TC4表面TiN/Ti涂层的热腐蚀行为研究及第一性原理计算

目的综合评估涂层性能、延长压气机叶片的使用寿命,进行TiN/Ti涂层及冲蚀后TiN/Ti涂层的热腐蚀行为机制研究。方法进行了完整TiN/Ti涂层及冲蚀后TiN/Ti涂层300℃/120h的热腐蚀实验,腐蚀介质为95%(质量分数)Na_(2)SO_(4)+5%(质量分数)NaCl。冲蚀实验采用形状不规则的SiO_(2)颗粒,冲蚀角为45°,冲蚀速度为130 m/s,供砂速率为6.4 g/min。建立了完整TiN涂层、表面具有孔洞的TiN涂层及表面具有Ti液滴的TiN涂层3种第一性原理腐蚀计算模型。结果TiN/Ti涂层热腐蚀后,液滴处发生氧化并且变得疏松;样品切割边缘产生腐蚀锈迹,最终出现鼓包和裂纹;冲蚀后,涂层表面的完整性受到破坏,相较于未冲蚀区域,冲蚀坑周围更容易出现腐蚀。在热腐蚀过程中,SO_(4)^(2-)中的O和完整TiN涂层中的Ti以及液滴中的Ti电子云团接触,存在电荷转移及成键倾向,具体为Ti失电子、O得电子,腐蚀主要发生在SO_(4)^(2-)中的O与Ti之间。结论第一性原理计算结果与热腐蚀的实验结果相一致,第一性原理计算结果可以从微观上反映液滴和孔洞等缺陷对涂层热腐蚀行为的影响,能够为分析涂层的热腐蚀机制提供理论依据。

Effects of surface roughness of substrate on properties of Ti/TiN/Zr/ZrN multilayer coatings

Ti/TiN/Zr/ZrN multilayer coatings were deposited on Cr_17Ni_2 steel substrates with different surface roughnesses by vacuum cathodic arc deposition method. Microstructure, micro-hardness, adhesion strength and cross-sectional morphology of the obtained multilayer coatings were investigated. The results show that the Vickers hardness of Ti/TiN/Zr/ZrN multilayer coating, with a film thickness of 11.37 μm, is 29.36 GPa. The erosion and salt spray resistance performance of Cr_17Ni_2 steel substrates can be evidently improved by Ti/TiN/Zr/ZrN multilayer coating. The surface roughness of Cr_17Ni_2 steel substrates plays an important role in determining the mechanical and erosion performances of Ti/TiN/Zr/ZrN multilayer coatings. Overall, a low value of the surface roughness of substrates corresponds to an improved performance of erosion and salt spray resistance of multilayer coatings. The optimized performance of Ti/TiN/Zr/ZrN multilayer coatings can be achieved provided that the surface roughness of Cr_17Ni_2 steel substrates is lower than 0.4μm.

Effects of nitrogen flux on microstructure and tribological properties of in-situ TiN coatings deposited on TC11 titanium alloy by electrospark deposition

In order to improve the tribological properties of titanium alloys,the in-situ TiN coatings were prepared by electrospark deposition（ESD） on the surface of TC11 titanium alloy.The effects of nitrogen flux on the microstructure and tribological properties of TiN coatings were investigated.The results show that the coating is relative thin when the nitrogen flux is small and mainly consists of Ti2N,α-Ti,Ti O and TiN phases,and the metastable phase of Ti2N is developed due to the rapid solidification of ESD.While in excessive nitrogen flux condition,many micro-cracks and holes might be generated in the coating.In moderate nitrogen flux,the coating is mainly composed of TiN phase,and is dense and uniform（50-55 μm）.The average hardness is HV0.2 1165.2,which is 3.4 times that of the TC11 substrate.The TiN coatings prepared in moderate nitrogen flux perform the best wear resistance.The wear loss of the coating is 0.4 mg,which is 2/9 that of the TC11 substrate.The main wear mechanisms of the coatings are micro-cutting wear accompanied by multi-plastic deformation wear.

