聚电解质膜PDAC/PSS诱导CaCO3结晶的研究

以模拟软体动物珍珠层的周期性基质控制形成过程制备仿生层状复合材料．将聚苯乙烯磺酸钠(PSS)与聚二烯二甲基氯化铵(PDAC)用逐层浸渍的方法使其组装成多层膜,用于诱导过饱和溶液中CaCO3的结晶,详细研究了膜紫外吸收随组装层数增加的线性变化．扫描电镜和X射线衍射表征了晶体的形貌和结构,(PDAC/PSS)15PDAC膜诱导获得的CaCO3晶体为六面体结构,晶体尺寸为30～40μm;(PDAC/PSS)15膜诱导CaCO3结晶,可以在膜表面获得形貌与珍珠层非常相似的CaCO3晶体,结晶10h获得的晶片结构呈规则的六边形,片尺寸约为10～20μm,X射线衍射结果表明两种晶体的晶格结构与天然珍珠层差异明显,说明静电作用为晶体形貌的主控因素之一,但不是晶格结构的决定因素．复合材料断面电镜照片表明其为层状结构。     

乙醇/水混合溶剂体系中碳酸钙晶体晶型和取向的控制

采用（NH₄）₂CO₃分解法,制备得到了晶型和形貌可控的CaCO₃晶体。研究结果表明,乙醇/水混合溶剂、陈化时间和L-半胱氨酸自组装单层模板对CaCO₃晶体的晶型、取向和形貌都具有重要影响。无单层模板情况下,溶液中主要得到了球霰石,球霰石的形貌随陈化时间从花朵外形变为树叶形。同样的醇/水体系中,在自组装单层上却得到了取向为（104）晶面的方解石。这与水溶液中同一自组装单层上主要获得（001）结晶面的方解石有明显不同。方解石的形貌也随陈化时间变化而改变。陈化时间为3h时,得到具有孔洞结构的方解石;陈化时间为12h时,得到表面光滑的菱面体方解石。     

CaCO3纳米微粒的层状液晶模板法制备及其生长过程中的形貌演变

在Triton X-100/n-C₁₀H₂₁OH/H₂O体系中，低角X射线衍射测试表明层状液晶的溶剂层厚度小于3 nm。利用层状液晶为模板制备了CaCO₃纳米微粒，并用透射电子显微镜(TEM)、X射线衍射(XRD)和选区电子衍射(SAED)进行了表征。TEM结果表明所得CaCO₃纳米粒子的形貌为球形，粒径在2～8 nm，分布较窄。XRD表明CaCO₃纳米微粒的物相为方解石型和球霰石型混合结构。在制备过程中，Ca(OH)₂的加入和CaCO₃纳米微粒的析出并未破坏层状液晶的对称性和长程有序性。此外，在Triton X-100/CH₃CH₂OH体系中，研究了CaCO₃纳米微粒的生长行为，发现小的纳米微粒先通过导向聚集生长成小的梭状物，然后小的梭状物继续生长，最后发生Ostwald陈化形成较为均一的两头尖的带状纳米结构，其宽度在50～200 nm，长度约为2 μm。     

PAMAM树形分子对CaCO3结晶影响的研究

研究了不同端基的聚酰胺胺(PAMAM)树形分子对CaCO₃在水溶液中结晶的影响。分别利用傅立叶变换红外光谱(FTIR)、X-射线衍射(XRD)、扫描电镜(SEM)等测试手段对样品进行了分析。结果表明:没有树形分子存在时CaCO₃是粒径为10μm的菱形方解石晶体;端基为-COONa的树形分子存在时CaCO₃则是粒径为1～2μm的球形球霰石晶体;-COOCH₃端基PAMAM树形分子存在时得到的CaCO_{3相似文献}   

纳米CaCO3微晶的晶格畸变和反常红外特性

利用TEM、SEM、X射线衍射(XRD)和Voigt函数单峰分析法讨论了纳米CaCO₃微晶结构,解释了纳米CaCO₃微晶的反常红外吸收特性,并认为微结构中的尺寸效应使得纳米CaCO₃晶格中存在较大的畸变应力,从而引起了碳酸钙微晶的红外ν₃吸收峰有约40 cm^-1的蓝移和明显窄化。     

CO2鼓泡法可控制备单层中空CaCO3微球:染料负载及细胞生物成像

在L-蛋氨酸（L-Met）的导向下,可控制备了一种单层中空CaCO₃微球。考察了L-Met的加入量、CO₂流速和反应温度等重要参数对CaCO₃形貌、尺度和晶相的影响。作为一种客体分子载体,该单层中空CaCO₃微球可负载罗丹明B（RhB）,得到一种发光复合材料（RhB@hollow-CaCO₃）。RhB@hollow-CaCO₃）对A-549肺癌细胞（A549 LCCs）和HO8910人卵巢癌细胞（HO8910 OCCs）表现出良好的生物相容性。     

