Spraying TiN by a Combined laser and low-pressure plasma spray system

The formation of a TiN-Ti composite coating by thermal spraying of titanium powder with laser processing of the subsequent coating in a low-pressure N₂ atmosphere was examined. A low-pressure plasma spray system was used in combination with a CO₂ laser. First, the coating was plasma sprayed onto a mild steel substrate using a N₂ plasma jet and titanium powder in a controlled low-pressure N2 atmosphere. The coating was then irradiated with a CO₂ laser beam in a N₂ atmosphere, and the coating was heated with a N₂ plasma jet. The amount of TiN formed in the coating was characterized by X-ray diffraction analysis. The influence of plasma spraying conditions such as plasma power, flow of plasma operating gases, chamber pressure, and laser irradiating conditions on the formation of TiN was investigated. The effect of TiN formation in the titanium coating on Vickers hardness of the coatings was examined. It was evident that coating hardness increased with an increase in TiN content in the coating and that a TiN-Ti composite coating with a hardness of more than 1200 H V can be obtained with the use of laser irradiation processing.     

TiN-TiB2 composite coatings reactively produced by electrothermally exploded powder spray

Composite coatings composed of titanium nitride, TiN, and diboride, TiB₂, were reactively produced by the electrothermally exploded powder spray technique, in which feedstock powder was prepared from titanium and boron nitride particles. The microstructure of the coating was composed of titanium-ceramic particles the size of which were on the order of several nanometers to a few hundred nanometers. Such reactive thermal spraying brought base-metal saturation into a coating layer at the early stages of coating formation. The ceramic composite spray using feedstock of TiN and TiB₂ particles preferentially brought a new phase of cubic titanium boronitride together with TiN and TiB₂ into a coating. On comparing such a coating to one produced by the conventional method, the reactive thermal spray coating was richer in TiN and TiB₂ due to the excess nitrogen in the feedstock.     

Study on Reactive Atmospheric Plasma-Sprayed In situ Titanium Compound Composite Coating

A titanium composite coating containing in situ synthesized oxides or nitrides was deposited on mild steel by reactive atmospheric plasma spraying. The relationships between the porosity, hardness, the phase composition of the sprayed coatings, and the spraying parameters were investigated. Titanium powders were used as starting powder materials. XRD analysis and microhardness test revealed that titanium oxides and nitrides were synthesized during the spraying process. The longer the spraying distance, the more the Ti nitrides’ content in the coating. It is shown that the Ti nitrides’ content has a significant influence on coating hardness. An in situ titanium composite coating with a hardness value of 1534HV_0.1 and an adhesive strength of 55.4 MPa was made with appropriate spraying parameters.     

Surface nitridation of titanium metal by means of a gas tunnel type plasma jet

The surface nitridation of titanium was carried out at a low pressure in nitrogen atmosphere using a gas tunnel type plasma jet. The titanium nitride (TiN) film, 10 μm thick and 2000 HV, could be formed in 10 s. The structure of the TiN film was investigated by XRD. The Vickers hardness on the surface of the film was measured. The effects of deposition conditions on the properties of TiN films (TiN thickness,Vickers hardness, etc.) were investigated, and the advantage of this deposition method was identified from those results.     

反应等离子喷涂 TiN 涂层的研究进展

TiN具有硬度高、韧性好、摩擦系数小、化学性能稳定等优点,广泛应用于刀具、装饰、表面防护等领域。目前制备TiN涂层的方法有很多,如气相沉积、热喷涂、电镀等,反应等离子喷涂则是最常用的金属-陶瓷复合涂层制备方法。概述了反应等离子喷涂技术的基本原理和分类,包括反应等离子喷涂涂层的形成过程及工艺的优缺点。综述了反应等离子喷涂TiN涂层的喷涂工艺及性能的研究进展,包括涂层的制备方法(原位合成法、烧结破碎法)和性能特点,重点分析了涂层的力学性能、耐磨损性能、耐腐蚀性能,并提出了可以依靠热处理工艺或封孔技术来提高涂层的耐腐蚀性能。依据实验和查阅的文献,反应等离子喷涂结合了自蔓延高温合成技术和等离子喷涂技术,可以制备质量优良的厚TiN涂层(500μm),是一种新型的低成本涂层制备技术,但是反应等离子喷涂制备TiN涂层存在孔隙率较高(5%~10%)、结合强度较低(50 MPa)的问题。分别从技术、设备、工艺、后处理四个方面总结了改善涂层质量的相应措施,展望了今后的研究发展方向。     

