In situ SAXS studies of the formation of sodium jarosite

This paper reports the results of time‐resolved synchrotron small‐angle scattering and powder diffraction experiments where natrojarosites were synthesized in situ in order to observe the species produced at the earliest stages of nucleation. The sample temperatures were 333, 353 and 368 K. These compounds were synthesized by co‐precipitation from solution on the Small and Wide Angle Scattering and Powder Diffraction beamlines at the Australian Synchrotron. Scattering data were collected continuously throughout the syntheses. The results presented here show that the first particles to form in solution appear to be amorphous and nucleate on the walls of the reaction vessel. Crucially, there is a single nucleation event which forms particles with an elliptical disc morphology which then grow uniformly before natrojarosite crystallization is observed in complementary powder diffraction data. This nucleation event may represent the key to controlling the growth of jarosites in industrial and environmental settings.     

The Effect of Zinc Oxide and Calcium Carbonate Nanoparticles on the Thermal Conductivity of Polypropylene

The thermal conductivity (TC) of compression-moulded polypropylene (PP) and PP filled with 5–15% zinc oxide (ZnO) or calcium carbonate (CaCO₃) nanoparticles, prepared by extrusion, was studied using a thermal conductivity analyzer (TCA). The effect of nanoparticle content and crystallinity on the thermal conductivity was investigated using conventional methods, including SEM, XRD, and DSC. The incorporation of nanoparticles improved the crystallinity and thermal conductivity simultaneously. The experimental TC values of the PP nanocomposites with different level of nanoparticles concentration showed a linear increase with an increase in crystallinity. The TC improvement in PP/ZnO nanocomposite was greater than that of PP/calcium carbonate nanocomposites. This fact can be attributed to the intrinsic, better thermal conductivity of the ZnO nanoparticles. Several models were used for prediction of the TC in the nanocomposites. In the PP/ZnO nanocomposites the TC values correlated well with the values predicted by the Series, Maxwell, Lewis and Nielson, Bruggeman, and De Loor models up to 10 wt%.     

Formation of Calcium Carbonate Sub‐Micron Particles in a High Shear Stress Three‐Phase Reactor

The production of precipitated calcium carbonate (PCC) was investigated experimentally under industrially relevant conditions, i.e. at high solid concentrations and increasing amount of solid product in the slurry. Temperature is an important parameter since it determines the crystal structure, the particle shape and, as a consequence, the viscosity of the slurry. Of course, the mass concentration of the raw material also has an important influence on the viscosity. From the particle size distributions of primary particles and agglomerates, it can be concluded that the nucleation process is governed by primary nucleation. Also, heterogeneous nucleation occurs on solid calcium hydroxide particles that are present in the slurry. Especially if the raw material contains impurities heterogeneous nucleation occurs and large and unwanted particles are formed. If the slurry is not stabilized, strong agglomeration occurs that can be influenced by the shear stress introduced to the slurry: a high shear stress which is linked to the viscosity of the slurry limits the upper particle diameter and leads to a steep particle size distribution of the product.     

水溶性BSA-羟基磷灰石-碳酸钙复合物的形成机理

本文以傅里叶变换红外光谱为手段,对不同反应摩经的牛血清蛋白（ＢＳＡ）、羟基磷灰石、碳酸钙固体在水溶液中反应后的滤液进行了研究,谱带峰位和强度的变化表明,ＢＳＡ与羟基磷灰石、碳酸钙以多种形式的络合配位及氢键等结合,使难溶钙盐的溶解度增加,形成三元水溶性复合物,其复合物的组成随反应摩尔比的改变而有差异,具有化学计量的性质。     

Effect of Filler Treatment on Crystallization,Morphology and Mechanical Properties of Polypropylene/Calcium Carbonate Composites

