TiB2涂层的制备及其应用研究进展

二硼化钛(TiB₂)作为金属硼化物中密度最小硬度最高的化合物,是重要的现代陶瓷材料之一。它不仅具有传统陶瓷材料所具备的高熔点、高硬度以及良好的化学稳定性,还具有传统陶瓷材料所不具备的优良导电性能。因此TiB₂陶瓷不仅可以用于耐磨材料以及真空镀铝用蒸发舟材料,更是成为硬质刀具、电解铝惰性阴极以及空天飞行器热障防护等领域重要的防护涂层材料之一。本文结合国内外研究现状,重点介绍了TiB₂陶瓷涂层的气相沉积法、电化学沉积法、热喷涂法、表面熔覆法、电火花沉积法和溶胶凝胶法等制备方法的特点及适用领域,总结了其在关键领域的重要应用,并对其未来的研究方向和发展前景进行了展望。     

Effects of CeO2 additive on the microstructure and mechanical properties of in situ TiB2/Al composite

In this paper, CeO₂ was investigated as an additive for in situ preparation of TiB₂/Al composite using an exothermic reaction process via K₂TiF₆ and KBF₄ salts. Experimental results indicated that when 0.5 wt.% CeO₂ additive was added, the dispersion of TiB₂ particles was improved significantly. Meanwhile, α-Al matrix grain was further refined. Compared with the composite without CeO₂, the ultimate tensile strength, yield strength, elastic modulus and tensile elongation increased by 8%, 7%, 26% and 14%, respectively in as-cast condition, and the tensile fracture behavior of the composite with CeO₂ belonged to a typical ductile fracture with microvoid coalescence.     

Fabrication of A356 composite reinforced with micro and nano Al2O3 particles by a developed compocasting method and study of its properties

Aluminum/alumina composites are used in automotive and aerospace industries due to their low density and good mechanical strength. In this study, compocasting was used to fabricate aluminum-matrix composite reinforced with micro and nano-alumina particles. Different weight fractions of micro (3, 5 and 7.5 wt.%) and nano (1, 2, 3 and 4 wt.%) alumina particles were injected by argon gas into the semi-solid state A356 aluminum alloy and stirred by a mechanical stirrer with different speeds of 200, 300 and 450 rpm. The microstructure of the composite samples was investigated by Optical and Scanning Electron Microscopy. Also, density and hardness variation of micro and nano composites were measured. The microstructure study results revealed that application of compocasting process led to a transformation of a dendritic to a nondendritic structure of the matrix alloy. The SEM micrographs revealed that Al₂O₃ nano particles were surrounded by silicon eutectic and inclined to move toward inter-dendritic regions. They were dispersed uniformly in the matrix when 1, 2 and 3 wt.% nano Al₂O₃ or 3 and 5 wt.% micro Al₂O₃ was added, while, further increase in Al₂O₃ (4 wt.% nano Al₂O₃ and 7.5 wt.% micro Al₂O₃) led to agglomeration. The density measurements showed that the amount of porosity in the composites increased with increasing weight fraction and speed of stirring and decreasing particle size. The hardness results indicated that the hardness of the composites increased with decreasing size and increasing weight fraction of particles.     

Al2O3/TiB2/Al复合材料的微观结构和高温力学性能

以细雾化铝粉和TiB₂颗粒为原料,通过粉末冶金和热轧制制备微米TiB₂和纳米Al₂O₃颗粒增强铝基复合材料。室温时,由于TiB₂和Al₂O₃的综合强化作用,Al₂O₃/TiB₂/Al复合材料的屈服强度和抗拉强度分别为258.7 MPa和279.3 MPa,测试温度升至350℃时,TiB₂颗粒的增强效果显著减弱,原位纳米Al₂O₃颗粒与位错的交互作用使得复合材料的屈服强度和抗拉强度达到98.2MPa和122.5 MPa。经350℃退火1000 h后,由于纳米Al₂O₃对晶界的钉扎作用抑制晶粒长大,强度和硬度未发生显著的降低。     

