枝状文石型碳酸钙的仿生合成及在PVC中的应用

利用生物矿化原理,以聚丙烯酸(PAA)为有机基质,采用碳化法合成了具有枝状形貌的文石型碳酸钙粒子.通过场发射扫描电镜(FESEM)、X射线衍射仪(XRD)和傅里叶变换红外光谱仪(FTIR)等检测手段研究了产物的结构和形貌,并初步探讨了粒子的生长机理.结果表明,在文石型碳酸钙粒子的合成中,有机基质和反应温度是非常重要的参数.同时将该产品填充于聚氯乙烯(PVC)中,测定了PVC塑料的力学性能和加工性能.     

水溶液中P123对CaCO3微粒形貌的调控

在三嵌段共聚物P123水溶液体系中,合成了特殊形貌的层面光滑的碳酸钙层状聚集体、具有多级结构的碳酸钙层状聚集体和仙人球状的碳酸钙粒子.探讨了反应时间、聚合物浓度和反应温度对碳酸钙粒子形貌和晶型的影响,采用扫描电子显微镜(SEM)、X射线粉末衍射(XRD)及红外吸收光谱对合成样品的形貌、结构进行了表征.结果表明,聚合物浓度和反应温度对碳酸钙粒子形貌和晶型具有重要的影响.利用周期键链(PBC)理论模型解释了层状结构碳酸钙聚集体的形成过程.     

天冬氨酸调控糖果状碳酸钙的仿生合成及性能

利用仿生合成原理,选取天冬氨酸作为诱导剂,采用沉淀反应法制备出糖果状球霰石型碳酸钙粒子,并对其结构和性能进行了表征.考察了反应温度、诱导剂用量和反应时间等对碳酸钙粒子晶型和形貌的影响，探讨了其反应原理.结果表明,所得碳酸钙粒子荧光性增强.此方法对碳酸钙的仿生合成与改性研究具有一定的指导意义.     

鲫鱼牙齿提取液对碳酸钙晶型和形貌的影响

25℃下,在鲫鱼牙齿提取液存在时,用Na_2CO_3和Ca(NO_3)_2·4H_2O作为原料合成碳酸钙,研究提取液的浓度和反应时间对产物组成和粒子形貌的影响。用粉末X-射线衍射仪(XRD)和红外光谱仪(FT-IR)对合成的产品进行了表征,用扫描电子显微镜(SEM)观察了粒子的形貌。研究结果显示,在反应时间是30s时,合成得到的产物是球霰石晶型和方解石晶型的混合物,并且随着提取液浓度的增加,球霰石所占比例呈现增加趋势;随着反应时间的增加,球霰石的含量会降低,但是产物粒子的形貌没有明显变化。结果说明,提取液的确能够影响碳酸钙的晶型和粒子形貌。     

多肽Langmuir膜控制下方解石晶体的生长

本文研究了聚β-苯甲基天门冬氨酸(PBA)Langmuir膜对碳酸钙成核和生长的诱导控制作用。在PBA Langmuir单分子膜作用下,我们得到形状规则、边缘清晰的花瓣状碳酸钙晶体。XRD分析表明所得碳酸钙晶体为沿(104)和(208)晶面取向生长的方解石晶型;AFM、TEM和SEM观察显示了方解石形貌的变化过程。结果表明多肽PBA Langmuir单分子膜对碳酸钙的结晶、生长取向和形貌具有良好的诱导和调控作用。     

巢状微结构银粒子的制备、形成机理及表面增强拉曼光谱研究

通过选择沉积电位、温度、电解液浓度等条件,调控银粒子的成核和生长速度,调控晶面的择优取向,诱导枝状生长,从而制得巢状微结构银粒子,并对其生长机理进行了研究.采用扫描电子显微镜(SEM)和X射线衍射光谱(XRD)对巢状微结构银粒子形貌和结构进行表征.以罗丹明6G为探针分子,研究了巢状微结构银粒子的表面增强拉曼光谱(SERS),并与无孔银粒子对照.结果表明:巢状微结构银粒子的SERS较无孔银粒子有明显增强,拉曼增强因子达到1.7×106.     

2,2’-联苯二酸和温度对CaCO_3晶型的影响

分别在90℃和120℃下,用2,2’-联苯二酸(bpdca)作为调控剂合成了具有不同晶型和形状Ca CO3晶体,研究羧酸浓度和温度对Ca CO3晶型和形貌的影响。用粉末衍射XRD、FT-IR表征了合成的产物,用扫描电子显微镜(SEM)观察研究了产物粒子的形状,调查研究了温度和bpdca浓度对Ca CO3粒子形貌和晶型的影响。结果表明,bpdca和温度均会对Ca CO3的晶型和形状有影响。     

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,...     

