纳米级碳酸钙粉末材料的制备研究

利用CO2-Ca(OH)2-H2O体系制备了纳米级碳酸钙粒子,探讨了无添加剂制备过程中CO2流量对粒子大小和分散性能的影响.碳化前,在体系中引入了能与Ca2 生成沉淀的化合物,研究了硅酸钠、草酸钾、硼酸等对促进碳酸钙成核的效果.利用TEM、XRD和粒度分布测试对产品进行了表征.结果表明:CO2的最佳流量为6～7mL/s.添加草酸钾后制得的产品,具有粒度均匀、分散性好等优点,粒子的平均粒径为60～70 nm.     

锯齿斜翅管表面碳酸钙析晶污垢初始阶段结垢特性

进行光管和锯齿斜翅管在不同碳酸钙浓度和流速下的动态结垢实验,得到碳酸钙浓度、流速和锯齿斜翅管对碳酸钙析晶污垢结垢过程的影响。结果表明：浓度增大使溶液中均相成核速率和所形成晶核的生长速率增大,使溶液换热表面界面的污垢晶粒浓度和成垢离子浓度均增大,前者使更多的污垢附着换热面而后者使表面异相成核速率和生长速率增大。流速增大使光管表面形成的晶核、污垢晶体和污垢热阻均减少而诱导期延长;使锯齿斜翅管初始成核增多,但诱导期延长、而结垢量和污垢热阻减小。锯齿斜翅管在清洁状态和结垢状态下均具有比光管更大的总换热系数、更小的污垢热阻,尽管结垢量略多。     

纳米碳酸钙表面处理对PVC／CaCO3性能的影响

采用硬脂酸与硅烷偶联剂表面处理、PMMA水解接枝处理等方法对CaCO3进行表面改性,考察改性纳米钙对PVC／CaCO3复合材料力学性能的影响。     

n-SiO2对PA12涂层非等温结晶速率及成核活度系数的影响

利用火焰喷涂技术制备了聚酰胺12(PA12)及PA12/纳米SiO2(n-SiO2)复合涂层,采用差示扫描量热法(DSC)对涂层的非等温结晶性能进行了分析,探讨了n-SiO2对PA12涂层的结晶速率常数及成核活度系数的影响.结果表明,当n-SiO2的添加量在0.5%～2.5%(质量分数,下同)时,RA12/n-SiO2...     

聚丙烯酰胺对草酸钙结晶的调控作用

采用扫描电子显微镜(SEM)和X射线粉末衍射(XRD)等方法, 研究了聚丙烯酰胺(PAM)对草酸钙形貌和晶相的调控作用, 讨论了聚丙烯酰胺浓度、溶液pH和草酸钙过饱和度变化对草酸钙结晶的影响. PAM可以诱导二水草酸钙(COD)晶体生成并改变COD和一水草酸钙(COM)晶体的形貌. 加入5.0g/L的PAM后, 不但诱导了30%(w/w)的COD晶体形成, 出现了较为少见的COD聚集体, 而且使得COM晶体的棱角圆钝. 从PAM的分子结构、不同pH条件下PAM的水解差异、PAM中羧基与钙离子相互作用、PAM与COM表面Ca²⁺的络合-离解平衡、静电作用等角度讨论了上述结果, 表明通过改变实验条件, 可制备出不同晶相和形貌的草酸钙晶体.     

玻璃形核与析晶的研究进展

研究玻璃的形核和析晶具有十分重要的科学意义，综述了近二十年来国内外采用热分析法研究玻璃形核与析晶的最新进展，重点分析了玻璃在非等温过程中的析晶动力学，同时也评述了研究玻璃形核与晶体长大速率比较科学的理论方法。     

Assembly of nano-superstructural aragonite CaCO3 by living bio-membrane

Biomimetic living templates, mung bean sprouts (MBS), were employed to control the crystallisation of calcium carbonate. Metastable aragonite superstructure can be readily generated in normal conditions. Some interesting morphologies including elaborate piny dendritic, flowerlike and rods were also prepared using citric acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid as cooperation modifiers in the mineralisation process, under the conditions of 0.01% of crystal modifier and ambient temperature. These morphologies were assembled by some elaborate substructures, similar to nanowire and featherlike crystals. The products were characterised by SEM, XRD and FTIR, respectively. The results indicated that the formation of aragonite polymorph of calcium carbonate was favoured in this system. A probable mechanism was proposed.     