Primary investigation of corrosion resistance of Ni-P/TiO2 composite film on sintered NdFeB permanent magnet

In this paper, an electroless nickel plating and sol-gel combined technique used to prepare the Ni-P/TiO₂ composite film on sintered NdFeB permanent magnet is described and the composite film was characterized by X-ray diffraction (XRD), environmental scanning electron microscopy (ESEM), and energy dispersive X-ray spectrometer (EDX). The corrosion resistance of Ni-P/TiO₂ film was studied by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) techniques. The self-corrosion current density (i_corr) of Ni-P/TiO₂ composite film is 2.38μA/cm² in 0.5mol/L H₂SO₄ solution about 33% of that of Ni-P coating and 0.22μA/cm² in 0.5mol/L NaCl solution about 14% of that of Ni-P coating, respectively. In 0.5mol/L H₂SO₄ and 0.5mol/L NaCl solutions, the polarization resistance (Rp) of the composite film is 12.5kΩ cm² and 120kΩ cm², about 1.6 and 2 times that of Ni-P coating, respectively. The results indicate that Ni-P/TiO₂ composite film has a better corrosion resistance than Ni-P coating.     

Investigation on the corrosion and oxidation resistance of Ni-Al2O3 nano-composite coatings prepared by sediment co-deposition

Ni-Al₂O₃ composite coatings were prepared by using sediment co-deposition (SCD) technique from a Watt's type electrolyte containing nano-Al₂O₃ particles. The corrosion resistance and high temperature oxidation resistance of resulting composite coatings were investigated. It was found that the incorporation of nano-Al₂O₃ particles in Ni matrix refined the Ni crystal and changed the preferential orientation of composite coatings. Meanwhile, the corrosion and oxidation resistance were improved after the incorporation of nano-Al₂O₃ particles into Ni matrix. The nano-Al₂O₃ content in deposits plays an important role for improving the corrosion and oxidation protection. The corrosion and oxidation resistance of Ni-Al₂O₃ nano-composite coatings produced via SCD technique are superior to that of CEP technique. Compared to pure Ni and Ni-Al₂O₃ composite coatings fabricated using CEP technique, the Ni-7.58 wt.% Al₂O₃ composite coating obtained by SCD technique exhibits better corrosion resistance and enhanced high temperature oxidation resistance. Moreover, the mechanism of corrosion and high temperature oxidation resistance of Ni-Al₂O₃ nano-composite coatings are discussed.     

In-situ TiB2 and Al2O3 formation by DC plasma spraying

In-situ plasma spraying (IPS) is a promising process to fabricate composite coatings with in-situ formed thermodynamically stable phases. In the present study, mechanically alloyed Al-12Si, B₂O₃ and TiO₂ powder was deposited onto an aluminum substrate using atmospheric plasma spraying (APS). It has been observed that, during the coating process, TiB₂ and Al₂O₃ are in-situ formed through the reaction between starting powders and finely dispersed in hypereutectic Al-Si matrix alloy. Also, obtained results demonstrate that in-situ reaction intensity strongly depends on spray conditions.     

热喷涂TiB2-Ni复合涂层组织结构和力学性能

采用团聚烧结方法制备TiB₂-Ni复合粉末喂料,并采用大气等离子喷涂和高速火焰喷涂两种喷涂方法制备了TiB₂-Ni涂层,比较分析了两种涂层的显微组织、物相组成、孔隙率、硬度和断裂韧性.结果表明,与等离子喷涂相比,高速火焰喷涂制备的TiB₂-Ni涂层具有更高的致密度,TiB₂含量,硬度和断裂韧性.两种涂层中TiB₂都没有发生明显的脱硼,氧化,但等离子喷涂过程中TiB₂向金属相中发生了溶解生成了大量脆性Ni₂₀Ti₃B₆相,并降低了涂层中TiB₂的含量,这是涂层硬度和断裂韧性相对较低的主要原因.     

