HA/SiO2/Fe2O3复合涂层的制备及其在 HEPES模拟体液中的生物活性

采用电泳沉积法制备了HA/CS/SiO2/Fe2O3复合涂层,经700℃烧结2 h后得到HA/SiO2/Fe2O3复合涂层,并通过FT-IR、SEM、EDS、XRD、万能材料试验机、电化学工作站进行测试与表征。同时研究了HA/SiO2/Fe2O3复合涂层材料对枯草芽孢杆菌的抑菌性能,采用2-[4-(2-羟乙基)-1-哌嗪基]乙磺酸(HEPES)模拟体液培养,对复合涂层的体外生物活性进行评价。实验结果表明,HA/SiO2/Fe2O3复合涂层与钛基体间的结合强度达31.9 MPa,在HEPES模拟体液中培养14 d后,复合涂层表面碳磷灰石化,同时复合涂层粉体对枯草芽孢杆菌的抑菌率达到81.9%。因此,HA/SiO2/Fe2O3复合涂层具有较强的结合强度和较高的生物活性,并且具有一定的抑菌性,有望开发成为人体骨骼替代植入材料。     

钛涂覆多孔羟基磷灰石/氧化铝生物陶瓷涂层的性能研究

通过电泳沉积的方法在生物医用钛基体表面制备羟基磷灰石(HA)/Al/壳聚糖(CS)复合涂层,通过高温烧结分解CS颗粒并制备钛基多孔HA/Al_2O_3复合生物陶瓷涂层。通过粘结-拉伸实验测定涂层与基材的结合强度;XRD和SEM对涂层的物相组成和形貌进行表征;CHI660C电化学工作站测试涂层在模拟体液中的耐蚀性能。研究表明,经过热处理后的涂层为表面可形成平均孔径为5μm的多孔HA/Al_2O_3,涂层厚度可达25μm,涂层中的HA颗粒致密粘连,Al在高温条件下反应成Al_2O_3从而使涂层与基体的结合强度最高可达30.5MPa,涂层的涂覆使Ti金属在人体模拟体液中具有良好的耐腐蚀能力。     

镁合金表面MAO/HA/CNTs涂层的电化学腐蚀性能

笔者采用化学沉淀法制备羟基磷灰石/碳纳米管复合粉体(HA/CNTs),并将这种复合粉体作为电解液的添加剂,采用微弧氧化的方法制备镁合金表面羟基磷灰石/碳纳米管(MAO/HA/CNTs)复合涂层。然后对制备的复合粉体分别采用扫描电子显微镜(SEM)、傅里叶红外光谱(FTIR)、X射线衍射分析(XRD)和电化学工作站研究其表面形貌、物相组成、以及对微弧氧化图层表面形貌和在模拟体液(SBF)中可以承受腐蚀的不同能力。研究结果显示,复合粉体在微弧氧化过程中均匀地沉积在镁合金表面,有很好的保护作用。所制备的羟基磷灰石/碳纳米管(HA/CNTs)复合粉体结晶良好,无任何杂质;电化学工作站中,MAO/HA/CNTs样品的腐蚀电位为-0.2～-2.0 V,通过在模拟体液中浸泡了7 d之后,其表面沉积了大量的亚纳米级的颗粒沉淀物,通过实验对镁基体和MAO样品进行试验,发现镁基体相比于MAO样品,具有的耐腐蚀性比较好,生物活性比较高。     

电泳沉积和反应结合制备羟基磷灰石/氧化铝复合涂层

在金属表面用电泳沉积(electrophoretic deposition, EPD)法制备羟基磷灰石(hydroxyapatite, HA)涂层的主要问题是结合强度较低.为了提高HA涂层与基体的结合强度,先采用EPD在钛表面制得羟基磷灰石/铝(hydroxyapatite/aluminum, HA/Al)复合涂层,然后采用反应结合方法(reaction bonding process)制备羟基磷灰石/氧化铝(hydroxyapatite/aluminum oxide, HA/Al2O3)复合涂层,并与相同条件下制备的HA单一涂层进行比较研究.用扫描电镜表征涂层的表面和横截面形貌.用能量散射X射线衍射(X-ray diffraction, XRD)谱分析HA/Al2O3复合涂层的化学组成.用XRD仪研究涂层的物相组成和热稳定性.通过黏结-拉伸实验测定HA涂层与基体的结合强度.结果表明:通过850℃热处理,HA/Al复合涂层中的Al粉发生氧化反应生成Al2O3,经反应结合得到HA/Al2O3复合涂层;反应结合提高了HA涂层的致密化程度且降低了基底钛表面的氧化程度;与单一HA涂层相比,HA/Al2O3复合涂层与基底间的结合强度得到明显提高.     

