Structure stability and corrosion resistance of nano-TiO2 coatings on aluminum in seawater by a vacuum dip-coating method

A stable nano-TiO₂ coating was prepared by vacuum dip-coating TiO₂ sol-gel onto the anodized aluminum surface. The effect of vacuum dip-coating method and anodization pretreatment on compactness and stability of the coatings was proved. The structure and composition of the coatings were characterized by means of scanning electron microscopy (SEM) and X-ray diffraction (XRD). The results indicate that the surface of coatings is uniform and compact, with high load capacity. The particles of TiO₂ anatase is filled into the Al₂O₃ nano-pores formed by anodization. The electrochemical measurements show that the nano-TiO₂ coatings significantly decrease the corrosion currents densities (i_corr), as simultaneously increased the values of polarization resistance (R_t) of aluminum. It indicates the nano-TiO₂ coatings exhibit excellent anticorrosion properties in sterile seawater at the room temperature.     

铝合金表面MoS2/Al2O3复合涂层制备及减摩性能研究

铝合金表面减摩涂层设计和制备是改善铝合金构件摩擦性能的关键技术之一。对于目前铝合金结构件易磨损的问题,本研究采用微弧氧化一步法在6063铝合金表面原位合成纳米MoS2,制备具有减摩作用的MoS2/Al2O3复合陶瓷涂层;讨论了硫盐浓度对涂层成分、形貌及摩擦性能的影响,分析了涂层减摩机理。结果表明：通过微弧氧化在6063铝合金表面成功制备出了含有MoS2的自润滑复合陶瓷涂层;涂层的摩擦系数随着硫盐浓度的升高呈现先下降后上升的趋势,当电解液中硫盐浓度为15g/L时涂层的摩擦系数为0.15,较常规微弧氧化涂层降低了76%。涂层中的MoS2分布在涂层的表面和内部,在与摩擦副接触与挤压的作用下形成均匀分布的MoS2润滑膜,表现出良好的减摩性能。     

ZL104合金表面化学镀镍磷合金层的研究

在ＺＬ１０４合金表面上进行Ｎｉ－Ｐ与Ｎｉ－Ｃｕ－Ｐ化学镀,以提高ＺＬ１０４合金材料的耐蚀性与耐磨性。结果表明：化学镀可以显著提高ＺＬ１０４合金表面的硬度,并改善其在５％ＮａＣｌ溶液中的耐蚀性;在２００～５２０℃温度下热处理后,镀层的硬度显著提高,但耐蚀性略有降低,这可能与镀层中的析出物Ｎｉ３Ｐ析出有关。     

Ce(SO4)2浓度对电喷镀Ni-W-Ce合金镀层性能影响

为了研究Ce(SO4)2浓度与合金镀层表面性能的关系,采用喷射电沉积法制备了一系列Ni-W-Ce合金镀层工件。用扫描电镜(SEM)观察了镀层的表面结构,并用能谱仪(EDS)检测镀层中的元素组成。XRD分析表明,镀层存在晶格畸变。LEXT4100激光共焦显微镜观察磨损痕迹,发现磨损机理发生了变化。结果表明,添加Ce(SO4)2改善了涂层的表面微观形貌,当浓度为0.5g/L时,涂层的表面质量最佳。同时,显微硬度、耐磨性和耐腐蚀性随浓度的增加呈现先好后坏的规律。当Ce(SO4)2浓度为0.5g/L时,显微硬度达到峰值519.69HV0.1。此时,镀层耐磨性最好,其耐磨性表征参数均取得最小值。且镀层的耐蚀性也最好,腐蚀电位为-0.5537V,电弧电抗半径最小。     

A study on water absorption in freestanding polyurethane films filled with nano-TiO2 pigments by capacitance measurements

The electrochemical impedance spectroscopy (EIS) was used to evaluate the water transport and dielectric properties of polyurethane films filled with nano-TiO₂ at different pigment/base (P/B) values in 0.5~mol/L NaCl solutions. EIS results were compared with gravimetric measurements on the freestanding films. The amount of water absorption showed great discrepancy between the two methods. The diffusion coefficient in the polyurethane film with P/B=30% was the smallest among those filled with nano-TiO₂ pigments. The dielectric constant  ε of the polyurethane varnish film obtained from the initial capacitance was in the range of typical values of polymers. SEM was used to measure the distribution of nano-TiO₂ particles in the polyurethane films.     