Microstructural Development and Deposition Behavior of Titanium Powder Particles in Warm Spraying Process: From Single Splat to Coating

Warm spraying has been developed by NIMS, in which powder particles are accelerated and simultaneously heated, and deposited onto a suitable substrate in thermally softened solid state. In this study, commercially available titanium powder was sprayed onto steel substrate by the spraying process. Microstructural developments and deposition behaviors from a deposited single particle to a thick coating layer were observed by high resolution electron microscopes. A single titanium particle sprayed onto the substrate was severely deformed and grain-refined mainly along the interfacial boundary of particle/substrate by the impact of the sprayed particle. A successive impact by another particle further deformed the previously deposited particle and induced additional grain refinement of the remaining part. In a thick coating layer, the severe deformation and grain refinement were also observed. The results have demonstrated the complex deposition behavior of sprayed particles in the warm spraying using thermally softened metallic powder particles.     

Investigating the microstructure and composition of cold gas-dynamic spray (CGDS) Ti powder deposited on Al 6063 substrate

The compositional variation, morphology and microstructure of cold gas-dynamic spray are of great importance for its proper application. This study investigates titanium powder deposition on an Al 6063 substrate using light optical microscopy, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The composition was examined using energy dispersive X-ray spectroscopy (EDX), X-ray diffraction, X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF SIMS). Optical and electron microscopy revealed heavily deformed Ti powder particles penetrating 10 to 30 μm into the Al substrate. Examination using TEM did not reveal any evidence of second phases at the interface suggesting a sharp transition between the two metals. The presence of nanocrystals and grain refinement of both the coating and the substrate suggest the formation of a partial hetero-epitaxy condition near the interface. EDX results from a dedicated high-resolution scanning transmission electron microscope showed a sharp compositional change with a maximum inter-diffusion region of about 5 nm. Bonding of the coating to the substrate is therefore thought to be achieved by the particle/substrate interlocking and direct metal to metal bonding. However, it is most likely that the refine crystalline structure near the interface will be beneficial to the adhesion of the coating. XPS and ToF SIMS provided evidence of nitrogen pick-up during the spray process in the form of N and TiN even when utilizing Helium as the gas carrier. The presence of TiN suggests reaction of the Ti with the entrained air during spraying which explains the occurrence of flashing jet outside the nozzle. Investigation of the material properties using nanoindentation showed reasonably consistent hardness and elastic modulus values throughout the titanium coating and at the transition region. The hardness was slightly higher than typical commercially available bulk Ti.     

Enhancement of Functional Ceramic Coating Performance by Gas Tunnel Type Plasma Spraying

A high-precision plasma system has been pursued for advanced thermal processing. The gas tunnel type plasma jet device developed by the author exhibits high energy density and also high efficiency. Among its various applications is the plasma spraying of ceramics such as Al₂O₃ and ZrO₂. The performance of these ceramic coatings is superior to conventional ones. Properties such as the mechanical and chemical properties of the zirconia coatings were reported in previous studies. In this study, the enhancement of the performance of functional ceramic coatings by the gas tunnel type plasma spraying method was carried out using different powders. Results show that the alumina/zirconia composite system exhibited improvements of mechanical properties and corrosion resistance. The alumina/zirconia composite coating has the potential for use as a high functionally graded thermal barrier coating. Another application of the gas tunnel type plasma is for surface modification of metals. As an example, TiN films were formed in 5 s and, thick TiN coatings were easily obtained by gas tunnel type plasma reactive spraying.     

Reactive thermal spray by high velocity ceramic jet and characterization of the coatings

A ceramic jet composed of molten particles in an electrothermally exploded powder spray was identified by the flash, soft x-ray radiography technique. The velocity of the leading edge of the jet was estimated to be 900 m/s. The coating obtained by a ceramic jet of titanium diboride consisted of a mixing layer of the substrate material and sprayed ceramics. A coating, which exhibited no pores or cracks, was formed through the dense deposition and solidification of spray droplets. The successive impacts of the droplets caused melting and stirring of the substrate surface to form a mixing layer. Some of these layers were formed due to capillary movement of the molten substrate material into the fractures of coarse ceramic particles. Thermal spray by chemical reaction between titanium and boron nitride particles resulted in a composite coating of TiN and TiB₂. The character of the mixing layer indicated that the depth profiles depended on the substrate material.     