Pimelic acid (PA) was used as a new surface modifier for CaCO₃. The effects of PA treatment on the crystallization, morphology, and mechanical properties of PP/CaCO₃ composites were investigated. Fourier transform infrared (FTIR) spectroscopy analysis revealed that PA bonded to CaCO₃ and formed a calcium pimelate surface layer after reacting with CaCO₃. The results of wide angle X-ray diffraction (WAXD), differential scanning calorimetry (DSC), and polarized light microscopy (PLM) proved that the PA treated CaCO₃ induced a large amount of β -iPP and decreased the spherulitic size of PP. The results of scanning electron microscopy (SEM) showed that the PA treatment enhanced the interfacial adhesion between the filler and the matrix, indicating the improvement of the compatibility between PP and CaCO₃. The toughness of the composites was improved by the more ductile β -form spherulites. When 1% of PA treated CaCO₃ was added, the notched impact strength reached its maximum, a value of 19.79 kJ/m², which was 3.64 times greater than that of the pure PP.     

碳酸钙对牛血清白蛋白微结构的影响

用紫外、紫外二阶导数谱和FT－IR光谱及曲线拟合等技术研究了水溶液中碳酸钙对牛血清白蛋白（BSA）微观结构的影响。结果表明,BSA的芳香族氨基酸残基受到干扰;二级结构也发生了变化。这些变化正是生物矿物形成的基础。     

碳酸钙结晶对胃蛋白酶二级结构的影响

本文通过傅里叶变换红外光谱及退卷积、曲线拟合等技术研究了碳酸钙结晶对胃蛋白酶二级结构的影响 ,结果表明 :在纯的胃蛋白酶中 ,α 螺旋、 β 折叠、转角及无规卷曲等四种结构的含量分别为2 4 38% ,2 9 91% ,39 2 2 % ,6 4 9% ;而在CaCO3 胃蛋白酶溶液中 ,四种结构的含量分别为 2 0 9% ,93 30 4 % ,4 6 0 %和 0 0 0 6 %。由此可以看出 :碳酸钙晶体的形成使胃蛋白酶的α 螺旋结构减少 ,β 折叠结构增多 ,本文讨论了这种变化的本质。     

离子液体热分解机理的原位变温多核核磁共振研究

利用原位变温核磁共振氢谱（¹H NMR）、核磁共振氟谱（¹⁹F NMR）和核磁共振磷谱（³¹P NMR）等NMR技术研究特定温度下离子液体的热分解机理．在温度低至80℃时,1-丁基-3-甲基咪唑阳离子（C₄mim⁺）和六氟磷酸根阴离子（PF₅-）组成的离子液体[C₄mim][PF₅]呈现1个缓慢但明显的分解过程．无水[C₄mim][PF₅]在温度高于80℃时开始分解,生成少量的五氟化磷（PF₅）和氟化氢（HF）,氟化氢中的氢原子来自于1-丁基-3-甲基咪唑环2位上的氢原子．在丢掉这个氢原子后,阳离子成环形成一个卡宾,并与PF₅形成卡宾/PF₅复合物．定量NMR分析显示在分解反应达到平衡状态时,自由态PF₅和卡宾/PF₅复合物的比例为7∶3．     

Group Theoretical Analysis of the v 1 (CO 3 2-) Vibration in Crystalline Calcium Carbonate

A group theoretical analysis, based on the correlation method, is presented for the symmetric stretch vibration of the carbonate ion in three crystalline forms of calcium carbonate: calcite, aragonite and vaterite. Numbers of Raman and infrared active components are calculated and compared with experimental data, including those from a recent Raman study of vaterite. It is shown that the splitting observed for v _l in vaterite is compatible with two of the proposed crystal structures for this compound.     