钼合金MoSi2涂层高温热震行为与裂纹扩展

采用料浆烧结法在钼合金表面制备了MoSi₂涂层,利用内热法测试了涂层室温～1600℃抗热震性能,通过扫描电镜(SEM)、电子探针(EPMA)、波谱分析(WDS)和X射线衍射(XRD)等测试手段分析了不同热震次数的涂层微观形貌、组织结构以及裂纹萌生扩展。结果表明：涂层可承受室温～1600℃热震400次,热震过程中涂层由原始的MoSi₂-Mo₅Si₃双层结构演变为SiO₂-MoSi₂-Mo₅Si₃多层结构,涂层热震初期形成纵向裂纹并不断向基体扩展,热震后期裂纹贯穿涂层到达基体,MoO₃挥发使涂层/基体界面应力增大产生横向裂纹,导致涂层剥落失效。     

The corrosion behavior of plasma sprayed Fe2Al5 coating in molten Zn

Aluminum coating was plasma sprayed on Fe-0.14-0.22 wt.% C steel substrate, and heat diffusion treatment at 923 °C for 4 h was preformed to the aluminum coating to form Fe₂Al₅ inter-metallic compound coating. The corrosion mechanism of the Fe₂Al₅ coating in molten zinc was investigated. SEM and EDS analysis results show that the corrosion process of the Fe₂Al₅ layer in molten zinc is as follows: Fe₂Al₅ → Fe₂Al₅Zn_x (η) → η + L(liquid phase) → L + η + δ(FeZn₇) → L + δ → L. The η phase and the eutectic structure (η + δ) prevent the diffusion of zinc atoms efficiently. Therefore the Fe₂Al₅ coating delays the reaction between the substrate and molten zinc, promoting the corrosion resistance of the substrate.     

ZrO2 加入量对Zr-8Al合金化学复合镀性能的影响

对Zr-8Al合金进行了化学复合镀Ni-P-ZrO_2处理,并研究了不同ZrO_2粒子加入量制备的复合镀层的显微结构、显微硬度、耐磨性和抗蚀性。结果表明,与单纯化学镀Ni-P镀层相比,Ni-P-ZrO_2复合镀层的显微硬度值显著提高,ZrO_2的添加量为4 g/L获得复合镀层显微硬度最高,耐磨性好;在3.5%(质量分数)NaCl溶液中耐蚀性虽有所下降,但腐蚀后镀层完整,仍具有较好的抗蚀性。Zr-8Al合金表面采用4 g/L ZrO_2粒子制备的Ni-P-ZrO_2复合镀层兼具很好的耐磨性和较好的耐蚀性,适用于既要耐磨又要抗蚀的空间活动构件。     

Characteristic of AlON-Al2O3 coatings on Al6061 alloy by electrolytic plasma processing in aluminate and nitride electrolytes

In this work, 6061 series aluminum alloy is used as the matrix material for its wide application in engineering to make AlON coating layers by the electrolytic plasma processing (EPP) method. The experimental electrolytes include: 10 g/L NaAlO₂ as alumina formative agent, 2 g/L NaOH as the electrolytic conductive agent, 0.4 g/L NaNO₃ as a nitride supply agent. A combined composition and structure analysis of the coating layer was carried out by X-ray diffractometer (XRD) and scanning electron microscopy (SEM) for the specimens EPP-treated at 25 °C in 5 to 30 min under a hybrid voltage of 260 V DC plus AC 50 Hz power supplies (200 V). In addition, microhardness values were measured to correlate the evolution of microstructure and resulting mechanical properties. A composite of AlON-Al₂O₃ coating was formed as a result of a reactive process between Al in the alloy itself and O-N supplied by the electrolyte, which presents high hardness and anti-abrasion behaviors.     