荧光碳点对生物体液中姜黄素的检测及细胞成像

本文以廉价易得的橘皮和柠檬酸为原料，通过一步水热法合成荧光碳点(CDs)。对CDs的形貌、结构、元素组成和光学性能等进行了表征，考察了离子强度、光稳定性和储存时间对CDs的影响。所合成CDs为粒径约为4 nm的类球形结构，具有较好的稳定性。通过对CDs与姜黄素(CM)检测体系的选择性实验，发现常见的离子及氨基酸对CM的检测几乎无影响。基于CM对CDs选择性荧光猝灭的现象，构建了检测姜黄素的荧光探针。在最佳实验条件下，该探针对CM检测的线性范围为5～40μmol/L,检出限为9.7 nmol/L。探讨了CDs和CM作用机理，发现其主要是静态猝灭。该CDs应用于健康人体体液(血液、尿液)中微量CM的测定，其加标回收率为104.0%～115.0%。橘皮合成碳点可用于A549细胞进行成像，并表现出低细胞毒性。实验结果表明，该CDs在CM的分析检测以及细胞成像中具有较好的应用价值。     

醇-水混合溶剂中双亲水嵌段共聚物对CaCO3粒子形貌的调控

合成形态、大小及结构受到人为调控的无机材料是现代材料科学的一个重要研究方向, 通过生物模拟方法可望实现各类有机添加剂及模板对无机物形貌与结构的有效调控[1,2]. 近年来, 一类新型的无机晶体生长调控剂--双亲水嵌段共聚物[3]已成功地用于多种无机粒子形貌的有效调控. 双亲水嵌段共聚物由2个与无机表面亲和作用不同的亲水链段构成, 在其水溶液中, 已实现了具有一系列特殊形貌的碳酸钙[4~6]、磷酸钙[7]及硫酸钡[8]粒子的生物模拟合成. 人们已陆续报道了在多种有机添加剂及模板作用下典型的生物矿物CaCO3的生物模拟合成[9,10]. 我们曾系统地研究了水溶液中双亲水嵌段共聚物对CaCO3粒子形貌的调控作用[6],最近又在双亲水嵌段共聚物-表面活性剂混合溶液中合成出具有新颖形貌(如空壳状等)的CaCO3粒子[11]. 本文考察了醇-水混合溶剂中双亲水嵌段共聚物对CaCO3粒子形貌的调控作用, 初步揭示了溶剂特性对该调控作用的显著影响.     

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.     

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。     

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.     

Preparation of poly(methyl methacrylate)/CaCO3/SiO2 composite particles via emulsion polymerization

A novel method to prepare organic/inorganic composite particles, i.e. poly(methyl methacrylate)/CaCO₃/SiO₂ three-component composite particles, using emulsion polymerization of methyl methacrylate with sodium lauryl sulfate as a surfactant in an aqueous medium was reported. CaCO₃/SiO₂ two-component inorganic composite particles were obtained firstly by the reaction between Na₂CO₃ and CaCl₂ in porous silica (submicrometer size) aqueous sol and the specific surface area of the particles was measured by the Brunauer–Emmett–Teller (BET) method. The results show that the BET specific surface area of the CaCO₃/SiO₂ composite particle is much smaller than that of the silica particle, indicating that CaCO₃ particles were adsorbed by porous silica and that two-component inorganic composite particles were formed. Before copolymerization with methyl methacrylate, the inorganic composite particles were coated with a modifying agent through covalent attachment. The chemical structures of the poly(methyl methacrylate)/CaCO₃/SiO₂ composite particles obtained were characterized by Fourier transform IR spectroscopy and thermogravimetric analysis. The results show that the surface of the modified inorganic particles is grafted by the methyl methacrylate molecules and that the grafting percentage is about 15.2%.     

Role of Polyelectrolytes in Crystallogenesis of Calcium Carbonate

The effects anionic polyelectrolytes, having various molecular weights and repeating unit structures, on the crystallization of calcium carbonate in supersaturated solutions are studied. The induction times of the crystals grown in the presence of the polymers were optically evaluated; X-ray diffraction and Scanning Electronic Microscopy (SEM) analyses were performed to determine, respectively, their crystalline structures and morphologies. The polyelectrolyte is found to lengthen the induction time and to reduce the size of CaCO₃ nanocrystallites, to an extent depending on the interaction efficiency between the polymer anionic repeating units and the calcium ions. Further, depending on their sizes and their crystalline structures (calcite, vaterite) the nanocrystallites aggregate and yield final calcium carbonate particles having various sizes and morphologies. The data indicate that nanocrystals having vaterite structure, as determined by X-ray analysis, give spherical CaCO₃ final particles, while nanocrystals having calcite structure lead to either acicular or flower shapes of CaCO₃ final particles.     