花瓣状微球MoS2/石墨烯复合材料的制备及其电化学性能

采用有利于二维层状结构形成的L-半胱氨酸作为硫源,钼酸钠作为钼源,制备聚乙烯基吡咯烷酮（PVP）辅助水热合成花瓣状微球形貌的MoS₂/还原氧化石墨烯复合电极材料（PVP-MoS₂/RGO）. X射线衍射（XRD）及透射电子显微镜（TEM）证实,经过PVP的适量添加,MoS₂有序堆垛结构的片层数目明显减少. 扫描电子显微镜（SEM）显示,添加适量PVP的MoS₂/石墨烯材料具有分散性更好的花瓣状微球形貌. 上述的少层有序堆垛结构及复合材料的良好分散性缩短了MoS₂中锂离子的嵌入/脱出路径,使其具有更高的容量、循环稳定性和倍率性能.     

超支化双亲水性嵌段共聚物对CaCO3结晶影响的研究

采用合成的聚乙二醇-超支化聚酯(PEG-hb-DMPA)的线性-超支化杂化二嵌段共聚物, 探讨了羧端基树状功能化的杂化嵌段共聚物对CaCO₃结晶的影响，并用FTIR、XRD、SEM等对产物进行了表征。结果表明，羧端基的双亲水性嵌段共聚物对CaCO₃结晶形貌乃至晶型均具有显著调控作用，比较高的浓度(1.67 g·L^-1, >10 min)或较低浓度作用较长时间(0.33 g·L^-1, 24 h)均得到了呈较均匀球粒形态的球霰石CaCO₃结晶。     

从P-Mo(Ⅴ)杂多化合物合成多形貌Al13基钼酸盐晶体

以H₃PMo₁₂O₄0·nH₂O、H₄PMo₁₁VO₄₀·nH₂O和(NH₄)₆P₂Mo₁₈O₆₂·nH₂O 3种杂多化合物为钼源，采用直接混合后陈化的方法合成了多形貌Al₁₃基钼酸盐晶体，相应Al₁₃基钼酸盐晶体的形貌和尺寸分别是斜方三棱柱形(80 μm × 30 μm)、星形(30 μm × 10 μm)和叶片形(500 μm × 150 μm)。粉末X射线衍射结果表明这3种多形貌Al₁₃基钼酸盐晶体结晶较好，在2θ为6.65°、8.00°和14.16°处都有强而尖锐的衍射峰。而以Na₂MoO₄·2H₂O为钼源时只能制得无定形簇合物。根据ICP、FTIR和TG/DTG结果给出多形貌的Al₁₃基钼酸盐晶体的化学简式为Na[AlO₄Al₁₂(OH)₂₄(H₂O)₁₂][MoO₄]₄·8H₂O。初步探讨了Al₁₃基钼酸盐晶体的形成机理。     

纳米CaCO3的改性、表面结构与流变行为研究

采用铝锆偶联剂和棕榈酸改性纳米CaCO₃ 粉体. 借助 XRD, FTIR, 接触角及流变学等测试方法对纳米CaCO₃ 的表面结构进行表征. XRD 分析表明: 改性纳米 CaCO₃保持原样品完整的体相结构, 为方解石型纳米微晶. FTIR 分析证明: 表面改性剂与纳米 CaCO₃ 表面是以化学键合和物理吸附方式相结合, 粒子表面存在羧基等有机官能团的红外吸收特征. 通过测定苯和水在改性纳米CaCO₃粉末压片上的接触角, 计算了改性纳米 CaCO₃的表面能和极性分量, 并与未改性纳米CaCO₃ 进行比较. 结果表明, 经表面改性, 纳米 CaCO₃ 的表面能和极性分量明显降低, 其在有机溶液中的吸附功增大, 界面张力大大降低; 经棕榈酸改性的纳米 CaCO₃ 表现出较好的亲油疏水性, 而铝锆偶联剂改性的纳米 CaCO₃ 同时具有亲水性和亲油性. 以液体石蜡为溶剂, 研究了表面改性对纳米CaCO₃悬浮液流变行为的影响. 实验发现: 经过表面处理, 纳米 CaCO₃ 粉体悬浮液流变行为发生较大的变化, 稳态剪切黏度大大降低, 表现出较小的动态弹性储能模量和黏性损耗模量, 而损耗因子较大.     

