水热电沉积法制备羟基磷灰石/氧化钛复合涂层的研究

采用水热电沉积法．在钛金属基体￡：成功制备了羟基磷灰石(hydroxyapatite,HA)氧化钛(HA／TiO2)复合涂层．对涂层的表面形貌、相组成、TiO2共沉积量、热稳定性和结合强度进iir研究。实验结果表明：复合涂层具有较均匀的微观结构。TiO2的加入明显改善了涂层与基体的结合强度．涂层中TiO2含量越高．结合强度的提高也越显著。在200℃．100g／L TiO2条件下．电沉积制备的HA／TiO2复合涂层的结合强度为21.0MPa,约为纯HA涂层的2倍。TiO2共沉积量随电解液中TiO2浓度的提高逐渐增加;随电解液温度的提高先增后降,在160C达到最大。涂层经800℃热处理后,TiO2促使HA部分分解为β-磷酸钙(β-tricalciumphosphate,β-TCP)和CaO;经1200℃热处理后,HA和TiO2发生相互作用生成α-TCP和CaTiO3。     

溶胶凝胶法制备羟基磷灰石/TiO2复合生物活性涂层的研究

通过溶胶凝胶法在纯钛基体上制备了羟基磷灰石/TiO2复合生物活性涂层.HA可以提高钛基的生物活性,TiO2可以提高涂层与基体的物理、化学相容性和结合强度.HA和TiO2溶胶由前驱体制得,按不同物质的量比直接混合两种溶胶来制备复合溶胶.使用XRD、SEM研究了不同温度下热处理后涂层的组成和结构.实验结果表明HA的结晶度和晶粒随着温度的升高而提高和变大;涂层表面为连续多孔结构.粘结拉伸结果表明复合涂层与基体结合良好,较纯HA涂层与基体的结合强度有较大提高.复合涂层试样于SBF中浸泡2d、7d和14d的SEM分析结果表明复合涂层表面的磷灰石形成量较高.电位动力学曲线分析表明复合涂层可以提高基体的耐蚀性.     

熔烧温度对Al-SiC硅酸盐基陶瓷涂层性能的影响

以硅酸盐溶液为基料,添加金属Al粉、SiC、TiO₂、玻璃料等陶瓷骨料,采用高温熔烧法在304不锈钢表面制备了硅酸盐基陶瓷涂层,使用扫描电子显微镜(SEM)、热重分析仪(TG)、X射线衍射仪(XRD)等研究了熔烧温度对涂层性能的影响。结果表明,涂层在700~1 100 ℃熔烧过程中,陶瓷涂层与金属基体之间呈冶金结合,伴随有Al₂O₃和TiO₂的晶相转变;涂层厚度为150 μm,并在800 ℃熔烧固化时,结合强度最高,为23.3 MPa;涂层经1 000 ℃高温熔烧后剩余固体含量为76.7%,表现出良好的耐高温性。     

钙添加剂对Na2CO3催化高铝煤焦水蒸气气化反应性的影响

以孙家壕高铝煤为实验煤样,将煤样在800℃制成煤焦,采用热重分析仪(TGA)研究了钙添加剂对孙家壕煤焦Na₂CO₃催化水蒸气气化反应性的影响。结果表明：Ca(OH)₂对孙家壕煤焦水蒸气气化具有催化作用,在对孙家壕煤焦进行800℃Ca(OH)₂催化水蒸气气化时,Ca(OH)₂的负载量在15%(质量分数,下同)时达到饱和;通过比较Na₂CO₃和Ca(OH)₂对孙家壕煤焦800℃水蒸气气化的催化活性,发现Na₂CO₃的催化气化活性比Ca(OH)₂的催化气化活性大,负载5%Na₂CO₃和10%Ca(OH)₂的孙家壕焦的800℃水蒸气气化反应性相等;添加10%Ca(OH)₂添加剂可以使负载10%Na₂CO₃的孙家壕煤焦在700℃...     