The effects of nano-SiO2 additive on the zinc phosphating of carbon steel

In this paper, nano-SiO₂ was used as an accelerator for improving the microstructure and the corrosion resistance of phosphate coating on carbon steel. The chemical composition and microstructure of the coatings were analyzed by X-ray diffraction analysis (XRD) and scanning electron microscopy (SEM). The effects of nano-SiO₂ on weight, roughness and corrosion resistance of the phosphate coatings were also investigated. Results show that the compositions of phosphate coating were Zn₃(PO₄)₂·4H₂O (hopeite), and Zn₂Fe(PO₄)₂·4H₂O (phosphophylite). The phosphate coatings became denser due to the addition of nano-SiO₂ which reduced the size of the crystal clusters. The average weight of phosphate coatings approximately linearly increased with the nano-SiO₂ content in the bath from 0 to 4 g/L, and the phosphate coatings formed in bath containing 2 g/L nano-SiO₂ showed the highest corrosion resistance in 5 wt.% sodium chloride solution at ambient temperature. Nano-SiO₂ would be widely utilized as a phosphating additive to replace the traditional nitrite, due to its less pollutant and its better quality of the coating.     

Improvement in the corrosion resistance of TiB2/A356 composite by molten-salt electrodeposition and anodization

This study reported a novel treatment to improve the corrosion resistance of TiB₂/A356 composites. The method was employed in combination of the molten-salt electrodeposition and subsequent electrochemical anodization technique. By means of molten-salt electrodeposition, the Al coatings were deposited on the surface of TiB₂/A356 composites. It was found that the morphology of the Al coatings is closely related to the current density. Thus, under the suitable condition, a dense and uniform Al coating can be obtained, with the crystal size in the range of 0.5–2 μm and the coating thickness of ~ 9 μm. This continuous Al layer can eliminate the adverse corrosion contribution of TiB₂ particles in Al matrix. The following step of anodization was designed to convert the Al film to an anodized Al oxide film for further corrosion protection. The electrochemical corrosion behavior was evaluated by potentiodynamic polarization curves and electrochemical impedance spectroscopy. These results showed the corrosion resistance was greatly enhanced in TiB₂/A356 composites with an anodized Al-coating than that of the anodized composites. It is evident that the new treatment of metal electrodeposition in molten salts and following anodization is an effective method of anti-corrosion in composites.     

Effect of MoSi2/rare earth composite particles on microstructure and mechanical properties of molybdenum

MoSi₂/La₂O₃ and MoSi₂/Y₂O₃ composite particles were prepared by mechanical milling and doped into molybdenum by solid-solid method, respectively. Rods with a diameter of 17 mm were made by pressing and sintering. The effects of different composite particles on microstructures and strength of the as-sintered molybdenum were investigated. Results show that the MoSi₂/La₂O₃ and MoSi₂/Y₂O₃ composite particles transformed to La₂O₃/Mo₅Si₃ and Y₂O₃/Mo₅Si₃ composite particles due to the in situ reaction between Mo and MoSi₂ during sintering process. Mo₅Si₃/La₂O₃ and Mo₅Si₃/Y₂O₃ composite particles can reduce the grain size and improve both strength and toughness of sintered molybdenum significantly. Mo₅Si₃/Y₂O₃ composite particles contribute more to the strength, while the effect of Mo₅Si₃/La₂O₃ on toughness is greater than that of Mo₅Si₃/Y₂O₃.     

Investigations on synthesis of HfB2 and development of a new composite with TiSi2

This paper presents the results of investigation carried out on synthesis and densification of monolithic HfB₂ and the effect of TiSi₂ as sinter additive. Pure phase HfB₂ was prepared by boron carbide reduction of HfO₂ and hot pressed to full density with the addition of TiSi₂. Isothermal oxidation study of this composite was carried out at 850 °C up to 64 h. Formation of HfB₂ was seen at 1200 °C but pure HfB₂ was formed at a much higher temperature of 1875 °C in vacuum. Hot pressing of HfB₂ at 1850 °C and 35 MPa pressure gave a compact of 80% TD. Addition of TiSi₂ helped in achieving a much higher density at a lower temperature of 1600 °C and a pressure of 20 MPa. A fully dense composite of HfB₂ and TiSi₂ was obtained with 15% TiSi₂. Hardness and fracture toughness of this composite were 27.4 ± 1.9 GPa and 6.6 ± 0.2 MPa m^1/2, respectively. Considerable deflection was observed in the crack propagation in composites. Oxidation studies indicated the formation of HfO₂, SiO₂, TiO₂ and HfSiO₄ with some glassy phase and the composite with 15% TiSi₂ was seen to be completely covered with a protective glassy layer.     