珍珠质基底上CaCO3晶体的仿生生长研究

珍珠质是一种典型的有机，无机层状复合材料．其中95％以上是文石（CaCO3的一种晶型1小板片，填充在板片之间的薄层有机基质仅占1％-5％。这种精细的组织结构不仅使珍珠质具有绚丽的光泽。还赋予珍珠质超乎寻常的强度和韧性（为合成CaCO3晶体的3000多倍）。虽然在珍珠质中有机质的含量不足5％．然而正是这些有机质对珍珠质的结构、性能、晶体取向等起着至关重要的调控作用。     

Influence of surfactants on the morphologies of CaCO3 by carbonation route with compressed CO2

Three surfactants, sodium dodecyl sulfate (SDS), cetyltrimethylammonium bromide (CTAB) and polyoxyethylene-80-sorbitan monooleate (Tween 80), were used to control the growth of CaCO₃ crystals by carbonation route using Ca(OH)₂ and compressed CO₂. The obtained CaCO₃ particles were characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD) techniques. The effects of surfactants on the morphology of the particles were studied. It was demonstrated that Tween 80 and SDS have obvious effect on the morphology of CaCO₃ particles, while CTAB does not affect morphology considerably. The possible mechanism has been discussed on the basis of the binding of the surfactants to the certain face of the crystals.     

Morphology and Kinetics of Growth of CaCO<Subscript>3</Subscript> Precipitates Formed in Saline Water at 30°C

The crystallization kinetics and morphology of CaCO₃ crystals precipitated from the high salinity oilfield water were studied. The crystallization kinetics measurements show that nucleation and nuclei growth obey the first order reaction kinetics. The induction period of precipitation is extended in the high salinity solutions. Morphological studies show that impurity ions remain mostly in the solution phase instead of filling the CaCO₃ crystal lattice. The morphology of CaCO₃ precipitates can be changed from a smooth surface (calcite) to rough spheres (vaterite), and spindle rod bundles, or spherical, ellipsoid, flowers, plates and other shapes (aragonite).     

Synthesis and characterization of sulfonated polymethylsiloxane polymer as template for crystal growth of CaCO3

The objective of this work was to synthesize a sulfonated polymethylsiloxane (S-PMS) by hydrosilylation and sulfonation reactions and to investigate their effect on the growth of CaCO₃ crystals using a gas diffusion method as a function of concentration, pH, and time. The result of IR and NMR shows good agreement with all proposed structures. Scanning electron microscopy images of CaCO₃ showed small well-defined calcite-forming short piles (ca 5 μm) and elongated calcite (ca 20 μm) crystals. The morphology of the resultant CaCO₃ crystals reflects the electrostatic interaction of sulfonate moieties and Ca²⁺ modulated by S-PMS adsorbed onto the CaCO₃ surface. X-ray diffraction confirmed the crystalline calcite polymorph. Energy dispersive spectroscopy of CaCO₃ crystals determined the presence of Si atoms from S-PMS. The use of PMS chemistry as an organic additive for the production of CaCO₃ particles is a viable approach for studying the biomineralization and could be useful for the design of novel materials with desirable shape and properties.     

St / AA共聚物的组成对碳酸钙结晶及形貌影响的研究

在聚苯乙烯-丙烯酸两亲共聚物(简称PAS)溶液中制备CaCO₃，用XRD、FTIR和SEM等研究随着PAS的亲水AA和亲油St单元组成的变化所引起的聚合物分子链段、溶解性质和胶束空间构象等的改变对CaCO₃晶型和形貌的影响。结果显示：随着亲水性AA单元组成的提高，可以由AA链段的晶面匹配成核调控碳酸钙为方解石纳米晶，并因PAS在水溶液中溶解性不同，形成了多种碳酸钙形貌的聚集体；当St和AA的物质的量比为3∶1时，合成出类珍珠岩层碳酸钙结构。根据PAS的结构性质和在水溶液中的溶解行为初步探讨了类珍珠岩层碳酸钙的形成机理，认为是PAS基质模板和羧酸根对钙的键合作用形成这一特殊形貌碳酸钙。     

Polyepoxysuccinic acid with hyper-branched structure as an environmentally friendly scale inhibitor and its scale inhibition mechanism

In order to improve the scale inhibition efficiency of existing polyepoxysuccinic acid (PESA) and to study the impact of their molecular structure on scale inhibition efficiency, a series of PESA with linear and hyper-branched structure have been designed and synthesized through co-polymerization reaction with glycidyl and epoxy succinate. The scale inhibition behavior of PESA with linear and hyper-branched structure against CaCO₃ and CaSO₄ scales was evaluated using static scale inhibition method, and their ability to retard deposition of CaCO₃ was also examined. The experimental results showed that, for CaCO₃ and CaSO₄, the PESA with hyper-branched structure provides a scale inhibiting efficiency as high as 95.9% and 94.3%, respectively, at an inhibitor concentration of 15?mg/L. In addition, the processes of crystal nucleation, growth and crystal morphology have been analyzed. The experimental results show that the PESA with hyper-branched structure not only prolongs the induction period of CaCO₃ crystal nucleation, but also reduces the number of crystal nuclei and changes the size and morphology of the CaCO₃ crystal. Moreover, the FTIR, SEM and XRD analyses showed that the PESA with hyper-branched structure can induce the irregularity of growing CaCO₃ crystal, destroy the formation of crystals and change the polymorphs of calcium scale crystal. This conclusion indicates that the prepared PESA with hyper-branched structure has great potential for applying in the treatment of industrial water.     

