水热法制备近红外发光NaLa(WO4)2∶Ln(Ln=Er, Nd)球形粒子的研究

利用水热法制备了NaLa（WO4）2∶Ln（Ln=Er,Nd）球形粉末,分别用XRD,TEM和发光光谱等对粉末的物相、形貌、发光性质进行研究。XRD和SEM结果表明：制得的NaLa（WO4）2∶Ln（Ln=Er,Nd）粉末为白钨矿晶型,分散性良好,粒度均匀,呈规则的球形,粒径为1μm左右。发光光谱的测试表明：样品的最佳掺杂浓度为1.0%;随着煅烧温度的增加,样品发光强度逐渐增大;700℃下煅烧时最佳煅烧时间是4 h。     

球形PVC-MnO2离子筛的制备及锂吸附性能

本实验室前期所制备的Li4Mn5O12超细粉末在卤水体系中对Li+具有较大的吸附容量和良好的选择性。但由于超细粉体的流动性和渗透性差,无法直接应用于固定床,需对粉末吸附材料进行成型造粒,以便于实际应用。本论文采用聚氯乙烯为粘结剂,制备出粒径约为2.0~3.5 mm的球形PVC-Li4Mn5O12,经盐酸处理后得到球形PVC-MnO2离子筛。并通过扫描电镜(SEM)、X射线衍射仪(XRD)、静态和动态连续锂吸附实验研究了球形离子筛形貌和锂离子吸附性能。结果表明,球形离子筛对Li+的吸附容量高达5.28 mmol.g-1,在混合溶液中对Li+具有良好的选择性,这对于在盐湖卤水或海水提锂具有重要的实用意义。     

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.     

均匀大颗粒球形碳酸钙的仿生合成

依据仿生矿化原理,采用难溶性CaSO4作为钙源,以柠檬酸钠为模板剂合成出了均匀大颗粒球形碳酸钙晶体,用X射线粉末衍射(XRD)分析、扫描电子显微镜(SEM)、傅立叶变换红外吸收光谱(FTIR)和热重分析等测试技术对所得碳酸钙样品进行了表征,探讨了其合成机理. 研究表明,柠檬酸钠对碳酸钙的晶形具有调控作用,在柠檬酸钠质量浓度为0.9%的条件下,能合成出大小均匀、分散性好、粒度为10～15 μm的大颗粒球形碳酸钙晶体.     

β－环糊精与碳酸钙结晶的相互作用

依据生物矿化的基本原理，以β－环糊精（β－CD）作为有机基质，采用仿生 的方法合成了具有独特形貌的文石型碳酸, 其中含有少量的β－环糊精。用X射线 粉末衍射（XRD）分析、扫描电子显微镜（SEM）、傅里叶变换红外吸收光谱（FT－ IR）和电导率测定等手段对所得复合碳酸钙进行了表征，结果发现CaCO3结晶过程 中，β－环糊精与CaCO3之间存在着相互作用，并讨论了这种作用的可能机理。     

简单方法制备羟基磷灰石中空微球

无需添加任何有机物和金属离子, 以易得的中空球形碳酸钙(CaCO3)与磷酸氢二钠(Na2HPO4)作为反应物在常压下制备出羟基磷灰石中空微球. 通过场发射扫描电子显微镜(FESEM)、扫描电子显微镜(SEM), X射线粉末衍射(XRD)等手段对制备的羟基磷灰石中空微球的结构、组成和形貌进行了表征, 考察了不同反应温度对中空球形貌的影响. 实验结果表明, 所制备的羟基磷灰石微球是由短针状的纳米粒子组成的, 直径为2-4 μm. 对反应机理进行了初步探讨.     

大庆油田三元复合驱结垢样品中碳酸钙的结晶特性及形貌特征

采用EDAX, XRD和SEM等方法对大庆油田三元复合驱结垢样品中碳酸钙的结晶特性及形貌特征进行了研究. 结果表明, 结垢样品中的碳酸钙呈现出球形、棒状和花状等形貌特征和层状生长的结晶特征. 部分水解聚丙烯酰胺(HPAM)降低了重烷基苯磺酸盐(HABS)表面活性剂的临界胶束浓度(cmc), 促进了其胶束化作用; HABS使溶液中HPAM链的刚性增强, 负电吸引能力增强; 二者均会形成模板, 导致结垢样品中的碳酸钙具有不同的形貌特征. 聚丙烯酰胺和表面活性剂的存在未改变结垢样品中碳酸钙的层状生长特征.     

