不同碱辅助的沉积沉淀法对三效催化剂稳定性的影响

老化处理会导致三效催化剂(TWCs)严重失活,因此提高催化剂的耐久性能是TWCs设计的目标.本工作采用不同碱辅助的沉积沉淀法,即尿素辅助沉积沉淀法和氨水辅助沉积沉淀法制备了Pt/Ce0.4Zr0.5La0.05Pr0.05O2(Pt/CZ)三效催化剂,分析了不同碱对催化剂物理化学性质、催化活性和耐久性的影响.结果表明,...     

光刻系统用氟化钙晶体的研究进展

解释了氟化钙晶体能被应用在光刻系统和掀起研究热潮的原因,概述了氟化钙晶体的研究和发展现状,指出了目前氟化钙晶体在研究和发展过程中要解决的重要问题和措施,最后对氟化钙晶体在光刻系统中的发展前景作了展望.     

沉淀法控制制备亚微米与纳米CaF2

本文在纯水溶剂和乙醇/水混合溶剂中沉淀制备亚微米和纳米CaF2粉体,对沉淀产物的粒径控制进行了研究。用TEM和XRD对CaF2沉淀的粒径和形貌进行表征。在纯水溶剂中,通过改变反应物浓度和反应物混合速度以控制形核和晶粒长大比例,成功制备了粒径分别为242nm,79nm和51nm的CaF2粉体。在混合溶剂中,通过改变水/乙醇的体积比改变混合溶剂的介电常数从而改变CaF2的溶解度的方法,在1∶1,1∶4和纯乙醇中分别获得粒径为31nm,23nm和12nm的CaF2粉体,沉淀粒径的倒数和混合溶剂介电常数的倒数间呈线性关系。结果表明,在水溶液中通过控制形核和晶粒长大比例适宜制备粒径较大的沉淀粉末,混合溶剂中改变CaF2的溶解度适合制备纳米级沉淀粉体,两种手段综合运用,可以在大范围内调节沉淀粉末粒径。     

Effects of Addition of Mannitol Crystals on the Porosity and Dissolution Rates of a Calcium Phosphate Cement

The bone defect repair functions of calcium phosphate cement (CPC) are related to its osteoconductivity and its gradual replacement by new bone. Adding mannitol to CPC may enhance its bone repair potential by increasing CPCs macroporosity and dissolution rate. The objective of the study was to assess microporosity and macroporosity and dissolution rates for CPC mixed with mannitol. Three groups of CPC discs were prepared by combining an equimolar mixture of tetracalcium phosphate and anhydrous dicalcium phosphate with (0 %, 10 %, or 50 %) mass fraction (hereafter expressed as mass %) of mannitol. Macroporosity and microporosity of the samples were calculated from volume and mass measurements of the discs. Discs were then placed in a pH 3.0 demineralizing solution simulating acidified physiological solution, and dissolution rates were measured by a previously described constant-composition titration method. Pure CPC exhibited no macropores and microporosity (mean ± s.d.; n = 5) of (46.8 ± 0.8) % volume fraction (hereafter expressed as vol %). Adding 10 mass % mannitol resulted in 15.6 ± 3.9 vol % macroporosity and 39.4 ± 1.8 vol % microporosity, and adding 50 mass % mannitol produced 54.7 ± 0.8 vol % macroporosity and 21.1 ± 0.4 vol % microporosity. The dissolution rates (mean ± s.d.; n = 5) of CPC with (0, 10, and 50) mass % mannitol incorporation were (30.6 ± 3.4, 44.8 ± 10.2, and 54.7 ± 3.6, respectively) μg · cm(-2) · min(-1), or (0.018 ± 0.002, 0.032 ± 0.007, and 0.072 ± 0.005, respectively) μL · cm(-2) · min(-1). Adding either 10 mass % or 50 mass % mannitol into CPC significantly (p < 0.05) increased CPC dissolution rates. Adding mannitol readily increased macroporosity and dissolution rate of CPC, which may enhance the capacity of CPC to be osteoconductive.     

