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。     

胆固醇对卵磷脂有序体中生成CaCO3晶型的影响

报道了在卵磷脂、胆固醇、橄榄油、电解质溶液组成的分子有序组合体中,胆固醇的加入影响了有序体的膜结构、表面特性,从而也影响到有序体微环境中所生成的CaCO₃晶体结构。随着胆固醇含量增加,在一定范围内球霰石的相对含量增大;油包水体系中生成的球霰石相对含量远大于水包油体系中生成的球霰石相对含量。     

溶剂和溶液酸碱性对碳酸钙晶型和形状影响研究

<正>CaCO3主要有三种晶型:方解石,文石和球霰石[1-3],方解石是CaCO3晶体最稳定的晶型,球霰石是最不稳定的,文石的稳定性介于两者之间。在生物矿物中经常发现有文石和方解石的存在,具有结构功能和光学等性能[4],是生物体硬组织中的主要无机成份之一。在珍珠、贝壳、甲壳、动物骨骼等生物组织中CaCO3与少量有机基质(生物大分子)结合,形成具有特定性质的有机/无机杂化材料[5],例如,方解石存在于骨头,牙齿等硬组织中,另外还具有在神经束中的光聚焦功能;     

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,...     

六偏磷酸钠对碳酸钙矿化的影响

常温下,在CaCl2与NaCO3反应体系中加入一定量的六偏磷酸钠调控合成CaCO3晶体,用粉末XRD衍射仪、FT-IR对合成的晶体进行了表征,用扫描电子显微镜观察分析了生成的CaCO3晶体的形貌,研究了六偏磷酸钠浓度对CaCO3晶型和形状的影响。研究表明:在水体系中,CaCl2与NaCO3反应生成CaCO3晶体,当加入六偏磷酸钠的量小于50mg时,得到的是纯的方解石晶型,当加入六偏磷酸钠的量大于80mg时,得到的是方解石和球霰石的混合体,随着六偏磷酸钠量的增加,生成的球霰石晶体增多,实验结果说明六偏磷酸钠对球霰石晶体有一定的稳定作用。     

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。     

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12 h时,得到表面光滑的菱面体方解石。     

方解石碳酸钙形成过程和热力学性质的研究

将CaCl₂ 和Na₂CO₃水溶液在强烈搅拌下快速混合，制备了碳酸钙。应用SEM 、FT-IR和XRD对所制备的样品进行了表征。结果表明，在反应10 s后生成了稳定的方解石型和不稳定的球霰石型碳酸钙。随着反应时间的进行，样品颗粒增大，球霰石逐渐转化为方解石。在反应180min，样品全部转化为方解石。用全自动绝热量热计测试了制备的方解石在80 至 390 K温区的等压摩尔热容。建立了其等压摩尔热容与温度的定量关系。根据热力学函数关系式，计算了方解石样品的焓、熵和吉布斯自由能。     

表面活性剂存在条件下脲醛树脂微球的合成反应过程

考察了酸性和不同表面活性剂存在条件下脲醛树脂微球的合成反应过程.中性Tween80和阳离子CTAB表面活性剂中生成的微球粒径分布窄,而阴离子表面活性剂中所得产物明显团聚,当预聚脲醛树脂粒子生成后加入中性和阳离子表面活性剂使产物微球的分散性和球形完整性明显改善.表面活性剂存在条件下产物的结晶性增强,初始反应的速率减慢,但中性和阳离子表面活性剂中初级粒子生成的诱导期延长、拉曼吸收增强、所得微球带正电荷;而阴离子条件下生成产物的相应特征正好相反.以上结果可以用表面活性剂的两亲性和电性对脲醛树脂微球的成核和生长过程的影响来解释.     

卵磷脂-水有序结构对CaCO3晶型的影响

Influence of the concentration of phosphatidylcholine (PC) in the solution of 0.5mol?L-1 CaCl2 on the crystal structure of CaCO3 has been studied by means of X-ray diffraction method. When the concentration of PC is below its CMC, the calcite CaCO3 is formed. It advantageous that CaCl2 reacts with Na2CO3 so as to form vaterite CaCO3 in the lipesome composed of PC more than in the water. The arnount of vaterite CaCO3 formed is increased with increase of concentration of PC. But if the concentration of PC is so increased as to form liquid crystal, then the amount of vaterite decreases obviously. The reason for the difference of crystal type formed has been discussed in the paper.     