氧化铝基体上羟基磷灰石/氟羟基磷灰石双层涂层的制备及性能

通过涂覆-烧结法在氧化铝(Al_2O_3)表面制得羟基磷灰石(HA)/氟羟基磷灰石(FHA)双层涂层,HA和FHA重复沉积在氧化铝基体上形成均匀涂层,然后在1300 ℃进行热处理.在此过程中,如果没有FHA中间层,HA会和Al_2O_3发生严重的反应,形成磷酸三钙和钙铝化合物.SEM、XRD及粘接拉伸试验表明:FHA中间层能有效地抑制HA与Al_2O_3的反应,所获得的双层涂层具有多孔粗糙的表面,但与Al_2O_3基体结合紧密.涂层经1300 ℃热处理后,其结合强度约为30 MPa.     

纯钛表面电沉积羟基磷灰石复合涂层组织及性能

采用水热电沉积法在纯钛基体表面制备前驱体,对其进行碱液处理和真空热处理后得到羟基磷灰石(HA)复合涂层.采用XRD、SEM和激光共聚焦显微镜分析涂层物相结构、组织形貌,利用热震法和模拟体液浸泡法表征涂层结合强度和生物活性.实验结果表明:前驱体主要成分为CaHPO4·2H2O、Ca3(PO4)2和CaTiO3,经室温碱液处理10 h后,涂层物相由Ca10(PO4)6(OH)2(简称:HA)、Ca3(PO4)2和CaTiO3组成,组织形貌由前驱体的块状转变为细针状HA晶体.当温度一定时,涂层厚度在4.5 V电压下达到最大值38μm,热震次数在4 V电压下达到最大值11次;当电压一定时,涂层厚度在40℃和50℃下均为最大值35μm,热震次数在40℃下达到最大值11次.沉积电压为4 V、水浴温度为40℃工艺条件下的涂层经体外生物活性测试表明:HA复合涂层表面可在模拟体液中形成新的HA晶核,并不断长大.     

医用Ti合金表面生物玻璃涂层的制备与研究

在医用Ti合金表面涂覆一层生物玻璃涂层可阻止金属离子的溶出并且提高其生物活性。本文采用溶胶-凝胶法在Ti合金基体上制备了SiO2-CaO-MgO-P2O5系生物玻璃涂层。利用差示量热扫描仪(DSC)、扫描电镜(SEM)、拉伸试验和模拟体液(SBF)浸泡等手段系统研究了涂层的表面形貌、粘附性能及生物活性。结果表明:热处理温度为800℃时涂层与基体间的粘附强度最大,涂层越薄涂层与基体间的粘附强度越大;在模拟体液中浸泡30天后,材料表面生成了大量磷灰石。用溶胶-凝胶法可在Ti合金基体上制备出SiO2-CaO-MgO-P2O5系生物活性高的生物玻璃涂层。     

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.     

NiO/MgO整体式催化剂上甲烷部分氧化制备合成气

甲烷部分氧化制备合成气反应过程具有反应速率快、能耗低和H₂与CO物质的量比适用于合成甲醇及F-T合成等优点,是一种有希望替代传统水蒸汽重整的方法。研究在NiO/MgO蜂窝陶瓷整体式催化剂上的甲烷部分氧化过程,主要考察涂层载体、活性组分Ni含量、涂层载体前驱体、焙烧温度和还原温度对催化剂反应性能的影响。采用XRD、H₂-TPR和N2吸附等表征前驱体及其负载活性组分NiO后的晶相、还原特性和吸附性能。结果表明,采用浸渍法制备催化剂时,Mg(NO₃)₂为涂层载体MgO前驱体,在NiO负载质量分数20%、焙烧温度（500~600） ℃和还原温度750 ℃条件下制备的催化剂NiO/MgO-N性能较好,活性较稳定;以NiO/MgO-N为催化剂,在反应温度800 ℃、n(O₂)∶n(CH₄)＝0.5和空速9 723 h^-1条件下,CH₄转化率94.4%,H₂选择性99.9%,CO选择性92.9%。     