氮化钛含量对热塑性涂层光热效应及自修复性能的影响

为了实现涂层破损的高效自修复,将纳米氮化钛与热塑性聚氨酯混合,制备了不同氮化钛含量的复合涂层。 利用扫描电子显微镜(SEM)、X 射线衍射仪(XRD)和紫外可见分光光度计(UV-Vis)分析了氮化钛的结构和光谱吸收特征;利用差示扫描量热仪(DSC)、热电偶、光学显微镜、扫描电子显微镜( SEM)、交流阻抗谱(EIS)等对复合涂层的热力学性能、光热转换性能、自修复性能及防腐性能进行测试。 结果表明:基于纳米氮化钛的表面等离激元特性,在热塑性聚氨酯中添加质量分数为 2%的氮化钛后,复合涂层具有良好的光热转换性能,在近红外激光照射后其表面温度高于聚氨酯的玻璃化转变温度。 当涂层表面有划口时,通过激光照射可以提高涂层的局部温度,使聚合物分子链运动并流向划痕界面,复合涂层的结构和防腐性能均得到恢复,并且修复后涂层中氮化钛仍分布均匀。 此外,氮化钛纳米颗粒还有助于填补涂层的微观孔隙,使复合涂层的防腐性能提高。     

钛合金表面激光熔覆Ti/Ni+Si3N4/ZrO2复合涂层组织与性能研究

目的 提高TA15合金的表面硬度,改善其耐磨性能.方法 以Ti/Ni+Si3 N4/ZrO2混合粉末为原料,利用激光熔覆技术,在TA15钛合金表面制备出以ZrO2颗粒和原位生成Ti5 Si3、TiN为增强相,以金属化合物TiNi、Ti2 Ni为基体的复合涂层.采用X射线衍射仪、扫描电镜及能谱仪等手段分析激光熔覆涂层的显微组织及磨损表面,通过硬度测试、摩擦磨损实验,对熔覆层的显微硬度和耐磨性进行评估.结果 熔覆层与基体形成了良好的冶金结合,熔覆层组织中TiNi和Ti2 Ni金属化合物基体上弥散分布着Ti5 Si3、TiN树枝晶和ZrO2颗粒;与不含ZrO2熔覆层相比,含有ZrO2熔覆层组织的晶粒得到细化;熔覆层中原位生成的TiN桥接在裂纹上,具有增韧的作用;熔覆层的显微硬度分布在835~1050 HV区间内,约为基体硬度的3倍左右;在干滑动摩擦磨损下,熔覆层的磨损量约为钛合金基体磨损量的1/6,其主要磨损机制为磨粒磨损和黏着磨损.结论 熔覆层中高硬度、耐磨陶瓷相和高韧性相的共同配合,显著提高了钛合金表面的硬度和耐磨性.     

DLC、TiN涂层对TC4钛合金抗砂尘冲蚀性能的影响

为提高TC4钛合金的抗砂尘冲蚀性能,采用金属蒸汽真空弧(MEVVA)离子源注入与磁过滤真空阴极弧(FCVA)沉积复合技术、磁控溅射技术在TC4钛合金表面制备DLC、TiN涂层。采用SEM、Raman、XRD、纳米压痕仪和划痕仪等方法对涂层的物相结构、硬度、弹性模量以及与基体的结合力进行表征。在冲蚀试验平台上考核试样在不同入射角度条件下的抗砂尘冲蚀性能。结果表明:DLC涂层表面结构致密,含有大量sp3键,硬度为62.1 GPa,弹性模量为391.64 GPa,结合力达80.4 N;TiN涂层表面存在许多熔滴颗粒及空穴,硬度为22.72 GPa,弹性模量为383.18 GPa,结合力达34.7 N。30°冲蚀条件下,涂层主要是通过提高基体表面硬度来抵抗砂尘粒子的微切削作用,从而提高TC4钛合金的抗砂尘冲蚀性能。90°冲蚀条件下,涂层通过延缓基体的塑性变形来实现TC4钛合金抗砂尘冲蚀性能的提高。     

Effect of Plasma Spraying Process on Microstructure and Microhardness of Titanium Alloy Substrate

