has undergone. A linear correlation is found between crystallization temperatures and the carboxylic acid content of ozonized lignin samples indicating the introduction of these functional groups plays an important role in enhancing its inhibitory effect. Scanning electron microscopy images of crystals grown in the presence of kraft lignins show significant morphological modifications. These are consistent with specific or pseudo specific interactions between the lignin and crystal faces of calcite to inhibit growth parallel to its c axis. The influence over crystal morphology demonstrated by modified kraft lignin increases with increasing ozonization. Also presented here are crystallization temperature data for a range of kraft lignin ultrafiltration fractions, which indicate that the optimal (nominal) molecular weight of kraft lignin for inhibiting the crystallization of CaCO(3) lies between 5000 and 10000.     

Block-copolymer-controlled growth of CaCO3 microrings

A novel way for directed solution growth of hollow superstructures of CaCO3 has been successfully developed on the basis of controlled self-assembly and polymer concentration gradients using a double-hydrophilic block copolymer with a hydrophobic modification as a directing agent. A formation mechanism of such rings is proposed on the basis of the formation of CaCO3 nanoparticles in unstructured block copolymer assemblies with subsequent aggregation of these primary nanoparticles. This leads to the formation of a polymer concentration gradient from the inside to the outside of the particle. As the polymer contains multiple chelating units, this leads to a selective dissolution of the center of the particle.     

孪生球状碳酸钙的直接混合沉淀法制备及表征

以醋酸钙和碳酸钠为原料, 柠檬酸三钠为晶形控制剂, 利用液相直接混合沉淀法合成了分散性好、粒度约1.5~3.0 μm、长短轴比约2∶1的孪生球形碳酸钙晶体. 利用扫描电子显微镜(SEM)、X射线衍射仪(XRD)、傅里叶红外光谱仪(FTIR)、原子力扫描探针显微镜(ASPM)和粒度分析仪等对样品进行了表征. 结果表明, 在不添加柠檬酸三钠的溶液中得到微米级的立方状碳酸钙晶体, 而添加柠檬酸三钠(质量分数30%~40%)后则得到具有不同表面粗糙度的孪生球状碳酸钙晶体. 同时, 用分形生长理论和成核限制聚集(NLA)模型对孪生球状碳酸钙粒子的形成机理进行了分析.     

Evidence of direct crystal growth and presence of hollow microspheres in magnetite particles prepared by oxidation of Fe(OH)2

We provide new information relevant to the crystallinity and growth mechanism of magnetite particles that were fabricated following the method of Sugimoto and Matijevi? [J. Colloid Interface Sci. 74 (1980) 227]. These authors observed that in a small excess of Fe(2+), particles grew by aggregation and recrystallization of smaller units, so that until now the resulting particles were thought to be polycrystalline. With the help of transmission electron microscopy (TEM) and selected area electron diffraction (SAED), we also detected the presence of monocrystalline particles, which are strong evidence of the occurrence of direct crystal growth. This growth mechanism seems to coexist with that of the aggregation of primary units proposed by Sugimoto and Matijevi?. Careful examination of electron microscopy micrographs also revealed the presence of many hollow polycrystalline microspheres.     

Early stages of crystallization of calcium carbonate revealed in picoliter droplets

In this work, we studied the heterogeneous nucleation and growth of CaCO(3) within regular arrays of picoliter droplets created on patterned self-assembled monolayers (SAMs). The SAMs provide well-defined substrates that offer control over CaCO(3) nucleation, and we used these impurity-free droplet arrays to study crystal growth in spatially and chemically controlled, finite-reservoir environments. The results demonstrate a number of remarkable features of precipitation within these confined volumes. CaCO(3) crystallization proceeds significantly more slowly in the droplets than in the bulk, allowing the mechanism of crystallization, which progresses via amorphous calcium carbonate, to be easily observed. In addition, the precipitation reaction terminates at an earlier stage than in the bulk solution, revealing intermediate growth forms. Confinement can therefore be used as a straightforward method for studying the mechanisms of crystallization on a substrate without the requirement for specialized analytical techniques. The results are also of significance to biomineralization processes, where crystallization typically occurs in confinement and in association with organic matrices, and it is envisaged that the method is applicable to many crystallizing systems.     

A systematic examination of the morphogenesis of calcium carbonate in the presence of a double-hydrophilic block copolymer

In this paper, a systematic study of the influence of various experimental parameters on the morphology and size of CaCO3 crystals after room-temperature crystallization from water in the presence of poly(ethylene glycol)-block-poly(methacrylic acid) (PEG-b-PMAA) is presented. The pH of the solution, the block copolymer concentration, and the ratio [polymer]/[CaCO3] turned out to be important parameters for the morphogenesis of CaCO3, whereas a moderate increase of the ionic strength (0.016 M) had no influence. Depending on the experimental conditions, the crystal morphologies can be tuned from calcite rhombohedra via rods, ellipsoids or dumbbells to spheres. A morphology map is presented which allows the prediction of the crystal morphology from a combination of pH, and CaCO3 and polymer concentration. Morphologies reported in literature for the same system but under different crystallization conditions agree well with the predictions from the morphology map. A closer examination of the growth of polycrystalline macroscopic CaCO3 spheres by TEM and time-resolved dynamic light scattering showed that CaCO3 macrocrystals are formed from strings of aggregated amorphous nanoparticles and then recrystallize as dumbbell-shaped or spherical calcite macrocrystal.     