聚合物控制碳酸钙晶型、形貌的研究

碳酸钙有不同的晶型和形貌,聚合物的加入在改变碳酸钙的晶型和形貌方面起着重要作用。本文综述了不同聚合物对碳酸钙的影响,重点讨论了生物高分子聚合物、双亲水基嵌段共聚物、树枝状聚合物等对碳酸钙晶型、形貌的调控,同时介绍了聚合物与其他添加剂相互协同作用对碳酸钙的影响,并对当前研究中存在的问题和不足进行了评述。通过对碳酸钙的研究,不仅有助于制备不同尺寸、各种形状和不同表面性能的碳酸钙产品,满足不同的工业需求,而且能够更加深入地了解生物矿化的机理,更好地仿生合成和制备各种功能材料。     

碳量子点诱导的多形碳酸钙粒子矿化及其形成机理

以在不同的热处理温度下合成的具有可变化学结构的碳点(CDs)为添加剂调控合成矿物碳酸钙。在室温条件下合成了花生状、哑铃状和球形碳酸钙颗粒。用扫描电镜(SEM)、傅里叶红外光谱仪(FTIR)、荧光光谱仪(PL)和X射线衍射仪(XRD)对样品进行了表征,详细研究了碳酸钙双球粒子的生长过程。CDs表面随处理温度可调变的极性官能团(主要为羧基、醛基、羟基等)被认为是导致合成碳酸钙粒子形貌变化的原因。对碳酸钙双球粒子的生长机理研究表明,Ostwald成熟和定向聚集机制是在CDs存在下最终双球粒子形貌形成的驱动力。     

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。     

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.     

Effect of ZSM-5 zeolite morphology on the catalytic performance of the alkylation of toluene with methanol

A series of ZSM-5 zeolites, with the morphologies of sphere, sphere with cubic particles on the surface, and cubic particles, were synthesized by hydrothermal method using n-butylamine as the template, assisted by the addition of NaCl and crystal seed. X-ray diffraction(XRD),scanning electron microscope(SEM), X-ray fluorescence(XRF) and temperature-programmed desorption of ammonia(NH3-TPD) were used to characterize these samples. The samples were tested with toluene methylation reaction. The modified sample composed of spherical particles with 3 μm crystal particles on the surface had a para-xylene selectivity of 95% and maintained 79% of the initial conversion after running the reaction for 50 h. This modified sample showed the best stability among the tested three modified samples.     

Preparation and formation mechanism of wood-block-like calcite particles

Pure calcite crystal with different morphologies such as wood-block and spherical aggregates were prepared by a precipitation reaction in the presence of citric acid. The as-prepared products were characterized with scanning electron microscope (SEM) and X-ray diffraction (XRD). The results showed that citric acid obviously influenced the formation of precipitates and the morphology of final products. The formation mechanism of wood-block-like particles was proposed according to theoretical deduction and the proposed growth mode.     

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.     

疏水球状碳酸钙的制备、表征及对聚丙烯力学性能的影响

以十二碳醇磷酸酯(DDP)为改性剂, 采用碳化法制备了分散性良好的球状碳酸钙粒子. 通过FESEM, XRD, FTIR及活化度和接触角测试对产物进行了表征. XRD分析结果表明, 随着DDP添加量的增加, 所得CaCO3由方解石型向文石型转变. FTIR结果表明, 改性剂与碳酸钙表面是以化学键合和物理吸附方式相结合. 当DDP含量达到2%时, 接触角为120.43°, 活化度达到99%, 碳酸钙粒子由亲水性转变为完全疏水性. 考察了反应温度和DDP含量对产物形貌与结晶行为的影响, 并对改性机理进行了初步探讨. 将产品填充到聚丙烯(PP)中, 测定了PP的力学性能.     

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.     

碳酸钙微米球的制备与表征

采用醋酸钙和碳酸钠为原料,在反应温度为5℃和柠檬酸三钠质量百分浓度为15%的条件下,采用沉淀法合成出了粒度为1～4μm、分散性好的球形碳酸钙粉体。用扫描电子显微镜(SEM)、X射线衍射仪(XRD)、红外光谱仪(IR)、原子力扫描探针显微镜(ASPM)、光学显微镜、粒度分析仪等对样品进行了表征,并用光学显微镜跟踪考察了碳酸钙微米球的形成过程。结果表明,碳酸钙微米球是由大量纳米级颗粒组装而成。     

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.     

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。     

Sol–gel synthesis of iron oxide–silica composite microstructures

Spherical silica particles doped with iron oxide have been synthesized via base-catalyzed one-pot sol?Cgel process using tetraethoxysilane (TEOS) and iron(III) ethoxide (ITE) as co-precursors. In the modified St?ber process adopted, depending on the concentration of ITE in the starting composition, materials of various morphologies were observed under a scanning electron microscope and an atomic force microscope. The presence of ITE significantly affected the formation process of particulate silica; the spherical particles were formed accompanied by the co-presence of irregular-shaped finer aggregates. The fraction of the aggregates with rough surfaces increased with an increase of the ITE content in the reaction mixture. Both the spherical particles and irregular-shaped aggregates contained iron hydroxide and they exhibited paramagnetic behavior. The chemical composition and physicochemical properties of the materials were determined using various complementary spectroscopic methods.