Low-temperature synthesis of N-TiO2 sol and characterization of N-TiO2 coating on cotton fabrics

To extend the application of N-TiO₂ to substrates with low thermal resistance, N-TiO₂ sol has been successfully synthesized at low temperature by reflux method and N-TiO₂ coating on cotton fabrics has been successfully prepared in a dip-coating process. Several characterization tools, such as X-ray powder diffraction, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, and UV–vis diffuse reflectance spectroscopy, were employed to study the phase structures, morphologies, the chemical states and optical properties of the samples. The photocatalytic properties of the prepared products were measured with the degradation of methyl orange at room temperature under visible light irradiation. In comparison with TiO₂-cotton, the remarkable enhancement in the visible light photocatalytic performance of the N-TiO₂-cotton could be attributed to the existence of N-TiO₂ with narrow band gap. The photocatalytic performances of the N-TiO₂-cotton were maintained for the cycling experiments, indicating that N-TiO₂-cotton could be used as stable and efficient visible-light-induced self-cleaning materials.     

等离子喷涂TiC/ZrO2复相涂层的抗烧蚀性能研究

针对TiC涂层在高温烧蚀过程中氧化生成熔融TiO₂。当温度高于2000℃时,熔融TiO2的厚度随之增加,这将进一步导致涂层结合强度降低,本文采用等离子喷涂方法制备了不同ZrO₂添加量的TiC/ZrO₂复相涂层,以提高涂层的抗冲刷性能。分别利用XRD、SEM和EDS对烧蚀前后材料的相结构、微观形貌和成分进行了分析,探讨了添加高熔点相ZrO₂的复合涂层的抗烧蚀机理。结果表明：TiC/ZrO₂复相涂层展现出更好的抗烧蚀性能,2000℃下的质量烧蚀率仅为1.5×10_-4 g.cm_-2.s_-1。烧蚀过程中产生的ZrO₂层可以阻止内部TiC的进一步氧化,并且可以在一定程度上降低氧乙炔焰对涂层的产生的剪切力,以提高涂层的康冲刷性能。     

Microstructure and properties of Cr3C2-modified nickel-based alloy coating deposited by plasma transferred arc process

The nickel-based alloy with 30 wt.% chromic carbide (Cr₃C₂) particles has been deposited on Q235-carbon steel (including 0.12 wt.% C) using plasma transferred arc (PTA) welding machine. The microstructure and properties of the deposited coatings were investigated using optical microscope, scanning electron microscope (SEM) equiped with X-ray energy spectrometer (EDS), X-ray diffraction (XRD), transmission electron microscopy (TEM), microhardness testes, and sliding wear test. It was found that the γ(Ni, Fe), M₇(C,B)₃, Ni₄B₃, and (Cr,Fe)₂B phases existed in the Cr₃C₂-free nickel-based alloy coating obtained by PTA process. The typical hypoeutectic structure and composition segregation in the solid solution could be found clearly. The addition of 30 wt.% Cr₃C₂ particles led to the existing of Cr₃C₂ phase and the microstructure changing from hypoeutectic structure into hypereutectic structure. The composition segregation in the solid solution could not be found clearly. The average microhardness of the Cr₃C₂-free nickel-based alloy coating increased by 450-500 HV after the addition of 30 wt.% Cr₃C₂ particles. The partial dissolution of Cr₃C₂ particles led to the enrichment of carbon and chromium in the melten pool, and hence caused the formation of more chromium-rich carbides after the solidification process. The undissolved Cr₃C₂ particles and the increasing of chromium-rich carbides was beneficial to enhance the hardness and wear resistance of the Cr₃C₂-modified nickel-based alloy coating deposited by PTA process.     