Precipitation and Solubility of Calcium Hydrogenurate Hexahydrate

Solid phases formed in the quaternary system: uric acid—calcium hydroxide —hydrochloric acid—water aged for 2 months at 310 K were studied to determine conditions for calcium hydrogenurate hexahydrate, Ca(C₅H₃N₄O)₂ · 6H₂O precipitation. The precipitates were identified by chemical and thermogravimetric analyses, x-ray powder diffraction, infrared spectroscopy, light microscopy, and scanning electron microscopy. In the precipitation diagram the concentration region in which calcium hydrogenurate hexahydrate precipitated as a single solid phase was established.The solubility of calcium hydrogenurate hexahydrate was investigated in the pH range from 6.2 to 10.1 at different temperatures. The total soluble and ionic concentration of calcium (atomic absorption spectroscopy and Ca-selective electrode), total urate concentration (spectrophotometry), and pH were determined in equilibrated solutions. The data are presented in the form of tables and chemical potential diagrams. By using these data the thermodynamic solubility products of calcium hydrogenurate hexahydrate, K_s = a(Ca²⁺) · a²(C₅H₃N₄O₃⁻), were determined: pKs=10.12±0.07at288K,pKs=9.81±0.09at298K,pKs=9.28±0.04at310K,andpKs=9.01±0.03at318K.The formation of calcium hydrogenurate hexahydrate crystals in urinary tract of patients with pathologically high concentrations of calcium and urates (hypercalciuria and hyperuricosiuria) is possible.     

沉淀碳酸钙(PCC)的发展及应用

简述碳酸钙的分类、用途、工业现状、国内外在碳酸钙多相合成体系流变学及转递行为、碳酸钙形成机理和形态控制技术以及结晶生长成核理论的研究成果 ,并讨论了碳酸钙粉末表面处理的方法、机理。对高档卷烟纸专用碳酸钙的性能要求进行了探讨     

化学沉淀法制备纳米硅酸钙及其在模拟体液中的活性行为

以Ca(NO3) 2 ·4H2 O和Na2 SiO3·9H2 O为原料 ,聚乙二醇为分散剂 ,采用化学沉淀方法制备了直径 4 0nm的无定型纳米硅酸钙粉末 ,80 0℃热处理后得到平均直径 10 0nm的 β 硅灰石粉末。把两种粉末压制成块浸泡在模拟体液中 ,研究了两种粉体在模拟体液中的生物活性行为。结果表明 :由于无定型硅酸钙具有比β 硅灰石小的颗粒尺寸 ,且处于亚稳态 ,Ca2 的活性较大 ,无定型硅酸钙具有比 β 硅灰石较高的生物活性。在无定型硅酸钙表面不仅沉积了羟基磷灰石 ,而且也沉积了碳酸钙 ,以致于在浸泡初期阶段阻止了羟基磷灰石的沉积。经长时间浸泡后 ,无定型硅酸钙和 β 硅灰石表面都能沉积一层羟基磷灰石。     

Properties of Calcium Phosphate Cements With Different Tetracalcium Phosphate and Dicalcium Phosphate Anhydrous Molar Ratios

Calcium phosphate cements (CPCs) were prepared using mixtures of tetracalcium phosphate (TTCP) and dicalcium phosphate anhydrous (DCPA), with TTCP/DCPA molar ratios of 1/1, 1/2, or 1/3, with the powder and water as the liquid. Diametral tensile strength (DTS), porosity, and phase composition (powder x-ray diffraction) were determined after the set specimens have been immersed in a physiological-like solution (PLS) for 1 d, 5 d, and 10 d. Cement dissolution rates in an acidified PLS were measured using a dual constant composition method. Setting times ((30 ± 1) min) were the same for all cements. DTS decreased with decreasing TTCP/DCPA ratio and, in some cases, also decreased with PLS immersion time. Porosity and hydroxyapatite (HA) formation increased with PLS immersion time. Cements with TTCP/DCPA ratios of 1/2 and 1/3, which formed calcium-deficient HA, dissolved more rapidly than the cement with a ratio of 1/1. In conclusion, cements may be prepared with a range of TTCP/DCPA ratios, and those with lower ratio had lower strengths but dissolved more rapidly in acidified PLS.     