聚对苯二甲酸乙二醇酯的结晶成核改性研究进展

聚对苯二甲酸乙二醇酯(PET)因其重复结构单元中含有刚性苯环而成核慢、结晶度低,从而导致综合力学性能与耐热性较差,限制了其工程化应用,故对PET进行成核改性以提高结晶速率与结晶度成为亟待解决的问题。综述了PET的4大类成核剂:无机填料、有机小分子、有机高分子及复合型成核剂;在此基础上,提出机理上不同于异相成核的"离子簇集诱导成核"的概念,即与离子共价相连的聚合物链段因离子簇集而在离子簇近围紧密堆砌,从而诱导"拥挤"链段结晶成核。无机填料类成核剂包括粘土、氧化物与氢氧化物、无机盐、Si_3N_4及碳纳米管/石墨等,其成核机理均为异相成核。有机小分子类成核剂涉及羧酸盐、二胺、双酰胺及改性山梨醇等,其中羧酸盐成核机理为离子簇集诱导成核,而其它均属于异相成核。有机高分子类成核剂分为结晶性聚合物、液晶高分子、嵌段共聚物及离子交联型聚合物等;其中前三者属异相成核,后者为离子簇集诱导成核。复合型成核剂为两种以上成核剂(或成核机理)配合使用协同促进PET结晶成核。对比发现,有机高分子与复合型成核剂效果较好,且不会引起PET的降解,为PET优良成核剂。异相与离子簇集诱导耦合高分子成核剂为PET结晶成核改性未来的重点发展方向之一。     

Exploration of Antigen Induced CaCO3 Nanoparticles for Therapeutic Vaccine

Therapeutic vaccines possess particular advantages and show promising potential to combat burdening diseases, such as acquired immunodeficiency syndrome, hepatitis, and even cancers. An efficient therapeutic vaccine would strengthen the immune system and eventually eliminate target cells through cytotoxic T lymphocytes (CTLs). Unfortunately, insufficient efficacy in triggering such an adaptive immune response is a problem that remains unsolved. To achieve efficient cellular immunity, antigen‐presenting cells must capture and further cross‐present disease‐associated antigens to CD8 T cells via major histocompatibility complex I molecules. Here, a biomimetic strategy is developed to fabricate hierarchical ovalbumin@CaCO₃ nanoparticles (OVA@NP, ≈500 nm) under the templating effect of antigen OVA. Taking advantage of the unique physicochemical properties of crystalline vaterite, cluster structure, and high loading, OVA@NP can efficiently ferry cargo antigen to dendritic cells and blast lysosomes for antigen escape to the cytoplasm. In addition, the first evidence that the physical stress from generated CO₂ induces autophagy through the LC3/Beclin 1 pathways is presented. These outcomes cooperatively promote antigen cross‐presentation, elicit CD8 T cell proliferation, ignite a potent and specific CTL response, and finally achieve prominent tumor therapy effects.     

Synthesis of superparamagnetic CaCO3 mesocrystals for multistage delivery in cancer therapy