三乙醇胺浓度对HA/TiO_2梯度复合涂层性能的影响

研究了不同三乙醇胺(TEA)浓度悬浮液对电泳沉积法制备的羟基磷灰石(HA)/Ti O_2梯度复合涂层性能的影响,并分析了悬浮液中TEA的分散机理。研究表明:当悬浮液中三乙醇胺(简称TEA)的体积浓度为30 m L/L时,悬浮液中HA/Ti O_2的平均粒径最小(24.47 nm),Zeta电位最高(67.7 m V),说明此时悬浮液的稳定性最高,HA/Ti O_2梯度复合涂层表面形貌均匀,而且没有团聚和裂纹出现,其厚度均匀,大约在25μm左右;涂层Ca与P的元素原子比为1.76,与人体骨中的钙磷比十分接近;涂层在模拟体液中浸泡1 h后,腐蚀电位最高(37.88 m V),腐蚀电流密度最小(0.21 m A/cm2),说明此时涂层的耐腐蚀性最好;当悬浮液中TEA浓度为30 m L/L时,涂层结合强度最高,拉伸法测得此时HA/Ti O_2梯度复合涂层的结合力达到8.85 MPa。     

Fe_3O_4@SiO_2@TiO_2-AC光催化降解水源水中腐殖酸

采用共沉淀法耦合溶胶-凝胶法制备了核壳结构的磁性颗粒Fe_3O_4@SiO_2@Ti O_2,将其负载在活性炭(AC表面,制得新型光催化剂Fe_3O_4@SiO_2@Ti O_2-AC。采用SEM、FTIR、XRD、VSM对材料进行表征,并探究该催化剂对水中腐殖酸(HA)的去除效能。结果表明,以400 W高压汞灯作为光源,投加量为200 mg/L时,60 min内对初始质量浓度为5 mg/L、pH为7的含HA水样去除率可达96.1%。Fe_3O_4@SiO_2@Ti O_2-AC对HA的光催化降解符合LangmuirHinshelwood(L-H)动力学模型。Fe_3O_4@SiO_2@Ti O_2与AC存在协同作用,可有效增强复合光催化剂的催化效能。材料具有较好的催化稳定性,5次重复使用后,对水样中HA的去除率仍能达到84.7%。     

镁合金表面羟基磷灰石/介孔SiO_2自修复耐蚀涂层的研究

通过旋涂法,在AZ31镁合金表面制备了聚多巴胺/羟基磷灰石复合涂层,并将负载有缓蚀剂2-巯基苯并咪唑(MBI)的介孔SiO_2纳米颗粒掺杂到复合涂层中,以改善镁合金的耐腐蚀性能。使用SEM、TEM、XRD和BET等手段表征介孔SiO_2纳米颗粒的形貌、结构及缓蚀剂的负载情况;通过傅里叶红外光谱(FTIR)和扫描电子显微镜(SEM)对涂层的成分和形貌进行表征;使用电化学阻抗谱(EIS)研究了不同涂层的耐蚀性能和自修复性能。结果表明,制备的二氧化硅为介孔纳米颗粒,可负载缓蚀剂。将负载有缓蚀剂MBI的介孔SiO_2纳米颗粒掺杂到聚多巴胺/羟基磷灰石复合涂层中,能够改善涂层的耐蚀性能,使涂层具有自修复性能。     

镁合金表面羟基磷灰石/介孔SiO_2自修复耐蚀涂层的研究

通过旋涂法,在AZ31镁合金表面制备了聚多巴胺/羟基磷灰石复合涂层,并将负载有缓蚀剂2-巯基苯并咪唑(MBI)的介孔SiO_2纳米颗粒掺杂到复合涂层中,以改善镁合金的耐腐蚀性能。使用SEM、TEM、XRD和BET等手段表征介孔SiO_2纳米颗粒的形貌、结构及缓蚀剂的负载情况;通过傅里叶红外光谱(FTIR)和扫描电子显微镜(SEM)对涂层的成分和形貌进行表征;使用电化学阻抗谱(EIS)研究了不同涂层的耐蚀性能和自修复性能。结果表明,制备的二氧化硅为介孔纳米颗粒,可负载缓蚀剂。将负载有缓蚀剂MBI的介孔SiO_2纳米颗粒掺杂到聚多巴胺/羟基磷灰石复合涂层中,能够改善涂层的耐蚀性能,使涂层具有自修复性能。     