AlF3-CsH5(PO4)2中温质子导体电解质的制备及性能

提出了一种磷酸五氢铯(CsH₅(PO₄)₂)与氟化铝(AlF₃)形成P-OH…F氢键的方法,同步提高了固体质子导体CsH₅(PO₄)₂的热机械稳定性和导电率。结果表明,AlF₃-CsH₅(PO₄)₂复合电解质即使在250℃的高温下也能保持坚固的固态,这比纯CsH₅(PO₄)₂的熔化温度提高了100℃。同时,在AlF₃-CsH₅(PO₄)₂复合电解质中,由于P-OH…F氢键的协同作用和CsH₅(PO₄)₂固有的质子导电性能,使得AlF₃-CsH₅(PO₄)_2<...     

Electrodeposition of graphene oxide-hydroxyapatite composite coating on titanium substrate

In this work, graphene oxide (GO)/hydroxyapatite (HA) composite coatings were successfully prepared on titanium substrate by electrophoretic deposition technology. Subsequently, microstructure, phase composition, adhesion strength, hydrophilicity, corrosion resistance, bioactivity, antibacterial activity and biocompatibility of the coating were evaluated. The adhesion strength of coating increased by 76% from 6.46 MPa to 17.81 MPa with 0 wt% GO to 12 wt% GO and the corrosion rate of coating with 8 wt% GO was achieved at the minima of (1.493 × 10^-3mm/a). Biomineralization experiment indicated the excellent bioactivity of GO/HA composite coatings. The water contact angle of the composite coatings increased from 20.6°(0 wt% GO) to 38.1°(12 wt%GO). The antibacterial rates of coating with 5 wt% GO was 96.7%, while declined to 25% after thermal treatment. In-vitro L929 cell culture experiments indicated the composite coatings with 5 wt% GO exhibited good biocompatibility.     

Ternary hydroxyapatite/chitosan/graphene oxide composite coating on AZ91D magnesium alloy by electrophoretic deposition

In this work, ternary HA/chitosan/graphene oxide (GO) coating was applied via electrophoretic deposition on AZ91D magnesium alloy as bone implants, successfully. Subsequently, phase composition, surface morphology, hardness, corrosion behavior, bioactivity and antibacterial of the composite coatings were studied. Hardness and Young's modulus of the composite coatings increased from 40 ± 1.5 MPa and 3.1 ± 0.42 GPa to 60 ± 3.12 MPa and 8 ± 0.53 GPa for composite coatings with 0 and 2 wt% GO, respectively. The results of the SBF solution soaking of the composites after 24 days, indicated the improvement of HA growth due to the increasing of the GO addition in composite coating. New HA grains with leaf-like morphology grew uniformly at higher amounts of GO (1 and 2 %wt) in a perfectly balanced composition. Rate of the substrate corrosion significantly decreased from 4.3 to 0.2 (mpy), when the amount of GO increased from 0 to 2 wt% due to reduction of the surface cracks at the presence of the GO reinforcement. Also, there was no Escherichia coli and Staphylococcus aureus bacteria growth in broth medium after 24 h and OD₆₀₀ results at 24 h post inoculation for the 2%wt GO addition in coating.     

Mechanical and Biological Performance of Calcium Phosphate Coatings on Porous Bone Scaffold

Composite coatings, consisting of calcium phosphate (CaP) ceramics and phosphate-based glass (P-glass), were obtained on a strong ZrO₂ porous scaffold to improve biocompatibility by combining mechanical properties and biological activity. Powder mixtures of hydroxyapatite (HA) and P-glass in varying composition and content were dip-coated on a ZrO₂ porous scaffold and heat-treated above 800°C for 2 h in air. During thermal treatment, substantial reaction and crystallization occurred, resulting in coating phases of HA, tricalcium phosphate (TCP), dicalcium phosphate (DCP), and surrounding glass. The CaP-glass coating layer was highly dense and uniform and adhered firmly to the ZrO₂ scaffold. The adhesion strength of the coating layer as tested on a nonporous disk increased with increasing glass addition and decreasing CaO content in glass. The highest strength was about 40 MPa, an improvement of twice as high as that of pure HA coating. The osteoblastic cells grew and spread actively through the coated scaffolds. The differentiation of cells on the CaP coatings was much higher than that on ZrO₂ substrate and comparable to or slightly higher than that on pure HA coating.     