乙醇/水混合溶剂沉淀制备纳米SrF_2及其粒径控制

本文采用水/乙醇混合溶剂沉淀法,制备了不同粒径的SrF2纳米粉体,也在不同pH值的水溶液和不同表面活性剂CTAB、SDS的水溶液中,研究制备了纳米SrF2。用XRD、TEM观测分析了粉体的粒径和形貌。在纯水和水/乙醇体积比3∶1,1∶1,3∶5,1∶4的混合溶剂中,获得SrF2沉淀的粒径分别为32nm,19nm,23nm,16nm和13nm,粒径总体上随混合溶剂中乙醇含量升高而减小,其分散性和形貌规则性也随乙醇含量升高而变好。水溶液的pH值和表面活性剂对SrF2沉淀粒径无明显影响,相比之下,混合溶剂对粒径的影响显著。     

Preparation of Nanocrystalline ZrO2 Film Using a Zirconium Naphthenate and In Vitro Formation of Calcium Phosphate

Bioactive nanocrystalline ZrO₂ coatings were prepared onto (100) Si substrates by using a chemical solution deposition with a zirconium naphthenate as a starting material. Precursor sol was spin-coated onto the substrates and prefired at 500°C for 10 min in air. Formation of crystalline ZrO₂ film was observed at 800°C by X-ray diffraction. Surface morphology and surface roughness of the film were characterized by field emission-scanning electron microscope and atomic force microscope. After soaking for 5 days in a simulated body fluid, formation of the calcium phosphate was observed on ZrO₂ film annealed at 800°C by energy dispersive X-ray spectrometer. Fourier transform infrared spectroscopy revealed that carbonate was substituted into the calcium phosphate.     

添加H2对SiH4/N2/Ar等离子体淀积的氮化硅电学和光学特性的影响

研究了加H2对SiH4/N2/Ar高密度、低离子能量的等离子体淀积的氮化硅薄膜(淀积的衬底温度为400℃)电学和光学性能的影响。实验结果表明,加入H2使氮化硅薄膜的光学带隙增加,其折射率以及在氢氟酸缓冲液中腐蚀速率减小,而XPS测试的N、Si原子比没有改变,均为1.3。FTIR测量表明,样品中Si-H键的密度低于仪器检测限,而添加H2的样品中N-H键密度稍增加。此外,由淀积的氮化硅膜构成的MIS结构的高频C-V测试(1 MHz)显示,当氢气流量从零增加到8sccm时,高频C-V的回滞幅度从(0.40±0.05)V降低到(0.10±0.01)V。基于这些实验结果和理论分析,表明了加适量H2能够促进弱的Si-Si键以及Si和N的悬挂键向Si-N键转化。     

Preparation and Properties of Nanoparticles of Calcium Phosphates With Various Ca/P Ratios

This study aimed at preparing and studying the properties of nanoparticles of calcium phosphate (nCaP) with Ca/P ratios ranging from 1.0 to 1.67 using a spray-drying technique. Micro-structural analyses suggested that the nCaPs with Ca/P ratios of 1.67 to 1.33 were nano-sized amorphous calcium phosphate (ACP) containing varying amounts of acid phosphate and carbonate. The nCaP with Ca/P ratio of 1 contained only nano-sized low crystalline dicalcium phosphate (DCP). BET measurements of the nCaPs showed specific surface areas of (12 ± 2 to 50 ± 1) m(2)/g, corresponding to estimated equivalent spherical diameters of (38 to 172) nm. However, dynamic light scattering measurements revealed much larger particles of (380 ± 49 to 768 ± 111) nm, owing to agglomeration of the smaller primary nano particles as revealed by Scanning Electron Microscopy (SEM). Thermodynamic solubility measurements showed that the nCaPs with Ca/P ratio of 1.33 - 1.67 all have similar solubility behavior. The materials were more soluble than the crystalline hydroxyapatite (HA) at pH greater than about 4.7, and more soluble than β-tricalcium phosphate (β-TCP), octacalcium phosphate (OCP) and DCP at pH above 5.5. Their solubility approached that of α-tricalcium phosphate (α-TCP) at about pH 7. These nCaPs, which cannot be readily prepared by other currently available methods for nanoparticle preparation, have potential biomedical applications.     