Fe3O4@SiO2@C@ZnO复合材料制备和 性能研究

采用溶剂热法制备了Fe_3O_4颗粒,并以CTAB为表面活性剂,采用改进后的St9ber法以及沉淀法制备出Fe_3O_4@SiO_2@C@ZnO的复合粉体材料。使用X射线衍射(XRD)和激光粒度,荧光光谱和热重分析等表征手段,结果证明SiO_2、ZnO和C层成功包覆在其表面。经磁性测试观察发现,Fe_3O_4@SiO_2@C@ZnO纳米颗粒有较好的磁性能;通过荧光光谱分析,结果表明该材料对于苯酚有较为优越的吸附性能。     

超级铝热剂Al/Fe_2O_3对硝化棉热分解特性的影响

采用水热法制备了纳米Fe_2O_3,并用超声分散法将其与纳米Al颗粒复合制备了超级铝热剂Al/Fe_2O_3,利用X-射线粉末衍射(XRD)、透射电子显微镜(TEM)、扫描电镜及能量散射光谱仪(SEM-EDS)对复合物的物相、组成、形貌和结构进行了分析表征,采用差示扫描量热法(DSC)和热红联用技术(TG-FTIR)研究了Al/Fe_2O_3对硝化棉(NC)热分解过程的影响。结果表明,Al/Fe_2O_3-NC和NC的热分解过程遵循Avrami-Erofeev方程f(α)=1.5(1-α)[-ln(1-α)]1/3;超级铝热剂Al/Fe_2O_3可降低硝化棉的表观活化能、临界点火温度和临界爆炸温度,在促进硝化棉O-NO_2键断裂和凝聚相二次自催化反应中起到至关重要的作用。     

Self-organized nano-crystallisation of BaF2 from Na2O/K2O/BaF2/Al2O3/SiO2 glasses

In glasses with the compositions (100 ? x)(2Na₂O·16K₂O·8Al₂O₃·74SiO₂)xBaF₂ (with x = 0 to 6), the glass transition temperature decreases with increasing BaF₂-concentration. Samples with x = 6 were thermally treated at temperatures in the range from 500 to 600 °C for 5–160 h. This leads to the crystallisation of BaF₂. The quantity of crystalline BaF₂ increases with increasing time of thermal treatment, while the mean crystallite size remains constant within the limits of error. The glass transformation temperature of partially crystallised samples increases with increasing crystallisation time and approaches a value equal to the temperature, at which the samples were treated. This is explained by the formation of a highly viscous layer enriched in SiO₂ which is formed during crystallisation. This layer acts as a diffusion barrier and hinders further crystal growth.     

Prediction of Immiscibility Boundaries of the Systems K2O-SiO2, K2O-Li20-SiO2, K20-Na2O-Si02, and K2O-BaO-SiO2

In earlier work, a prediction method of the immiscibility boundary of a ternary silicate glass system was developed involving two known binary immiscibility boundaries and a measured immiscibility temperature of one ternary glass composition. In the present work, the method is extended to the case where one of the two binary immiscibility boundaries is not known and is applied as an example to ternary silicate systems containing K₂O. First, the immiscibility boundary of the system K₂O-SiO₂ is estimated by measuring the immiscibility temperatures of three glasses in the system K₂O-Li₂O (or Na₂O)-SiO₂. Using this result the immiscibility boundaries of the systems K₂O-Li₂O-SiO₂, K₂O-Na₂O-SiO₂, and K₂O-BaO-SiO₂ are estimated. The results agree reasonably well with the experimentally determined immiscibility temperatures at selected compositions.     

The System Na2O-CaO-SiO2-H2O

A portion of the quaternary phase diagram for Na₂O-CaO-SiO₂-H₂O has been constructed. Plotting concentrations as their 10th roots allows compounds having solubilities which differ by several orders of magnitude to be represented on a single diagram. The compositional relationships among sodium-substituted calcium silicate hydrate, calcium-substituted sodium silicate hydrate, calcium bydroxide, a quaternary compound of approximate composition 0.25Na₂O · CaO · SiO₂· 3H₂O, sodium hydroxide monohydrate, and miscellaneous sodium silicate hydrates are presented. The quaternary diagram constructed shows the quaternary compound to exist in equilibrium with sodium-substituted calcium silicate hydrate and calcium hydroxide. Conditions in concrete pore solutions which favor the formation of this quaternary compound may also favor the occurrence of the alkali-silica reaction.     

复合固体超强酸SO42-/ZrO2-Al2O3催化合成乳酸正丁酯的研究

合成了几种不同Zr、Al原子比的SO42-/ZrO2-Al2O3复合固体超强酸,将其用于催化乳酸与正丁醇的酯化反应,均有较好的催化活性,尤以ZrAl=12的催化效果最好,经济性优于ZrO2超强酸催化剂.其最佳反应条件为酸醇摩尔比为13,催化剂用量为乳酸质量的10%,反应时间2～2.5h,酯化率达96.9%.该催化剂具有制备容易、催化活性高、不污染环境、可重复使用的优点.     