3种变性淀粉与CaCO3相互作用的红外光谱研究

通过仿生合成的方法,以羧甲基淀粉、醚化淀粉、磷酸酯淀粉作为有机基质,在制备CaCO3晶体的过程中,通过傅里叶变换红外光谱对3种变性淀粉进行了跟踪测试表征。结果表明：3种变性淀粉分子中的C-O谱峰的强度均发生了变化,随着反应时间的增加,C-O峰强度不断减小,且减小的幅度非常大。对3种变性淀粉与CaCO3的作用机理进行了初步探讨。     

羟基磷灰石-碳酸钙-BSA水溶性复合物中蛋白质微观结构的研究

利用傅里叶变换红外光谱，结合二阶导数谱、退卷、积和曲线拟合等计算机解析方法，对牛血清白蛋白（BSA）－羟基磷灰灰石－碳酸钙水溶性复合物中BSA的二级结构进行了研究。结果表明，BSA的α－螺旋结构的含量增加，蛋白质结构趋于有序化；紫外光谱和紫外二阶导数谱的研究发现，BSA的芳香族氨基酸残基的微环境受到扰动，在生物体内，正是蛋白质结构的这些变化导致生物矿化过程的发生和进行。     

Properties and Morphology of Poly(Lactic Acid)/Calcium Carbonate Whiskers Composites Prepared by a Vane Mixer based on an Extensional Flow Field

Binary composites of poly(lactic acid) (PLA)/calcium carbonate whiskers (CCW) with different weight fractions were prepared with a vane mixer based on extensional rheology. The mechanical properties, thermostability, crystallization behavior, rheology behaviors and micromorphology of the composites were analysed to study the effect of the CCW fibers on the composite's properties; a pure PLA sample was also prepared for comparison. Scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) revealed that the CCW fibers had excellent compatibility with the PLA matrix and the CCW fibers were dispersed and distributed evenly in the PLA matrix under the action of the extensional flow field produced by the vane mixer. Differential scanning calorimetric (DSC) analysis showed that introducing a vane mixer into the PLA processing could increase the degree of crystallization (χ_c) of the composites significantly, and moderate CCW fibers adding could further increase its χ_c value. Thermogravimetric analysis (TGA) revealed that adding the CCW fibers reduced the thermostability of the composites. The G′, G″, η* and the torque, T_N, of the composites, obtained from rheology analyses, declined obviously, because of the hydrolysis and chains scission induced by residual water and fatty acid when the CCW content less than 4%. Tensile tests proved that filling moderate amounts of CCW fibers into PLA could increase its tensile strength and strain at break, increasing by 5% and 29.6%, respectively.     

Increased Flame Retardant,Smoke Suppressant and Mechanical Properties of Semi-Rigid Polyvinyl Chloride (PVC) Treated with Zinc Hydroxystannate Coated Dendritic Fibrillar Calcium Carbonate

Zinc hydroxystannate (ZHS) coated dendritic fibrillar calcium carbonate (ZHSCC-_D) and ZHS coated cubic calcium carbonate (ZHSCC_-C) were prepared in the water solution of cetyl trimethyl ammonium bromide (CTAB)/glycerin and in a pure water solution, respectively. Compared with the semirigid polyvinyl chloride (PVC) treated with ZHSCC_-C, when the addition level and the effective flame retardant component of ZHS were the same, the semi-rigid PVC treated with ZHSCC_-D showed a higher value of tensile strength, elongation and impact strength, and a lower smoke density rating (SDR) value than those of the semi-rigid PVC treated with ZHSCC_-C; except for the semi-rigid PVC treated with 10 g ZHSCC_-C (1:10) or ZHSCC_-D (1:10) per 100 g PVC, the semi-rigid PVC treated with ZHSCC_-D had almost the same LOI value as that of the semi-rigid PVC treated with ZHSCC_-C. The semi-rigid PVC treated with 10 g ZHSCC_-D (1:10) per 100 g PVC had the best integrated properties.     