Microstructure and mechanical properties of TiN/TiAlN multilayer coatings deposited by arc ion plating with separate targets

TiN/TiAlN multilayer coatings were prepared by arc ion plating with separate targets. In order to decrease the unfavorable macroparticles, a straight magnetized filter was used for the low melting aluminium target. The results show that the output plasmas of titanium target without filter and aluminium target with filter reach the substrate with the same order of magnitude. Meanwhile, the number of macropartieles in TiN/TiAlN multilayer coatings deposited with separate targets is only 1/10-1/3 of that deposited with alloy target reported in literature. Al atom addition may lead to the decrease of peak at （200） lattice plane and strengthening of peak at （111） and （220） lattice planes. The measured hardness of TiN/TiAlN multilayer coatings accords with the mixture principle and the maximum hardness is HV2495. The adhesion strength reaches 75 N.

基于机械干态颗粒涂层技术制备cBN@TiN粉体

采用机械干态颗粒涂层技术分别制备了cBN@TiO_(2)(TiO_(2)包覆立方氮化硼)粉体和cBN@(TiO_(2)+C)(TiO_(2)+碳包覆立方氮化硼)粉体,然后在1600℃、N_(2)气氛下进行高温热处理制备cBN@TiN(TiN包覆立方氮化硼)粉体,研究了高温热处理前后粉体的物相组成与微观形貌以及高温反应机理。结果表明:机械干态颗粒涂层技术可以使纳米TiO_(2)和纳米TiO_(2)+C颗粒均匀包裹在cBN颗粒表面。在高温热处理过程中,TiO_(2)与cBN反应生成液相B_(2)O_(3),促进了cBN相变成六方氮化硼(hBN),cBN的高温稳定性差,以cBN@TiO_(2)为原料制备的cBN@TiN粉体颗粒表面形成由TiN相和hBN相组成的片状结构层;当存在碳时,TiO_(2)会优先与碳发生还原反应生成TiN,抑制B_(2)O_(3)的生成,从而降低cBN相变量,此时cBN的高温稳定性好,以cBN@(TiO_(2)+C)为原料制备的cBN@TiN粉体颗粒表面形成主要为TiN相的颗粒结构层。

TLM钛合金表层TiN/Sn复合涂层的制备及磨损行为研究

为了提高Ti-25Nb-3Zr-2Sn-3Mo(TLM)钛合金的耐磨性能,采用表面机械复合强化(SMCS)工艺在合金表层制备了复合涂层并研究了复合涂层的显微组织、微观力学性能和摩擦学性能。结果表明:采用表面机械复合强化技术可在合金表层成功制备TiN/Sn复合涂层,随着Sn含量的增加,复合涂层的厚度和粗糙度不断增大,10%、20%、30%、40%Sn涂层的厚度分别为9.08、14.05、18.33、23.55μm;10%、20%、30%、40%Sn涂层的表面硬度分别为590、529、465、400 HV,相比基体硬度(~230 HV)有所提高。复合涂层的磨损量随Sn含量的增加先减小后增大,20%Sn样品具有最低的磨损量;在干磨损试验中,原样的磨损机制以黏着磨损为主,同时伴随磨粒磨损,复合强化样的磨损机制为磨粒磨损、黏着磨损,同时伴随氧化磨损。

TiN/TiNO/SiO_(2)太阳能选择性吸收涂层的优化设计及热稳定性评价

目的太阳能选择性吸收涂层是太阳能热利用的核心材料。方法采用磁控溅射法制备Ti N/TiNO/SiO_(2)太阳能选择性吸收涂层,测定红外反射层Ti N、吸收层Ti NO的折射率n、消光系数k,对Ti N层建立Tauc-Lorentz模型进行数据迭代优化拟合,对Ti NO层建立Drude模型进行数据迭代优化拟合。通过TFCalc光学镀膜设计软件,设置连续目标在300~1500 nm光谱区反射率低于5%,得到软件优化的反射率曲线、各层的最优厚度,确定优化的工艺参数。利用UV-VIS-NIR、FTIR、SEM、XRD、EDS、AFM和XPS表征优化涂层的光学性能、评价热稳定性。结果优化后的涂层,吸收率为0.906、发射率为0.0852;经265℃、600 h热处理后,涂层的吸收率和发射率分别为0.933和0.1033,PC值小于0.01。随热处理时间的增长,α有小幅上升;热处理时间对ε的影响较小;这与表面Si O_(2)氧化物薄膜层在一定程度上阻止了晶粒的长大有关。热处理后,发现涂层表面局部位置有少量的小坑,但涂层的表面成分不变。非晶基质Si O_(2)和Ti O_(2)的再结晶是吸收率提高的主要原因;热处理后的涂层表面非常致密,粗糙度的降低有利于阻碍氧原子向内层的扩散,可以有效提高涂层的热稳定性。结论优化的Ti N/TiNO/SiO_(2)涂层,选择性吸收性能及热稳定性得到有效提高,具有较好的实际应用前景。