To develop a new system for site-specific targeting, superparamagnetic CaCO(3) mesocrystals with the properties of biocompatibility and biodegradability are designed and synthesized. They serve as carriers for the co-delivery of drug and gene nanoparticles via a multistage method for cancer therapy. With a porous structure, the mesocrystalline CaCO(3) particles encapsulate doxorubicin (DOX), Au-DNA, and Fe(3)O(4)@silica nanoparticles for magnetic control and therapy. As stage 1 microparticles (S1MPs), the nanoparticles-CaCO(3) system is designed to protect functional sections from degradation and phagocytosis in blood circulation. After the particle margination in vascular walls, the Au-DNA nanoparticles (stage 2 nanoparticles, S2NPs) and DOX are gradually released from S1MPs by degradation towards targeted tissues for biomedical therapy. The nanoparticles-CaCO(3) system exhibits high efficiency of intracellular delivery, especially in nuclear invasion. The successful expression of reporter gene and intracellular transport of DOX in vitro suggest potential as a co-delivery system for drug and gene therapy. In a mouse tumor model, the system with particle margination and two-step strategy affords the protection of functional nanoparticles and drug from clearance and inactivation by enzymes and proteins in vivo. The targeted delivery of S2NPs into tumors by this system is tenfold more efficient than that of the nanoparticles themselves. The drug is observed to be widely distributed in tumor slices. Thus, this platform exhibits an efficient approach in the targeted delivery of therapeutic nanoparticles and molecules via a multistage strategy, and can be used as a potential system in co-delivery of multiple agents for biomedical imaging and therapy.     

形核剂对Li2O-Al2O3-SiO2系微晶玻璃晶化过程的影响

采用差热分析(DTA),X射线衍射分析(XRD),扫描电镜(SEM)等分析手段研究了 TiO₂和TiO₂+ZrO₂两种形核剂对Li₂O-Al₂O₃-SiO₂(LAS)系微晶玻璃的形核和晶化的影响. 结果发现,样品经过不同温度的预形核处理后,采用TiO₂单一形核剂,晶化峰值温度和晶化峰 高度的变化较大,而采用TiO₂+ZrO₂复合形核剂,晶化峰值温度和晶化峰高度的变化较小. 当形核时间为2h,两种形核剂样品的最佳形核温度分别为745和760℃.晶化后均可得到纳米 结构的β-石英石固溶体晶相,其中采用TiO₂+ZrO₂复合形核剂样品的晶粒更细小.研究表 明采用复合形核剂的LAS微晶玻璃的形核过程对温度的敏感性小,有利于对形核过程进行控 制,同时形核效率高.     

碳化法制备超细碳酸钙反应中凝胶现象的研究

为了研究制备超细碳酸钙过程中凝胶现象对反应过程及产物性能的影响,本文中以碳化法制备超细碳酸钙中的凝胶现象为例,研究了不同工艺参数(温度、石灰乳浓度、碳化气体流量、添加剂)对凝胶现象的影响,探讨了凝胶产生的微观原因,并提出了加入适当成核添加剂以避免凝胶产生的新方法。研究结果表明,避免凝胶出现或减轻凝胶现象的主要方法是在保持产品粒径达到要求的前提下控制反应温度在一定范围内,CO2的气体流量不能过大,石灰乳液浓度不能过高。选择适当的能产生微晶的添加剂来优化反应进程,能够与体系中的反应物作用产生微晶的物质,避免凝胶的发生。     

A micro-sphere catalyst complex with nano CaCO3 precursor for hydrogen production used in ReSER process

This paper describes the preparation and evaluation of a micro-sphere catalyst complex for the hydrogen production in a Reactive Sorption Enhanced Reforming (ReSER) process. The catalyst complex made by a spray technique has a dual function containing Ni as a catalytic material and a CaO as an adsorption material used in the ReSER process. The attrition characteristics of the catalyst complex are acceptable for the commercial used. The nano CaCO3 material used as a precursor of CaO showed a desirable durability with a CO2 sorption capacity of 0.6 molCO2/kg after 10 repeating cycles under the carbonation temperature of 600°C, a CO2 partial pressure of 0.02 mPa, and a calcinations temperature of 750°C in N2 measured by a thermal gravimetric analyzer. The testing of the catalyst complex for ReSER showed a hydrogen yield of over 95% (v/v) in the laboratory fixed fluidized bed reactor. The catalyst system has an attractive prospect in the ReSER process for hydrogen production, especially in the fluidized mode where reactor and regenerator combined in a cycling process.     