二氧化硅气凝胶隔热复合材料的高温疏水改性及失效机制

SiO₂气凝胶隔热复合材料已经广泛应用于航空航天、石油化工等隔热保温领域,通过疏水改性可大幅拓展其应用场景。为了使SiO₂气凝胶隔热复合材料在更高温度仍保持良好的疏水性能,采用聚硅氧烷改性硅酸盐涂料对SiO₂气凝胶隔热复合材料进行表面刷涂疏水改性,然后研究了涂层厚度对裂纹扩张的影响以及涂层在高温下疏水性能的失效机制和刷涂改性前后复合材料的耐磨损性能。结果表明,当涂层厚度大约为13 μm时,所制备的涂层表面无裂纹,接触角可达(113±2)°,经450 ℃高温热处理1 800 s后接触角依然可以保持在105°左右,表现出良好的热稳定性,同时涂层显著提高了复合材料的耐磨损性能。     

Processing and Performance of Hydroxyapatite/Fluorapatite Double Layer Coating on Zirconia by the Powder Slurry Method

A hydroxyapatite/fluorapatite (HA/FA) double layer was coated on ZrO₂ by a powder slurry method. The FA layer between the HA layer and the ZrO₂ substrate was effective in suppressing the reaction between HA and ZrO₂. The rheological properties of the slurry and the thermal treatment conditions were optimized. Addition of small amounts of tri-ethyl phosphate dispersant and polyvinylbutyral binder (up to 5 wt%) was effective in reducing the slurry viscosity, even at high loadings of HA powder. Each layer (HA, FA) was deposited on ZrO₂ repeatedly to induce a uniform layer, and the final heat treatment was carried out above 1200°C to consolidate the coating layer. During this process, without the FA-intermediate layer, a severe reaction between HA and ZrO₂ occurred to form tri-calcium phosphate and CaZrO₃ products. However, the presence of the FA layer between HA and ZrO₂ effectively suppressed the reaction up to 1300°C. The obtained HA/FA double coating layer was micro-porous and relatively rough, but was firmly adhered to the ZrO₂ substrate, having a bonding strength of approximately 25 MPa after heat treatment above 1200°C. The osteoblast-like cells cultured on the HA/FA coating layer spread and proliferated favorably, having a cell proliferation rate comparable to that of a plastic control and HA bulk ceramic.     

Effects of Sn residue on the high temperature stability of the H_2-permeable palladium membranes prepared by electroless plating on Al_2O_3 substrate after SnCl_2–PdCl_2 process: A case study

The stability of composite palladium membranes is of key importance for their application in hydrogen energy systems. Most of these membranes are prepared by electroless plating, and beforehand the substrate surface is activated by a SnCl_2–PdCl_2 process, but this process leads to a residue of Sn, which has been reported to be harmful to the membrane stability. In this work, the Pd/Al_2O_3 membranes were prepared by electroless plating after the SnCl_2–PdCl_2 process. The amount of Sn residue was adjusted by the SnCl_2 concentration, activation times and additional Sn(OH)_2coating. The surface morphology, cross-sectional structure and elemental composition were analyzed by scanning electron microscopy(SEM), metallography and energy dispersive spectroscopy(EDS), respectively. Hydrogen permeation stability of the prepared palladium membranes were tested at450–600 °C for 400 h. It was found that the higher SnCl_2 concentration and activation times enlarged the Sn residue amount and led to a lower initial selectivity but a better membrane stability. Moreover, the additional Sn(OH)_2coating on the Al_2O_3 substrate surface also greatly improved the membrane selectivity and stability.Therefore, it can be concluded that the Sn residue from the SnCl_2–PdCl_2 process cannot be a main factor for the stability of the composite palladium membranes at high temperatures.     