Study on CaCO3/PMMA nanocomposite microspheres by soapless emulsion polymerization

A soapless emulsion polymerization method was applied to synthesize CaCO₃/PMMA spherical composite with different loading of CaCO₃. CaCO₃ nanoparticles were pretreated with oleic acid after the carbonation process of Ca(OH)₂ slurry by CO₂, in order to improve the compatibility between the CaCO₃ particles and MMA monomer in emulsion system. The results of photon correlation spectroscopy (PCS) showed the particles size of composites were bigger than the pure PMMA. And the size increased with the increase of the content of CaCO₃ nanoparticles. TEM images showed that the morphology of the composite microspheres was uniform and CaCO₃ nanoparticles can be well encapsulated in the polymeric microsphere, and were located at the edge of the spheres. The results of DTG and TG indicated that the CaCO₃ nanoparticles could improve the thermal stability of PMMA. Moreover, capsulation of CaCO₃ by PMMA can increase the acid-resistant of CaCO₃ nanofillers.     

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.     

Synthesis and characterization of well-defined poly(methyl methacrylate)/CaCO3/SiO2 three-component composite particles via reverse atom transfer radical polymerization

The attempt to prepare structurally well-defined polymer/inorganic composite particles, i.e., poly(methyl methacrylate) (PMMA)/CaCO₃/SiO₂ three-component composite particles, via reverse atom transfer radical polymerization (ATRP), using 2-2′-azo-bis-isobutyronitrile as initiator and Cu(II) bromide as catalyst was reported. CaCO₃/SiO₂ two-component composite particles were first obtained through sol–gel method, and their morphology and surface element information were determined by transmission electron microscopy and X-ray photoelectron spectroscopy, respectively. The results indicate that the CaCO₃ was encapsulated by the obtained SiO₂. After being modified by silane coupling agent, the CaCO₃/SiO₂ composite particles copolymerized with methyl methacrylate (MMA) under standard reverse ATRP conditions to produce PMMA/CaCO₃/SiO₂ three-component composite particles. In the case concerned, first-order kinetic plots and linear increase of molecular weight (Mn) vs conversion and narrow molecular weight distribution for the graft polymer samples were observed. Furthermore, the gel permeation chromatography results illustrated that both the free PMMA chains from the solvent and the graft PMMA chains from the surface of CaCO₃/SiO₂ two-component composite particles were growing at the same rate. Characterizations of the PMMA-grafted CaCO₃/SiO₂ composite particles were done by Fourier transform infrared and thermogravimetric analysis. The results showed that the surface of the modified inorganic particles was grafted by the MMA and that the grafting percentage was about 8.7%.     

Surface modification of CaCO3 filler and its characterization using inverse gas chromatography (IGC)

A CaCO₃ filler was treated by generally used coupling agents and a special one — ethylene-octene copolymer (POE)-g-maleic anhydride (MAH). Fourier transform infrared spectroscopy (FTIR) results show that the special coupling agent POE-g-MAH, in a chemical reaction with CaCO₃, can produce an interfacial layer stronger than simple physical adhesion attained with usual coupling agents. Inverse gas chromatography (IGC) was used to investigate the surface free energy of CaCO₃ after surface modification and to optimize the monolayer content of coupling agents. Based on the IGC results, it can be deduced that the monolayer cover is around 1.9% for CaCO₃ treated with a titanate coupling agent. Scanning electron microscope (SEM) observation results show that the separated morphology existed in the ternary composites containing CaCO₃ after surface treatment with coupling agents, whereas the core-shell morphology was obtained in the ternary composites with POE-g-MAH. The encapsulation of the CaCO₃ filler treated with POE-g-MAH was caused by the strong chemical reaction between the elastomer and CaCO₃ particles. __________ Translated from Journal of Northwestern Polytechnical University, 2007, 25(2): 274–278 [译自: 西北工业大学学报]     

Use of Taguchi approach for synthesis of calcite particles from calcium carbide slag for CO2 fixation by accelerated mineral carbonation

This study is focused on the conversion of harmful materials (calcium carbide slag [CCS] and flue gas) into CaCO₃ particles through an accelerated mineral carbonation process. The influences of reaction temperature, amount of Na-oleate, solid-to-liquid ratio, and stirring speed on the properties of CaCO₃ particles were determined using XRF, XRD, SEM, FTIR, TG, and contact angle measurements. Experiments were designed based on an orthogonal array L9 (3⁴) of the Taguchi approach. The gas mixture of CO₂/N₂ (16.3% of CO₂ cons.) gas was used to represent the flue gas for each experiment. The formation of CaCO₃ particles from CCS depending on time was monitored via SEM. Experiments showed that the presence of Na-oleate in the slurry played a curial role in the carbonation process, and the conversion ratio of CO₂ into a solid carbonate phase was higher than that in the experiments conducted without Na-oleate. The crystallite size of CaCO₃ particles varied between 11.55 and 38.11 nm depending on the production conditions. Each obtained CaCO₃ particles were identified as calcite (cubic-like rhombohedral), which is in high demand in many industrial applications.