喷砂时间对TiCN/α-Al_(2)O_(3)/TiN涂层金属陶瓷刀片表面状态和磨损性能的影响

采用化学气相沉积法在金属陶瓷基体表面沉积了MT-TiCN/α-Al_(2)O_(3)/TiN涂层,再对CVD涂层金属陶瓷刀片进行喷砂处理,分析经不同喷砂时间处理后的涂层金属陶瓷刀片的表面形貌、力学性能以及耐磨性能。结果表明:喷砂时间对涂层金属陶瓷刀片表面的冲蚀程度影响较大。未经喷砂处理的涂层表面粗糙度较高且存在较大的残余拉应力,而喷砂处理后的涂层金属陶瓷刀片的表面粗糙度与表面残余应力大幅下降,且表面硬度和耐磨性大幅提高。当喷砂时间为10s时,涂层金属陶瓷刀片获得了最低的表面粗糙度,与未喷砂的涂层刀片相比,表面残余拉应力降低了85%。基于不同喷砂时间处理后的涂层表面粗糙度、硬度、残余应力以及后刀面磨损形貌,得到的最佳喷砂时间为10s。

Pitting corrosion behavior and corrosion protection performance of cold sprayed double layered noble barrier coating on magnesium-based alloy in chloride containing solutions

Nitrogen processed, cold sprayed commercially pure(CP)-Al coatings on Mg-based alloys mostly lack acceptable hardness, wear resistance and most importantly are highly susceptible to localized corrosion in chloride containing solutions. In this research, commercially pure α-Ti top coating having good pitting potential(~1293 mV_(SCE)), high microhardness(HV_(0.025): 263.03) and low wear rate was applied on a CP-Al coated Mg-based alloy using high pressure cold spray technology. Potentiodynamic polarization(PDP) curves indicated that the probability of transition from metastable pits to the stable pits for cold spayed(CS) Al coating is considerably higher compared to that with the CS Ti top coating(for Ti/Al/Mg system). In addition, CS Ti top coating was in the passivation region in most pH ranges even after 48 h immersion in 3.5 wt% NaCl solution. The stored energy in the CS Ti top coating(as a passive metal) was presumed to be responsible for the easy passivation. Immersion tests indicated no obvious pits formation on the intact CS Ti top coating surface and revealed effective corrosion protection performance of the CS double layered noble barrier coatings on Mg alloys in 3.5 wt% NaCl solution even after 264 h.

Effect of N_(2) partial pressure on comprehensive properties of antibacterial TiN/Cu nanocomposite coating

Foreign body reactions to the wear debris and corrosion products from the implants,and bacterial infections are the main factors leading to the implant failures.In order to resolve these problems,the antibacterial TiN/Cu nanocomposite coatings with various N_(2) partial pressures were deposited on 304 stainless steels(SS)using an arc ion plating(AIP)system,named TiN/Cu-x(x=0.5,1.0,1.5 Pa).The results of X-ray diffraction analysis,energy-dispersive X-ray spectroscopy,and scanning electron microscopy showed that the N_(2) partial pressures determined the Cu contents,surface defects,and crystallite sizes of TiN/Cu nanocomposite coatings,which further influenced the comprehensive abilities.And the hardness and wear resistances of TiN/Cu coatings were enhanced with increase of the crystallite sizes.Under the co-actions of surface defects,crystallite sizes,and Cu content,TiN/Cu-1.0 and TiN/Cu-1.5 coatings possessed excellent corrosion resistance.Besides,the biological tests proved that all the TiN/Cu coatings showed no cytotoxicity with strong antibacterial ability.Among them,TiN/Cu-1.5 coating significantly promoted the cell proliferation,which is expected to be a novel antibacterial,corrosion-resistant,and wear-resistant coating on the surfaces of medical implants.