Influence of Block Copolymer on Formation and Acid Resistant Properties of Hybrid CaCO_3 Particles

Block copolymer polystyrene-b-poly(acrylic acid)(PS-b-PAA) was used as structural template for the synthesis of CaCO3 microparticles. Through this procedure, acid resistant hybrid CaCO3 micro-spheres were obtained. Acid resistant properties of this type of hybrid CaCO3 were studied. Size mea-surement shows that the acid resistant properties of the hybrid particles are different in different solutions, such as HCI, EDTA, and H2SO4 solutions.     

Synthesis of size-controlled acid-resistant hybrid calcium carbonate microparticles as templates for fabricating "micelles-enhanced" polyelectrolyte capsules by the LBL technique

Size-controlled, low-dispersed calcium carbonate microparticles were synthesized in the presence of the amphiphilic block copolymer polystyrene-b-poly(acrylic acid) (PS-b-PAA) by modulating the concentration of block copolymer in the reactive system. This type of hybrid microparticles have acid-resistant properties. By investigating the aggregation behaviors of PS-b-PAA micelles by transmission electron microscopy (TEM), the mechanism of hybrid calcium carbonate formation illustrated that the block copolymer served not only as "pseudonuclei" for the growth of calcium carbonate nanocrystals, but also forms the supramicelle congeries, a spherical framework, as templates for calcium carbonate nanocrystal growth into hybrid CaCO(3) particles. Moreover, this pilot study shows that the hybrid microparticle is a novel candidate as a template for fabricating multilayer polyelectrolyte capsules, in which the block copolymer is retained within the capsule interior after core removal under soft conditions. This not only facilitates the encapsulation of special materials, but also provides "micelles-enhanced" polyelectrolyte capsules.     

Interaction between biopolyelectrolytes and sparingly soluble mineral particles

We investigate the complex physicochemical behavior of dispersions containing calcium carbonate (CaCO(3)) particles, a sparingly soluble mineral salt; and carrageenans, negatively charged biopolyelectrolytes containing sulfate groups. We reveal that the carrageenans suspend and stabilize CaCO(3) particles in neutral systems by absorbing on the particle surface which provides electrosteric stabilization. In addition, carrageenans provide a weak apparent yield stress which keeps the particles suspended for several months. The absorption measurements of carrageenan on the CaCO(3) particle indicate that more carrageenan is removed from the solution than expected from the case of a simple monolayer adsorption. Confocal laser scanning microscopy observations confirm that polyelectrolyte-containing precipitate is formed in both CaCO(3)-carrageenan and CaCl(2)-carrageenan mixtures. On the basis of these results, we confirm that in the presence of carrageenan some CaCO(3) dissolves and the Ca(2+) ions interact with the sulfate groups leading to aggregation and formation of particle-like structures. These new insights are important for fundamental understanding of other mineral-polyelectrolyte systems and have important implications for various industrial applications where calcium carbonate is used.     

Properties of amorphous calcium carbonate and the template action of vaterite spheres

The fast mixing of aqueous solutions of calcium chloride and sodium carbonate could immediately result in amorphous calcium carbonate (ACC). Under vigorous stirring, the formed ACC in the precipitation system will dissolve first and, then, transform within minutes to produce crystalline forms of vaterite and calcite. After that, the solution-mediated mechanism dominates the transformation of the thermodynamically unstable vaterite into the thermodynamically stable calcite. Although ACC is the least stable form of the six anhydrous phases of calcium carbonate (CaCO(3)), it could be, however, produced and stabilized by a variety of organisms. To better understand the formation-transformation mechanism of ACC and vaterite into calcite, ex-situ methods (i.e., scanning electron microscopy, Fourier transform infrared spectroscopy, and X-ray diffraction spectroscopy) were used to characterize the formation-transformation process of ACC and vaterite in aqueous systems without organic additives, showing that ACC sampled at different conditions has different properties (i.e., lifetime, morphology, and spectrum characterization). It is also very interesting to capture the obviously polycrystalline particles of CaCO(3) during the transformation process from vaterite to calcite, which suggests the formation mechanism for the calcite superstructure with multidimensional morphology.     

纳米级CaCO_3粒子与弹性体CPE微粒同时增韧PVC的研究

研究了平均粒径为 30nm的超细级纳米CaCO3 与氯化聚乙烯 (CPE)对聚氯乙烯 (PVC)共混体系二元协同增韧效应及机制 .结果表明 ,当共混体系中有一定量的CPE时 ,纳米CaCO3 的加入可以明显地提高共混物的韧性 ,而不降低共混物的强度和刚性 .纳米CaCO3 在PVC基体中达到了纳米级的分散 .当纳米CaCO3 的用量为 8份 (质量 )时 ,PVC CPE 纳米CaCO3 共混物的冲击断面产生了大量的有规则的网丝状结构 ,共混物的缺口冲击强度达到 81 1kJ m2 ,比不加纳米CaCO3 的共混体系高 7 3倍 .CPE的加入对共混体系的加工流动性能无影响 ,纳米CaCO3 的加入使共混体系的加工流动性能变差