Preparation of CaCO_3 Hollow Spheres in an Aqueous Binary-additive System

CaCO3 hollow spheres were prepared easily in anion surfactants （sodium dodecylbenzenesulfonate （SDBS）） and aspartic （Asp） acid binary-additive system by using an easy rapid agitation method. The as-prepared products were characterized with scanning electron microscopy （SEM）, FT-IR and X-ray diffraction. The results suggested that the CaCO3 hollow spheres have diameters ranging from 1 to 2 μm, and their wall is constituted of many nano-particles. Moreover, the possible formation mechanism of the hollow spherical structure was proposed.     

Na_5P_3O_(10)-Ca(OH)_2-CO_2-H_2O体系纳米CaCO_3的成核与生长

通过化学分析、SEM显微分析技术结合RosinRamiler概率统计理论从介观层次研究Na5P3O10CaOH2CO2H2O体系纳米CaCO3的合成反应及其成核和生长过程。结果表明Na5P3O10对CaOH2的碳化反应具有抑制作用。随着Na5P3O10的增加体系中CaCO3的成核速率B0逐渐增大。在Na5P3O10=0ppm时CaCO3结晶的生长由长程扩散和凝聚生长控制Na5P3O10=380.4760.9ppm时前期受短程扩散和界面反应控制、后期受长程扩散控制。Na5P3O10的存在抑制了纳米CaCO3的晶体生长。     

用PAANa掺杂的纳米CaCO_3的合成及其产品表征

在反应物经超声波预处理和聚丙烯酸钠PAANa分散剂的掺杂下运用化学沉淀方法制备出窄粒径纳米碳酸钙。将所获纳米粒子运用现代分析测试手段进行结构、晶形、组成等的表征。结果表明纳米级超细碳酸钙在红外区有蓝移40cm-1和峰形窄化现象纳米粒子的高表面能及CO32-存在的共轭体系CaO键的相互作用以及表面配位的不饱和性和晶体生长的人为终止是存在表面效应的主要原因。     

Biomimetic Nucleation and Morphology Control of CaCO_3 in PAAm Hydrogels Synthesized from Lyotropic Liquid Crystalline Templates

Hydrogels have been thought to be the material which can provide appealing replacements of biological organisms. Pores of hydrogels synthesized from lyotropic liquid crystalline (LLC) templates were smaller in size and more uniform than those of traditional hydrogels. LLC poly‐acrylamide (PAAm) hydrogels were used as the growth media of CaCO₃. After copolymerized with acrylic acid and 2‐acrylamido‐2‐methylpropanesulfonic acid (AMPS), LLC hydrogels were modified with COOH and SO₃H, respectively. The effect of functional groups on the biomimetic mineralization of CaCO₃ was studied. Most of crystals from traditional hydrogels are rhombohedral and could not form aggregates. Only a few could aggregate and have a particular morphology with irregular orientation of subcrystal. Compared with crystals separated from traditional hydrogels, crystals growing in the LLC hydrogels were much more regulated and could form aggregates with particular morphology and regular orientation, that is, face (104) of rhombohedral subcrystals parallel to the surface of the macrocrystals. Modification of COOH and SO₃H groups made CaCO₃ subcrystal align more tightly. COOH had minor influences on the crystal orientation and small modification to the aggregate morphology. SO₃H groups could change the crystal orientation and morphology effectively. The aggregates are pseudo‐spherical and the face perpendicularity to the face (104) parallels to the surface of the aggregates.     