High-temperature titanium alloys are considered as good candidate materials for many aerospace applications. In order to increase the usable temperatures and oxidation resistance of titanium alloys, plasma spraying thermal barrier coatings (TBCs) on the titanium alloys is considered as an effective method. The effect of plasma spraying process on microstructure and microhardness of the titanium alloy (Ti-6.6Al-3.61Mo-1.69Zr-0.28Si in wt.%) was investigated by scanning electron microscope, energy dispersion analytical X-ray spectroscopy (EDAX) and microhardness test. The results show that the microstructure of the titanium alloy inside the substrate keeps unchanged after plasma spraying, and no interaction and atomic diffusion happen evidently at the bond coat/substrate interface. However there exists a thin layer of plastic deformation zone in the substrate beneath the bond coat/substrate interface after plasma spraying. The residual stresses are induced inside the titanium alloy due to the thermal expansion mismatch and the temperature gradient inside the substrate during plasma spraying, and lead to generating microcracks in the surface beneath the bond coat/substrate interface and the increase of microhardness in the substrate.     

Effect of prior plasma nitriding applied to a hot-work tool steel on the scratch-resistant properties of PACVD TiBN and TiCN coatings

Ternary TiBN and TiCN coatings on a hot-work tool steel substrate with and without plasma nitriding (PN) prior to plasma-assisted chemical vapour deposition (PACVD) were investigated. Compositional analysis with a radio frequency glow discharge optical emission spectroscope (rf-GDOES) showed mixtures of TiBN + TiN and TiCN + TiN in the PACVD TiBN and TiCN coatings, respectively. Each coating layer had a compositional gradient across the coating depth and slightly into the substrate. The microhardness profiles (HV_0.1) of the substrate with and without PN from the interface with the coating to the substrate core were determined. The depth of the effective nitrided diffusion layer was confirmed from the examination of its optical microstructure. The adhesion of these two coatings to the substrate was evaluated through scratch tests in the progressive mode. It was found that with increasing load, both of the coatings on the substrate with and without prior nitriding deteriorated in the same failure modes. Critical loads corresponding to the first microcracking related to cohesive failure, spallation related to adhesive failure, breakthrough and worn out were determined and used to quantify the scratch resistance of these coatings. With PN prior to PACVD, both the cohesion and adhesion properties of the TiBN and TiCN coatings were remarkably improved. This improvement was attributed to a functionally gradient hardness configuration from the coating through the nitrided diffusion layer to the substrate.     

The dependence of hardness and corrosion protection power of ion- beam-assisted deposition TiN coatings on the ion beam impact angle

Hard coatings such as titanium nitride are often porous and therefore not necessarily very corrosion resistant. Possibilities for reducing the film porosity are densification and multilayer structures. These methods are studied in our laboratories at present.

Ion-beam-assisted deposition (IBAD) TiN films were deposited changing the angle between the substrate normal and the ion beam incidence direction.

The films were characterized by transmission electron microscopy, scanning electron microscopy and X-ray diffraction analyses, the hardness was determined by means of a dynamic Vickers hardness tester and the corrosion behaviour was evaluated using current-potential measurements in a multicycle voltammogram mode.

The results are strongly dependent on the changes in the crystal orientation induced by the ion flux under different angles. Careful optimization may lead to coatings with high hardness and excellent corrosion protection potential. These results are compared with Ti/TiN multilayers deposited by IBAD and magnetron sputtering and with a sputtered TiN single layer.     

In Situ Synthesis of TiC-Fe Composite Overlays from Low Cost TiO2 Precursors Using Plasma Transferred Arc Deposition

A direct conversion of TiO₂ into TiC during plasma transferred arc deposition is a cheap and novel approach to produce wear resistant coatings. The present study explored the use of a low cost titanium ore as precursor for titanium carbide in metal matrix composite overlays. The deposited layers were characterized using optical microscopy, scanning electron microscopy, x-ray diffraction and microhardness testing. A carbothermic reduction of the titanium oxides took place during the deposition of the coating by plasma transferred arc. The overlays produced in this way consisted of fine titanium carbides evenly dispersed in an iron matrix. The opportunities and limitations of this approach are discussed.     