Some Properties of the System Na2O-NaF-B2O2-H2O

It was first shown that the enamel slips which have the best suspnding characteristics contain equal amounts of Na₂O and B₂O₃ and at least a moderate amount of NaF. The solubilities of mixtures of Na₂O, NaF, and B₂O₃ were then investigated. The pH of these solutions and the primary crystalline phases separating on evaporation also were determined. The solubility data obtained at room temperature were summarized. When the solutions were evaporated, NaF was the first crystalline phase to separate from a large proportion of the mixtures investigated. It was concluded that the desirable handling characteristics of enamels whose mill liquors contain the proper proportion of Na₂O, NaF, and B₂O₃ are not due to the formation of complex salts but to the following combination of properties: (1) the presence of salts with a moderate solubility which changes very slightly with temperature, (2) a moderate pH of about 10 in a probably well-buffered solution, (3) a relatively stable crystalline material, NaF, as a primary phase, and (4) a secondary phase which crystallizes slowly with relatively little shrinkage.     

固体超强酸SO^2—4／TiO2催化合成尿囊素的研究

用固体超强酸SO42/TiO2为催化剂,以尿素和乙醛酸为原料合成了尿囊素。得到最佳条件为TiO2在1mo1·L-1H2SO4溶液中浸渍12h,再在600℃焙烧3h;尿素与乙醛酸摩尔比3.51,催化剂9％,时间3h,温度72℃～75℃,产率达57.4％。     

Photocatalytic activity of Cu2O/TiO2, Bi2O3/TiO2 and ZnMn2O4/TiO2 heterojunctions

Cu₂O/TiO₂, Bi₂O₃/TiO₂ and ZnMn₂O₄/TiO₂ heterojunctions were studied for potential applications in water decontamination technology and their capacity to induce an oxidation process under VIS light. UV–vis spectroscopy analysis showed that the junctions-based Cu₂O, Bi₂O₃ and ZnMn₂O₄ are able to absorb a large part of visible light (respectively, up to 650, 460 and 1000 nm). This fact was confirmed in the case of Cu₂O/TiO₂ and Bi₂O₃/TiO₂ by photocatalytic experiments performed under visible light. A part of the charge recombination that can take place when both semiconductors are excited was observed when a photocatalytic experiment was performed under UV–vis illumination. Orange II, 4-hydroxybenzoic and benzamide were used as pollutants in the experiment. Photoactivity of the junctions was found to be strongly dependent on the substrate. The different phenomena that were observed in each case are discussed.     

Phase Diagrams for the Systems MgCl2-MgF2, CaCl2-MgF2, and NaCl-MgF2

Equilibrium phase diagrams for the systems MgCl₂-MgF₂, CaCl₂-MgF₂ and NaCl-MgF₂ were determined by differential thermal analysis, thermal analysis, and temperature-composition equilibrium techniques. Simple eutectics were observed at 78.0±0.5 mol% MgCl₂ and 628°±2°C in the MgCl₂-MgF₂ system, at 87.5±0.5 mol% CaCl₂ and 694°±2°C in the CaCl₂-MgF₂ system, and at 95.5±0.5 mol% NaCl and 786°±3°C in the NaCl-MgF₂ system. The phase diagrams determined for these systems were compared with phase diagrams that were computed using Temkin's model. The phase diagrams of the CaCl₂-MgF₂ and NaCl-MgF₂ systems were also compared with diagrams that were computed using the expression suggested by Flood et al. for reciprocal systems. The experimentally determined and computed phase diagrams agreed for the MgCl₂-MgF₂ system but not for the CaCl₂-MgF₂ and NaCl-MgF₂ systems.     

Crystallization of zeolite L from Na2O-K2O-Al2O3-SiO2-H2O system

Zeolite L powder was prepared from the substrate mixture of Na₂O-K₂O-Al₂O₃-SiO₂-H₂O system at temperatures of 373-443 K. In order to investigate the factors which influence the synthesis outcome, a reference system which yields zeolite L in a reproducible manner was chosen and subjected to controlled changes in synthesis parameters. The crystalline zeolite L samples obtained were characterized by elemental chemical analysis, X-ray diffraction (XRD), and scanning electron microscopy (SEM). It was established that phase purity, morphology, and the size of crystals of crystalline product were affected by molar ratios of the substrate, such as SiO₂/Al₂O₃, (K₂O+Na₂O)/SiO₂, Na₂O/(K₂O+Na₂O), and H₂O/(K₂O+Na₂O). Amorphous silica powder (Zeosil) was the preferred silica source, and the crystallization rate was promoted by introducing gel aging, seeding, and rapid heating rate.