硼化钽增强聚醚醚酮复合涂层的制备及性能评价

采用阴极电泳沉积技术在纯钛基板表面沉积聚醚醚酮（PEEK）/硼化钽（TaB₂）复合涂层。采用透射电子显微镜、扫描电子显微镜、X射线衍射仪和摩擦磨损试验机等方式对电泳沉积液分散性、PEEK/TaB₂复合涂层表面形貌、微观结构、结晶行为、摩擦学性能和生物学性能进行表征。结果表明，通过调节电泳沉积参数可以制备形貌均匀、具有一定厚度的PEEK/TaB₂复合涂层，在390 ℃热处理后，涂层均匀致密无孔隙；热处理可以提高PEEK/TaB₂涂层的结晶性能，TaB₂颗粒的加入使PEEK涂层获得更高的结晶度；添加较低含量的TaB₂颗粒时，复合涂层在小牛血清（fetal bovine serum，FBS）介质中表现出良好的摩擦学性能，与纯PEEK涂层相比，磨损率分别下降了48.1 %，69.1 %；但过量TaB₂颗粒在PEEK基质中出现明显的团聚现象， 摩擦系数和磨损率呈现上升趋势；细胞实验表明，TaB₂良好的生物活性促进了样品表面细胞增殖。     

Al（OH）3@Zn（OH）2双层包覆氧化铁黄合成及其耐热性能研究

采用共沉淀法对铁黄颜料进行Al（OH）₃/Zn（OH）₂双层异相包覆,提升其耐热性能,并通过XRD、TG-DTA、FT-IR、SEM&EDS等手段对包覆前后铁黄颜料的微观结构进行表征。研究结果表明,包覆质量分数为40%的Al（OH）₃时铁黄颜料的耐热性能较好;第二层包覆Zn（OH）₂,最优包覆质量分数为30%,样品在240 ℃时色差值为1.84。XRD测试结果表明,Al（OH）₃和Zn（OH）₂包覆并没有改变氧化铁黄的特征峰,两者可能以无定形态包覆在铁黄粒子表面。SEM、EDS、FT-IR测试表明,Al（OH）₃/Zn（OH）₂已成功对铁黄颜料进行了包覆;此外,还出现了片状结构对应Al（OH）₃自身成核现象,包锌后出现了团聚现象。TG-DTA表征显示,包覆后样品升温脱水分两步,低温吸热峰对应包覆层物质的脱水,高温吸热峰偏向更高温度,对应包覆颜料耐热性能的提升。     

Nano-Sized Hydroxyapatite Coatings on Ti Substrate with TiO2 Buffer Layer by E-beam Deposition

A nano-sized hydroxyapatite (HA) layer was coated on a Ti substrate with a titanium oxide (TiO₂) buffer layer by the electron-beam deposition method. The morphological features as well as the mechanical and biological properties of the HA/TiO₂-layered coating were noticeably different from those of a conventional HA coating on Ti. The HA on the TiO₂ layer replicated the fine grain structure of the TiO₂ layer, with grain sizes of just a few tens of nanometers. The TiO₂ buffer layer was highly effective in preserving the adhesion strength of the coating layer following the heat treatment at 500°C, which was necessary to crystallize the structure. Moreover, in contrast to the HA single coating wherein severe cracking was observed under moist conditions, the HA/TiO₂ coating retained its mechanical stability under the same conditions. The dissolution of the HA/TiO₂ coating in a physiological saline solution exhibited a more favorable pattern than that of the HA single coating, with a reduced initial burst and a subsequent steady release rate. Preliminary in vitro cellular tests showed that osteoblastic cells expressed a significantly higher alkaline phosphatase level on the HA/TiO₂ coating than on the HA single coating. Conclusively, the nano-sized HA coating with the TiO₂ buffer layer holds great promise as a bioactive coating system.