Structural and electrical characteristics of chemical solution derived (Bi3.2La0.4Nd0.4)Ti3O12 thin films

(Bi_3.2La_0.4Nd_0.4)Ti₃O₁₂ (BLNT) thin films were prepared on Pt/Ti/SiO₂/Si substrates by using chemical solution deposition technique, and the effects of annealing temperatures in the range of 550-750 °C on structure and electrical properties of the thin films were investigated. X-ray diffraction analysis shows that the thin films have a bismuth-layered perovskite structure with preferred (117) orientation. The surface morphology observation by field-emission scanning electron microscopy confirms that films are dense and smooth with uniformly distributed grains. The grain size of the thin films increases with increasing annealing temperature; meanwhile, the structural distortion of the thin films also increases. It was demonstrated that the thin films show good electrical properties. The dielectric constant and dielectric loss are 191 and 0.028, respectively, at 10 kHz for the thin film annealed at 600 °C, and the 2Pr value of the thin film annealed at 700 °C is 20.5 μC/cm² at an electric field of 500 kV/cm.     

化学溶液沉积法制备Nd和Sc/Al/( Sc,Al)共掺杂钛酸铋铁电薄膜的电性能研究

利用化学溶液沉积法在Pt/Ti/SiO2/Si(100)基底和700℃条件下分别制备了Nd和Sc/Al/( Sc,Al)共掺杂的钛酸铋薄膜Bi3.15 Nd0.85 Ti2.94 Sc0.06O12 (BNTSc)、Bi3.15 Nd0.85 Ti2.94 Al0.06O12(BNTAl)和Bi3.15Nd0.85 Ti2.94(Sc0.03,Al0.03)O12(BNT(Sc,Al)),并研究和对比了这一系列薄膜的微结构、介电、铁电和漏电流等特性.结果发现BNT( Sc,Al)薄膜具有较高的剩余极化强度和介电常数,其漏电流密度低于BNTAl薄膜.另外,还讨论了相关的物理机制.     

Energy of Grain Boundaries of Different Type in fcc Solid Solutions,Ordered Alloys and Intermetallics with L12 Superstructure

The study of the triple junctions of the grain boundaries in some fcc solid solutions, ordered alloys and intermetallics with L12 has been carried out using the optical metallography and TEM methods. Two-types of the triple junctions were found in the alloys investigated (1), consisting of the boundaries of the random (RT), and (2), consisting of the RT boundary and the special boundaries (ST). The relative values of the RT and ST boundary energy were determined on the basis of the measurements of the angles between the grain boundary planes. It has been shown that the energy of ST boundaries increases with the increase of the stacking fault (SF) energy. The energy of the RT boundaries does not depend on the SF energy.     

N掺杂Cu2O薄膜的低温沉积及快速热退火研究

采用氧化亚铜(Cu_2O)陶瓷靶,利用射频磁控溅射沉积法在氮气和氩气的混合气氛下制备了N掺杂Cu_2O(Cu_2O∶N)薄膜,并在N_2气氛下对薄膜进行了快速热退火处理,研究了N_2流量和退火温度对Cu_2O∶N薄膜的生长行为、物相结构、表面形貌及光电性能的影响。结果显示,在衬底温度300℃、N_2流量12sccm条件下生长的薄膜为纯相Cu_2O薄膜;在N_2气氛下对预沉积薄膜进行快速热退火处理不影响薄膜的物相结构,薄膜的结晶质量随退火温度(450℃)的升高而显著改善;快速热退火处理能改善薄膜的结晶质量和缺陷,降低光生载流子的散射,增强载流子的传输,预沉积Cu_2O∶N薄膜经400℃退火处理后展示出较好的电性能,薄膜的霍尔迁移率(μ)为27.8cm~2·V~(-1)·s~(-1)、电阻率(ρ)为2.47×10~3Ω·cm。研究表明低温溅射沉积和快速热退火处理能有效改善Cu_2O∶N薄膜的光电性能。     

1mol/L HCl中不同浓度维生素B1和B6对碳钢的缓蚀性能及机理

通过研究盐酸硫胺(维生素B1),吡哆醇(维生素B6)作为缓独剂对碳钢的缓蚀行为及其作用机制,可为新型环境友好缓蚀剂的开发和应用提供一定的理论基础.利用失重法、极化曲线法和交流阻抗法、量子化学方法研究了不同浓度维生素B1和B6在1mol/L盐酸溶液中对Q235碳钢的缓蚀性能及机理.结果表明:碳钢的腐独速率随缓性剂浓度的增...