TiC-Fe coatings prepared by flame spray synthesis process

A new process, flame spray synthesis (FSS), has been developed for producing ceramic containing composite coatings. By combining self propagation high temperature synthesis (SHS) and flame spraying, the cermet based material was synthesized and deposited simultaneously. TiC Fe coatings were deposited from commercial ferrotitanium, iron and graphite powders by the flame spraying synthesis process. Microstructure analyses revealed that TiC was synthesized during spraying, and that submicron and round TiC particles were dispersed within an iron matrix. Flame spray synthesized coatings were composed of alternate soft and hard layers, whose hardness were 3.0～6.0 GPa and 11～13 GPa, respectively.

Effect of Al and Si additions on microstructure and mechanical properties of TiN coatings

Ti-X-N (X=Al,Si or Al+Si) coatings were grown onto cemented carbide substrates by cathodic arc evaporation. The hardness of the coatings was obtained by nanoindentation and the microstructure was investigated by XRD,XPS and SEM. Solid solution hardening results in a hardness increase from 24 GPa for TiN to 31.2 GPa for TiAlN. The higher hardness values of 36.7 GPa for TiSiN and 42.4 GPa for TiAlSiN are obtained by the incorporation of Si into TiN (TiAlN) coatings due to the formation of special three-dimensional net structure consisting of nanocrystalline (nc) TiN (TiAlN) encapsulated in an amorphous (a) Si3N4 matrix phase. Furthermore,the nc-TiAlN/a-Si3N4 coating shows the best machining performance.

Structure and wear resistance of TiN and TiAlN coatings on AZ91 alloy deposited by multi-arc ion plating

In order to investigate the microstructure of TiN and TiAlN coatings and their effect on the wear resistance of Mg alloy, TiN and TiAlN coatings were deposited on AZ91 magnesium alloy by multi-arc ion plating technology.TiN and Ti70Al30N coatings were prepared on the substrate,respectively,which exhibited dark golden color and compact microstructure.The microstructures of TiN and Ti70Al30N coatings were investigated by X-ray diffractometry(XRD)and scanning electron microscopy(SEM).The micro-hardness and wear resistance of TiN and Ti70Al30N coatings were investigated in comparison with the uncoated AZ91 alloy. The XRD peaks assigned to TiN and TiAlN phases are found.The hardness of TiN coatings is two times as high as that of AZ91 alloy, and Ti70Al30N coating exhibits the highest hardness.The wear resistance of the hard coatings increases obviously as result of their high hardness.

Effects of process parameters on microstructure and wear resistance of TiN coatings deposited on TC11 titanium alloy by electrospark deposition

In the present study,the effects of process parameters(output voltage x,nitrogen flux l and specific strengthening time s)on the microstructure and wear resistance properties of TiN coatings prepared by electrospark deposition(ESD)were investigatedsystematically.The microstructure of the coatings was characterized for thickness(TOC),content of TiN(CON)and porosity(POC).A statistical model was developed to identify the significant factors affecting the microstructure and wear resistance of the coatings.The results show that the output voltage x and nitrogen flux l present significant effects on majority of the evaluation indexes such asTOC,friction coefficient(COF)and wear mass loss(Id),while the specific strengthening time s has a significant effect on POC and asmall effect on the other indexes.The optimal process parameters were obtained as follows:output voltage(x,60V),nitrogen flux(l,15L/min)and specific strengthening time(s,3min/cm2).The variation of wear mass loss(Id)by the variation of the outputvoltage(x)and nitrogen flux(l)is attributed to the change of wear mechanisms of TiN coatings.The main wear mechanism of TiNcoating prepared under optimal process parameters is micro-cutting wear accompanied by micro-fracture wear.