MoS2颗粒表面包覆Al2O3及其在镀层中的应用

采用非均匀形核法将Al2O3包覆到MoS2颗粒表面,提高颗粒的亲水性能。研究了溶液pH值、Al(NO3)3的摩尔浓度和预处理工艺对包覆率的影响;采用SEM及EDS分析了包覆前后MoS2颗粒的微观形貌和表面成分;通过测量接触角研究了颗粒表面的亲水性。结果表明,颗粒表面均匀包覆了一层Al(OH)3;溶液pH值对包覆率的影响最大,Al(NO3)3的摩尔浓度次之。最佳工艺为:溶液pH值为5.5,Al(NO3)3浓度为0.15mol/L,预处理过程不添加表面活性剂。随着包覆率的提高,MoS2颗粒的亲水性提高。利用包覆Al2O3的MoS2制得了Ni-P-MoS2化学复合镀层,提高了镀层中沉积粒子的均匀致密性。     

铝基表面等离子喷涂Al2O3-TiO2-Ta涂层的制备及防腐性能

采用等离子喷涂技术在铝基表面构建Al₂O₃-TiO₂涂层和Al₂O₃-TiO₂-Ta涂层。由于钽元素的引入,Al₂O₃-TiO₂-Ta涂层表面形貌更均匀、致密。同时钽金属具有极强的耐酸碱特性,因此,Al₂O₃-TiO₂-Ta涂层相对于Al₂O₃-TiO₂涂层具有更强的耐腐蚀性。Tafel曲线结果显示,Al₂O₃-TiO₂涂层使得基体的腐蚀电位仅正移了99.6 mV,Al₂O₃-TiO₂-Ta涂层使得铝基体腐蚀电位正移了208.9 mV。因此,由于耐蚀性极强的Ta金属的掺入,Al₂O₃-TiO₂涂层的防腐性得到了极大的增强,Al₂O₃-TiO₂-Ta涂层有效地防止铝合金腐蚀。     

锆合金激光熔覆镍基复合层微观组织及界面特征

以Ni35自熔性合金粉末为熔覆材料,采用激光熔覆技术在锆合金表面原位生成了NiZr₂/陶瓷增强镍基涂层.利用金相显微镜、扫描电镜、X射线衍射仪等对熔覆界面附近的微观组织、物相组成及界面结合特征进行分析.结果表明,熔覆层基体组织为NiZr+Ni₁₀Zr₇,增强相NiZr₂以细针状均匀分布在熔覆层上部和底部,块状及棒状的陶瓷相Zr₅（Si_xNi_1-x）₄/Zr（Si_xNi_1-x）分布在熔覆层中部,熔覆层与基体间实现良好的熔焊冶金结合,界面结合区组织不均匀,分布有等轴状NiZr及晶间的α-Zr,熔覆层的显微硬度分布均匀,平均值约为1 100 Hv.     

不同催化剂对镁合金表面SiO_2-ZrO_2涂层耐蚀性的影响

镁合金表面溶胶凝胶涂层存在易析出氢气、涂层缺陷多及防腐性能提升不明显等问题。为改善这些问题利用Ce(NO_3)_3催化制得SiO_2-ZrO_2溶胶并旋涂3层于AZ91D镁合金表面,并与HCl催化制得的镁合金表面SiO_2-ZrO_2溶胶涂层进行对比分析。采用扫描电镜和傅里叶红外光谱等分析涂层微观形貌和化学成分;通过接触角测试涂层亲疏水性;利用极化曲线和电化学阻抗谱对比研究不同催化剂加入的溶胶凝胶层在3.5%NaCl溶液中的耐腐蚀性能。结果显示:与HCl催化制得的镁合金表面SiO_2-ZrO_2溶胶涂层相比,Ce(NO_3)_3催化制得的涂层表面微观缺陷少;接触角由84.2°增大到93.5°;同镁合金基体自腐蚀电流密度1.480×10~(-4) A/cm~2相比,HCl催化和Ce(NO_3)_3催化涂层的自腐蚀电流密度分别为2.562×10~(-6) A/cm~2和7.821×10~(-7) A/cm~2,其耐蚀性提升明显;HCl和Ce(NO_3)_3催化涂层阻抗极化电阻值由镁合金基材的224.9Ω分别增大至4 401Ω和53 888Ω,HCl催化涂层的失效时间为1 d,Ce(NO_3)_3催化涂层失效时间延长为3 d。可见,两种催化剂制备的涂层,Ce(NO_3)_3催化涂层防护更持久,耐蚀性更好。