钛合金表面百微米级Ti/TiN多层复合涂层性能研究

目的提高TiN硬质涂层的厚度及各项力学性能。方法采用等离子增强PVD技术在钛合金(TC4)基体表面制备多层复合Ti/TiN涂层,对涂层进行扫描电镜(SEM)分析,采用划痕法表征涂层的结合强度,用维氏显微硬度计测试涂层的显微硬度,利用销盘式摩擦磨损试验仪评价涂层的摩擦磨损性能。结果制备的多层复合Ti/TiN涂层厚度最高可达100μm,且未发生剥落等失效,结合强度相对于单层TiN提高了近3倍。由于Ti、TiN的多层复合调制作用,制备的Ti/TiN显微硬度测试表明复合涂层的显微硬度高达2700 HV0.025,同时,涂层在原有耐磨性能优良的基础上具备自润滑减摩作用,经过近20 000 m的磨损测试,复合涂层的摩擦系数低至0.25左右,且未完全失效。结论多层复合结构能够有效提高TiN硬质涂层的厚度,制备的Ti/TiN多层复合涂层的各项力学性能显著提高。     

Nitride formation in synthesis of titanium aluminide matrix composite coatings by reactive RF plasma spraying

This paper presents an in situ process to form intermetallic matrix composite coatings by reactive radio frequency (RF) plasma spraying with premixed elemental powder. The typical splat morphology of impinged titanium droplets on a stainless steel substrate is a disk with an outer peripheral fringe. If the supplied titanium powder size becomes finer or the nitrogen partial pressure in the plasma gas increases, splats containing prominent asperities with a smaller flattening ratio appear along with the plain disk type. An increase in nitrogen content is detected in all the splats sprayed with finer titanium powder and/or higher nitrogen partial pressure. The splats containing prominent asperities, which correspond to TiN, are twice as high in nitrogen content than the plain disk type. Aluminum splats are also classified into two categories: a disk type with an irregular outer periphery and a seminodular type. Oxygen exists on the splat surfaces, on which there are nitrogen concentrated areas corresponding to AlN. Consequently, the nitride formation proceeds on titanium and aluminum droplets during the flight as well as on the substrate. If the substrate temperature is higher than 873 K just before spraying with premixed titanium and aluminum powder, the formation of TiAl and Ti₂AlN proceeds on the substrate because of negligible mutual collisions during the flight. Titanium aluminide matrix in situ composites sprayed with premixed titanium and aluminum powder contain more nitrides than those sprayed with TiAl compound powder, because of the higher nitrogen absorption in titanium and aluminum droplets that results in an exothermic reaction.     

钛合金表面激光熔覆 h-BN 固体润滑涂层

目的优化钛合金激光熔覆固体润滑涂层的熔覆工艺参数,提高钛合金表面耐磨性能。方法采用Nd∶YAG激光器,分别在高功率和低功率条件下,在TC4钛合金表面制备h-BN固体自润滑涂层。观察分析熔覆陶瓷层的宏观形貌、物相组成、显微组织和硬度,采用摩擦磨损试验仪对熔覆层的摩擦学性能进行研究。结果低激光功率下,熔覆材料上浮流失严重,熔覆层的相成分主要是Ti N,Ti B,Ti B2等硬质相,硬度较高,存在裂纹。高激光功率下,基材的熔化稀释较好地抑制了润滑相h-BN的上浮,减少了溅射损失,发生了包晶反应,生成了单质金属Ti,熔覆层硬度低,但摩擦磨损试验表明,涂层中润滑相h-BN含量的增加使得形成了更好的润滑膜,降低了摩擦系数。结论在输出电流400 A,脉宽5 ms,频率12Hz,扫描速度120 mm/min,搭接率50%~60%的条件下进行激光熔覆,所得熔覆层的表面状态平整,耐摩擦性能最好。     

Hard and wear-resistant titanium nitride coatings for cemented carbide cutting tools by pulsed high energy density plasma

Hard and wear-resistant titanium nitride coatings were deposited by pulsed high energy density plasma technique on cemented carbide cutting tools at ambient temperature. The coating thickness was measured by an optical profiler and surface Auger microprobe. The elemental and phase compositions and distribution of the coatings were determined by Auger microprobe, x-photon electron spectroscope, and X-ray diffractometer. The microstructures of the coatings were observed by scanning electron microscope and the roughness of the sample surface was measured by an optical profiler. The mechanical properties of the coatings were determined by nanoindentation and nanoscratch tests. The tribological properties were evaluated by the cutting performances of the coated tools applied in turning hardened CrWMn steel under industrial conditions. The structural and mechanical properties of the coatings were found to depend strongly on deposition conditions. Under optimized deposition conditions, the adhesive strength of TiN film to the substrate was satisfactory with the highest critical load up to more than 90 mN. The TiN films possess very high values of nanohardness and Young’s modulus, which are near to 27 GPa and 450 GPa, respectively. The wear resistance and edge life of the cemented carbide tools were improved dramatically because of the deposition of titanium nitride coatings.