Thermal Stabilities of Poly(Vinyl Chloride)/Calcium Carbonate (PVC/CaCO3) Composites

Poly(vinyl chloride)/calcium carbonate (PVC/CaCO₃) composites with micrometer or nanometer CaCO₃ as fillers were prepared by the solution blending method. The thermogravimetric analysis (TGA) of the composite films conducted in N₂ atmosphere showed that the addition of the CaCO₃ fillers could improve their thermal stabilities. It was also found that the nanometer CaCO₃ filler provided better thermal stabilities than the micrometer fillers even with a smaller amount. The mechanism of the improvements was investigated by a facile chemical analysis developed to examine the thermal stabilizing effect of calcium carbonate particles with different sizes in PVC/CaCO₃ composites after the pyrolysis of the samples in an air atmosphere in an oven.     

表面合金电催化剂上甲酸氧化的原位FTIR反射光谱研究

运用原位红外反射光谱(FTIRS)和电化学循环伏安法(CV)研究了甲酸在三种不同电极上的电催化特性。结果表明甲酸在碳载铂电极(Pt/GC)上的电催化氧化机理与本体铂电极(Pt)相类似,即可以通过活性中间体或毒性中间体氧化至CO_2。Pt/GC对甲酸的氧化比Pt具有更高的电催化活性。Pt/GC表面以Sb吸附原子修饰的电极(Sb-Pt/GC)上,甲酸氧化的起始电位(E;)提前至-0.10V,氧化电流峰电位(Ep)提前至0.34V,氧化峰电流(jp)值增加了7.28倍,半峰宽(FWHM)为0.30V。同样,Surface al-loy/GC电极上,E_I为-0.12V,E_p为0.32V和j_p为7.25mA·cm~(-2),相对Pt/GC分别负移了0.22,0.02V和增大了8.15倍,半峰宽(FWHM)为0.5V。表明Sb-Pt/GC和Surface alloy/GC电极不仅能够有效地抑制毒性中间体CO的生成,而且还可以显著地提高其对活性中间体的氧化的电催化活性。     

固/液界面原位红外显微镜和步进扫描时间分辨FTIR反射光谱及其在纳米材料科学中的应用

结合红外显微镜和步进扫描FTIR光谱仪 ,发展了固 /液界面电化学原位显微镜红外反射光谱和步进扫描快速时间分辨FTIR反射光谱 ,并应用于纳米材料特殊性能和电化学反应动力学的研究。研制纳米结构Pt微电极 ,获得CO吸附的红外特征随纳米结构和纳米尺度变化的原位显微镜红外谱图。利用纳米结构Pt微电极的异常红外效应 ,显著提高电化学原位红外反射光谱的灵敏度 ,获得分辨率达 5 0 μs的步进扫描时间分辨光谱。不仅发展了固 /液界面显微镜原位红外反射光谱新方法 ,并且拓展了电化学原位红外反射光谱在纳米材料科学研究中的应用。     

纳米薄膜合金电极上二氧化碳电催化还原的红外光谱研究

运用电化学循环伏安和原位ＦＴＩＲ反射光谱，研究ＣＯ２的电催化还原过程。结果表明，纳米薄膜合金材料Ｓｂ－Ｐｂ－Ｐｔ／ＧＣ对ＣＯ２还原具有较高的活性。还原产物以小分子羧酸和伯醇为主。     

载钯分子筛修饰电极上CO吸附的原位红外反射光谱研究

制备载Ｐｄ的分子筛电极,以ＣＯ吸附为探针电化学原位ＦＴＩＲ反射光谱,首次发现限定在分子筛超笼中的纳米Ｐｄ微粒对ＣＯ的吸附具有增强红外吸收效应。     

甲酸在Pt(100)/Sb电极上氧化的时间分辨原位FTIR反射光谱研究

以电化学原位时间分辨ＦＴＩＲ反射光谱和循环伏安方法研究甲酸在不同Ｓｂ覆盖度修饰的Ｐｔ（１００）单晶电极上的氧化。发现Ｓｂａｄ的修饰抑制了甲酸的解离吸附,使反应经活性中间体直接氧化至ＣＯ２。电化学和红外光谱数据表明,θＳｂ＝０．２４的Ｐｔ（１００）／Ｓｂ电极具有最高的电催化活性。