纳米碳酸钙改性分散及其在钻井液中的应用研究

为探讨无机纳米材料在钻井液中的应用现状,利用自然沉降和紫外-可见分光光度法优化了分散剂对纳米碳酸钙的分散改性条件,讨论了分散剂种类、分散剂用量、分散时间和温度等因素对纳米碳酸钙分散效果及分散稳定性的影响.研究表明:优化条件下制得的分散体系润湿性和分散性有很大改善;添加改性和未改性纳米碳酸钙基浆均具有一定的降滤失性,二者表观黏度、塑性黏度和动切力均表现为降低趋势;泥浆流变性能得到一定改善,改性纳米碳酸钙较未改性纳米碳酸钙颗粒的封堵效应更好.     

改性CaCO_3填充聚四氟乙烯复合材料的制备和力学性能

以石蜡为改性剂,分别采用干法和湿法对重质CaCO_3进行表面处理,然后采用冷压烧结工艺制备聚四氟乙烯(PTFE)/CaCO_3复合材料,并对其力学性能进行研究。利用红外光谱分析石蜡包覆改性前后的CaCO_3的结构变化,研究了2种改性方法对PTFE/CaCO_3复合材料的力学性能的影响。结果表明,2种改性方法都可以提高PTFE/CaCO_3复合材料的断裂伸长率和拉伸强度,当质量分数为30%的湿法改性CaCO_3填充PTFE时,复合材料的断裂伸长率仍能达到200%以上。另外,采用不同改性方法和改性剂比例及CaCO_3含量所制备的复合材料力学性能相差很大,其中,当CaCO_3质量分数为5%,湿法改性的改性剂石蜡质量分数为1%时,复合材料的各项力学性能达到最佳,远好于未经改性的CaCO_3填充聚四氟乙烯复合材料。     

碳酸钙填充对PVC增塑糊黏度的影响

文章研究了碳酸钙(CaCO_3)未填充和填充情况下,3种不同生产方法、相近聚合度的聚氯乙烯(PVC)糊树脂在对苯二甲酸二辛脂(DOTP)和乙酰柠檬酸三正丁酯(ATBC)2种增塑体系中的黏度性能,以及黏度性能与增塑糊中粒子颗粒形态关系。结果表明,无论CaCO_3填充与否,增塑糊黏度在DOTP体系下均比ATBC的大,主要与增塑剂分子结构有关;未填充CaCO_3时,增塑糊黏度性能主要受PVC糊树脂和增塑剂间相容性的影响,3种糊树脂与DOTP的相容性均比ATBC的好;填充CaCO_3后,几种增塑糊黏度均增大,黏度性能主要受相容性和树脂与CaCO_3粒子颗粒形貌的共同影响。     

纳米碳酸钙湿法表面改性的研究

利用季铵型阳离子表面活性剂对纳米碳酸钙进行了湿法表面改性。对湿法改性前后的纳米碳酸钙进行了红外光谱(FTIR)、X射线衍射(XRD)及透射电镜(TEM)分析。采用Zeta电位、分散体系浊度、沉降体积、表观粘度等分析方法对改性前后纳米碳酸钙在水中的界面行为进行评价。另外,通过激光粒度仪对改性前后纳米碳酸钙分散液的粒度分布进行了测定。实验结果表明,经湿法表面改性后,纳米碳酸钙在水中的润湿性及分散性有很大改善。     

碳酸盐矿化菌调控碳酸钙结晶动力学、形态学的研究

选用实验室自培育碳酸盐矿化菌,研究了体系、细菌体体系、细菌分泌物液体系对碳酸钙结晶动力学,晶体形貌影响.研究发现细菌液浓度增加,抑制碳酸钙成核动力学"平台区"由0增加到7.8min;细菌体作为异相成核点加速结晶过程;分泌物抑制晶体成核,并随着与Ca2 混合时间的不同,"平台期"延长.球形碳酸钙的产生是由细菌分泌物调控;Ca2 同有机质表面-COO-和CO结合,并且随着相互间作用程度的增加,球状碳酸钙不规整表面逐步转变为光滑表面.本研究对于微生物诱导碳酸钙的工程性应用如混凝土微裂缝修复、古建筑表面防护处理、微纳米碳酸钙颗粒制备等具有一定指导意义.