化学气相沉积法制备 TiB2涂层工艺的研究

以TiCl4-BCl3-H2为反应体系,采用化学气相沉积技术,在低碳钢和石墨表面成功沉积了TiB2涂层,并研究了沉积温度、气体流量和基体类型对涂层显微结构和显微硬度的影响.结果表明:沉积温度较高时,低碳钢表面的TiB2涂层晶粒取向随机,结晶度较好,沉积温度较低时则呈柱状晶,晶粒取向随机时的显微硬度高于呈柱状晶时的显微硬...     

TiB2涂层熔盐电沉积制备与表征

炭阴极在铝电解槽中受熔盐和铝液腐蚀而影响寿命,而TiB₂涂层是铝电解槽理想的阴极材料。本文以石墨为基体,在KF-KCl-K₂TiF₆-KBF₄熔盐中以0.4-0.7A.cm_-2^{电流密度、}700-800℃温度电沉积TiB₂涂层,通过XRD衍射仪、SEM-EDS、表面粗糙度测量仪及附着力测试仪对不同电流密度和温度下制备的涂层进行表征。结果表明：在石墨基体上可以得到均匀连贯的TiB₂涂层;增大电流密度、降低电解温度可以细化涂层晶粒,提高涂层致密性;在0.6 A.cm_-²、750℃最优电沉积条件下制得的TiB₂涂层的厚度为229 μm,择优取向为<110>,表面粗糙度为14.85 μm,涂层与石墨基体的结合力为6.39 MPa。     

原位合成TiB2的定量计算及Cu-TiB2复合材料性能的研究

以Ti粉、B粉和Cu粉为原材料,球磨后,采用原位热压法合成Cu-15wt%TiB₂复合材料。详细讨论了Cu-Ti-B体系的反应过程。通过XRD、SEM、EDS、XPS等手段,确定了Ti和B在Cu基体中原位合成了TiB₂,并利用XRD制作TiB₂和Cu的定标曲线,采用外标法计算出不同烧结温度下TiB₂的合成率,结果表明,在一定的温度范围内,温度越高,合成率越高,在1000℃时TiB₂的合成率可达99.27%。并测试Cu-1.5 wt%TiB₂块状试样的维氏硬度,电导率和三点弯曲强度,分别为125.68 MPa、80.1% IACS和755.2 MPa,在100℃时的热膨胀系数和导热系数分别为9.3×10_-6 /K和260 W/mK。     

Structural evolution of mechanically alloyed Al-12Si/TiB2/h-BN composite powder coating by atmospheric plasma spraying

In the present study, mechanically alloyed Al-12Si/TiB₂/h-BN composite powder was deposited onto an aluminum substrate by atmospheric plasma spraying. The effect of mechanical alloying (MA) and plasma spray parameters on composite powder and coating structure were investigated. It has been observed that the MA process has a significant effect on the composite powder morphology and reactivity between the selective powders. Results also demonstrate that, at relatively high milling time h-BN decomposes into B and N and forms a solid solution. Also, it has been found that, the relative amount of the in-situ formed AlN through the reaction between h-BN and Al and/or the decomposition of Al-B-N solid solution is independent from the plasma parameters (arc current and secondary gas flow rate). However, spray parameters remarkably affects the coating hardness due to coarsening of Si during the solidification of the coating.     

The performances of TiB2-contained iron-based coatings at high temperature

The TiB₂-contained composite Fe-B-C coatings are deposited by the plasma transferred-arc (PTA) powder surfacing process. The coating's thermal ability, arc ablation resistance and wear resistance at high temperature were analyzed. It is concluded that TiB₂-contained composite Fe-B-C coating having excellent wear resistance at 600 °C and tempering resistance at 900 °C. Furthermore, this coating can effectively resist the arc ablation (120 A arc currents) within 7 s.     