以多孔CaCO3微球为模板制备聚乙烯超疏水表面

以聚苯乙烯磺酸钠（PSS）掺杂的多孔碳酸钙（CaCO3）微球层为模板,通过热压低密度聚乙烯（LDPE）并结合酸蚀刻的方法制得了具有多层粘联微球结构、而非常见蜂窝状多孔结构的LDPE稳定超疏水表面（接触角152.8±2.5°,滚动角约6°）。元素分析表明,表面粘联微球为纯LDPE而非LDPE包覆的CaCO3。将多孔CaCO3微球稀疏地撒在LDPE表面并加热熔融,发现微球会自发沉降到熔体内部,酸蚀刻后形成了类似莲蓬的表面微结构,即坑内包含小球。结合CaCO3微球生成原理和多孔结构,认为粘联微球结构和莲蓬结构均是由于LDPE熔融大分子自发沉积到多孔CaCO3微球内部,“反模”形成了LDPE微球所致。本发现为多孔CaCO3微球的应用开辟了新方向。     

The Effect of Ionic Liquids on the CaCO3 Crystal Growth

In this paper, the effect of ionic liquids on the CaCO3 crystal growth has been studied for the first time. The obtained CaCO3 crystals were charactcred by the X-ray diffraction and scanning electron micrographs. The results showed that the control ability of ionic liquids for CaCO3 crystals growth was dependent on the counter anion very much.     

双亲水性嵌段共聚物对CaCO3结晶的影响

以合成的带有磺酸基为端基的线型-超支化二嵌段共聚物PEG-b-PEI-SO3H为模板,探讨了其对CaCO3结晶的影响,并用FTIR、XRD、SEM、TEM等对产物进行了表征.结果表明,带有—SO3H端基的线型-超支化双亲水性嵌段共聚物PEG-b-PEI-SO3H对CaCO3晶体形貌和晶型表现出较强的调控能力.培养1天时得到空心环状方解石型CaCO3晶体,但当培养时间为3天和5天时,得到的CaCO3晶体形貌既有河蚌状也有类球状,同时其晶型既有方解石也有球霰石,而当培养时间达到7天后,得到的就只有球状球霰石CaCO3晶体.     

Feature Designed Growth of 3D Flower-like SiO2 Growing on Polyethyleneimine Modified CaCO3 Microparticles

We report on the ability to create complex 3D flower-like SiO₂ in vitro via CaCO₃ micropar-icles supported by polyethyleneimine mediated biosilicification under experimentally altered chemical influences. The morphology, structure, composition of the product have been inves-tigated with the X-ray photoelectron spectrum, scanning electron microscope, transmission electron microscope, and energy-dispersive spectroscopy. The overall morphologies could be controlled to shift from a characteristic network of flower-like silica sphere to a sheet-like structure by adjusting physical adsorption of different amount of polyethyleneimine onto the surface of the CaCO₃ microparticles.     

三元添加剂水溶液体系制备CaCO3空心球

利用原位聚合方法, 通过加入一定量的引发剂使甲基丙烯酸原位聚合, 在三嵌段共聚物(P123)、聚甲基丙烯酸(PMAA)和十二烷基硫酸钠(SDS)的三元添加剂混合溶液体系中成功地制备了CaCO3空心球. 采用扫描电子显微镜(SEM)和X射线粉末衍射(XRD)对合成样品的形貌、结构进行了表征. 结果显示, 方解石CaCO3空心球直径约0.5-2 μm. 空心球壁由直径约25-35 nm的圆形粒子组成, 壁厚约100-300 nm. 利用核鄄壳机理解释了空心球结构的形成过程.     

Controllable Synthesis of CaCO3 Micro/Nanocrystals with Different Morphologies in Microemulsion

Lens-like vaterite CaCO 3 microrings composed of CaCO3 nanoparticles were synthesized via a micro-emulsion-mediated route at room temperature with ethanol and n-hexanol as co-surfactant. This process did not de-mand any additional energy such as heating or continuous agitation. It was the first time to use ethanol as co-surfactant in the synthesis of micro or nanomaterials. And the ethanol was believed to play an important role in the aggregation fashion of CaCO 3 nanoparticles. Moreover, shuttle-shaped nanorods, hexagonal nanoplates, and rice-like nanoparticles were also fabricated by modulating the growth parameters. Additionally, the introduce of ethanol into microemulsions as co-surfactant may be generalized as a novel green route to control the structure of other functional materials.