Superparamagnetic Composites Based on Ionic Resin Beads/CaCO3/Magnetite

The preparation of superparamagnetic composites obtained by CaCO₃ mineralization from supersaturate aqueous solutions is presented. The preparation was conducted in the presence of oleic acid stabilized magnetite nanoparticles as a water‐based magnetic fluid and insoluble templates as gel‐like cross‐linked polymeric beads. The presence of the magnetic particles in the composites provides a facile way for external manipulation using a permanent magnet, thus allowing the separation and extraction of magnetically modified materials. Two ion exchangers based on divinylbenzene/ethyl acrylate/acrylonitrile cross‐linked copolymer—a cation ion exchanger (CIE) and an amphoteric ion exchanger (AIE)—were used, as well as different addition orders of magnetite and CaCO₃ crystals growth precursors. The morphology of the composites was investigated by SEM, the polymorphs content by X‐ray diffraction, and the thermal stability by thermogravimetric analysis. Polymer, CaCO₃, and magnetite in the composite particles were shown to be present by energy dispersive X‐ray (EDX), XPS, and TEM. The sorption capacity for Cu^II ions was tested, as compared to samples prepared without magnetite.     

Biomimetic growth of CaCO3 pancakes on the leaves of Epipremnum aureum

Rhombohedral, disk-like and pancake-like calcite crystals were synthesized in the different reaction condition via facial vegetal bio-templates, the leaves of Epipremnum aureum. The resultant crystals were characterized by scanning electron microscopy (SEM), X-ray powder diffractometry (XRD), and Fourier transform infrared (FT-IR) spectroscopy. The results showed that disk-like and pancakes calcite were obtained on the surface of Epipremnum aureum leaves in 50 mM CaCl₂ solution at starting pH values of 9.7 and 11.7, respectively. The dynamic process of formation of multiple crystals was analyzed by monitoring the continuous morphological and structural evolution and components of crystals in different crystal stages. Moreover, it is found that the surface structure of the leave and starting pH value of reaction solution provide profound influence on the morphology of CaCO₃ crystals. This provides a facile and novel method to prepare hierarchical CaCO₃ crystals.     

Preparation of azo polyelectrolyte self-assembled multilayers by using N,N-dimethylformamide/H2O mixtures as solvents

N,N-Dimethylformamide (DMF)/H₂O mixtures were used as solvents to fabricate azo polyelectrolyte (PEAPH)/poly(diallyldimethyl ammonium chloride)(PDAC) self-assembled multilayers with the layer-by-layer electrostatic adsorption technique. PEAPH is a copolymer of acrylic acid and azobenzene-containing acrylate. The effect of the ratio of DMF to water on the multilayer growth, structure and surface morphology was studied in some details. Results show that DMF/H₂O mixtures are proper media for PEAPH/PDAC multilayer fabrication. The ratio of DMF to water in the mixture has significant influence on the multilayer structure and surface morphology. With the increase of DMF content, the multilayer thickness has a better linear growth relationship with the bilayer number, and the multilayer surface becomes smoother. Moreover, azo chromophores show less H-aggregation when the multilayers are fabricated from DMF/H₂O mixtures with higher DMF contents. These studies demonstrate that using organic solvent and water mixtures is an effective way to control the multilayer construction by adjusting the media properties. This method can be applied to multilayer fabrication of other water-insoluble polyelectrolytes. __________ Translated from Acta Polymerica Sinica, 2005, (4) (in Chinese)     

Preparation of porous CaCO3/PAM composites by CO2 in water emulsion templating method

Emulsion templating is an effective method to prepare well-defined porous polymeric materials. In this paper, porous CaCO₃/polyacrylamide (PAM) composites were prepared by emulsion templating polymerization in supercritical CO₂(scCO₂) by using a commercial grade surfactant (FC4430), therefore, the amount of the fillers and the pore size distribution of the composites can be modulated based on the demands of those potential applications as biomaterials. Calcium carbonate crystals can be in situ synthesized in the porous PAM matrix, and the morphology of CaCO₃ varied with the conditions of the reaction, the results indicated that three kinds of crystals were observed in the porous matrix. The results of scanning electron microscopy (SEM) and mercury intrusion porosimetry (MIP) showed that the macropores in PAM were interconnected and with narrow pore size distributions.