磨损条件对等离子熔覆TiB2-TiC/Ni复合涂层磨损性能的影响

利用等离子熔覆技术以Q235低碳钢为基体制备了TiB_2-TiC强化Ni基复合材料涂层,涂层中的主要物相为TiB_2、TiC和γ-Ni,硬度达1 050 HV0.5,涂层与基体呈冶金结合状态。分别采用Al2O3陶瓷球和不锈钢球为对摩副,在30、60和120 N磨损载荷下进行往复干滑动摩擦磨损试验。结果表明:Al2O3陶瓷球为对摩副时,低载荷下(30 N)表现为微切削磨损形式;60 N载荷时,出现压实层的结构,降低了摩擦因数,磨损机理转变为粘着磨损的形式;当载荷增加到120 N时,磨损机理为氧化磨损和剥层磨损。而采用不锈钢磨球时,涂层硬度大于对摩不锈钢球硬度,磨球发生剪切破坏,部分转移到涂层表面,相对于Al2O3陶瓷磨副时具有更大的粘着效应,且随着载荷的增大转移量增加,粘着磨损加剧,所以摩擦因数呈现出随着载荷加大一直上升的趋势。     

钛合金表面氩弧熔覆原位合成TiB2-TiN涂层组织及耐磨性能

以BN和Ni60A合金粉末为熔覆材料,采用氩弧熔覆技术在TCA合金表面原位合成TiB2-TiN增强颗粒耐磨涂层．利用x射线衍射仪、扫描电子显微镜和摩擦磨损试验机对熔覆层的组织和性能进行分析测试．结果表明,复合涂层的显微组织沿层深方向分为熔覆区、结合区和热影响区;熔覆层与基体呈良好冶金结合,TiB2-TiN颗粒弥散分布,...     

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.     

Investigation on microstructure and internal friction for low density TiB2/ZL114 composites

TiB₂/ZL114 composites with the density of 2.733 g/cm³ were fabricated through reaction of K₂TiF₄ and KBF₄ (LSM method). The composites were characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM). The internal friction measurements were performed on DTM-II-J dynamic modulus damping analyzer and the mechanisms were investigated. Experimental results indicate that reinforced particles are well-distributed in the matrix and the internal friction value of TiB₂/ZL114 composites is up to a maximum of 9.04x10^-3, almost twice that of ZL114. The internal friction results form dislocation vibration within the material, the sliding of grain boundary and phase interface, and together with the micro-plastic deformation caused by difference in coefficients of thermal expansion and elasticity modulus of various phases. The average internal friction values of samples with the sizes of 40 mmx4 mmx2 mm, 40 mmx8 mmx2 mm and 40~mm$\times 25 mmx2 mm are 8.83x10^-3, 8.89x10^-3, and 8.93x10^-3, respectively. Thus, the developed composites are of low density, high internal friction, and the sizes of samples have no relation to the internal friction behavior.     

Synthesis, microstructure and mechanical properties of reaction-infiltrated TiB2-SiC-Si composites

TiB₂-C preforms formed with different compositions and processing parameters were reactively infiltrated by Si melts at 1450 °C to fabricate TiB₂-SiC-Si composites. Phase constituent and microstructure of these composites were analyzed by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The resulting composites are generally composed of TiB₂ and reaction-formed β-SiC major phases, together with a quantity of residual Si. Unreacted carbon is detected in the samples with a starting composition of 2TiB₂ + 1C formed at higher pressure and in all of the ones at the composition of 1TiB₂ + 1C. The distribution of these phases is fairly homogeneous in microstructure. TiB₂-SiC-Si composites show good mechanical properties, with representative values of 19.9 GPa in hardness, 395 GPa in elastic modulus, 3.5 MPa m^1/2 in fracture toughness and 604 MPa in bending strength. The primary toughening and strengthening mechanism is attributed to the crack deflection of TiB₂ particles.     

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.     

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。