Pulsed DC plasma enhanced chemical vapor deposited TiN/Ti(C,N) multilayer coatings

TiN single coatings and TiN/Ti(C,N) multilayer coatings deposited on Cr12MoV substrate have been completed by pulsed DC plasma enhanced chemical vapor deposition(PCVD) process. The SEM, XRD and microvicker’s hardness as well as the indentation test were used to study the microstructure and mechanical properties of TiN/Ti(C,N) multilayer coatings. The results show that TiN/Ti(C,N) coatings are fine and have free column structure, and carbon atoms take the place of some nitrogen atoms in Ti(C,N) coatings when lower flow ratio of CH 4 is used. The microvicker’s hardness and interfacial adhesion between TiN/Ti(C,N) coatings and Cr12MoV substrate increases more obviously than that of TiN single hard coatings due to the more dense and free column structure when process is optimized.

Salt spray corrosion test of micro-plasma oxidation ceramic coatings on Ti alloy

Ceramic coatings were prepared on Ti-6Al-4V alloy in NaAlO2 solution by micro-plasma oxidation （MPO）. The salt spray tests of the coated samples and the substrates were carded out in a salt spray test machine. The phase composition and surface morphology of the coatings were investigated by XRD and SEAM. Severe corrosion occurred on the substrate surface, while there were no obvious corrosion phenomena on the coated samples. The coatings were composed of Al2TiO5 and a little α-Al2O3 and mille TiO2, and the salt spray test did not change the composition of the coatings. The weight loss rate of the coatings decreased with increasing MPO time because of the increase in density and thickness of the coatings. The surface morphology of the coatings was influenced by salt spray corrosion test. Among the coated samples, the coating prepared for 2 h has the best corrosion resistance under salt spray test.

Structural characteristics and high-temperature tribological behaviors of laser cladded NiCoCrAlY−B_(4)C composite coatings on Ti6Al4V alloy

In order to improve the hardness and tribological performance of Ti6Al4V alloy,NiCoCrAlY-B_(4)C composite coatings with B_(4)C of 5%,10%and 15%(mass fraction)were fabricated on its surface by laser cladding(LC).The morphologies,chemical compositions and phases of obtained coatings were analyzed using scanning electronic microscope(SEM),energy dispersive spectrometer(EDS),and X-ray diffraction(XRD),respectively.The effects of B_(4)C mass fraction on the coefficient of friction(COF)and wear rate of NiCoCrAlY-B_(4)C coatings were investigated using a ball-on-disc wear tester.The results show that the NiCoCrAlY-B_(4)C coatings with different B_(4)C mass fractions are mainly composed of NiTi,NiTi_(2),α-Ti,CoO,AlB_(2),TiC,TiB and TiB_(2)phases.The COFs and wear rates of NiCoCrAlY-B_(4)C coatings decrease with the increase of B_(4)C content,which are contributed to the improvement of coating hardness by the B_(4)C addition.The wear mechanisms of NiCoCrAlY-B_(4)C coatings are changed from adhesive wear and oxidation wear to fatigue wear with the increase of B_(4)C content.

AFM Analysis of TiN, TiAlN, and TiAlSiN Coatings Prepared by Cathodic Arc Ion Plating

The TiN, TiAlN, and TiAlSiN coatings were prepared on YT14 cutting tool surface with CAIP（cathode arc ion plating）, the surface morphologies and phases were analyzed with FESEM（field emission scanning electron microscopy）, and XRD（X-ray diffraction）, respectively, and the coating parameters such as 3D surface micro-topography, grain size, surface height, hierarchy, profile height, and power spectral density, etc, were measured with AFM（atomic force microscope）. The results show that the phases of TiN, TiAlN, and TiAlSiN coatings are TiN, TiN＋TiAlN, TiN＋Si_3N_4＋TiAlN, respectively, while the surface roughness Sa of TiN, TiAlN, and TiAlSiN coatings is 75.3, 98.9, and 42.1 nm, respectively, and the roughness depth Sk is 209, 389, and 54 nm, respectively, the sequence of average grain sizes is TiAlN〉TiN〉TiAlSiN. The surface bearing index Sbi of TiN, TiAlN, and TiAlSiN coatings is 0.884, 1.01, and 0.37, respectively, and the sequence of surface bearing capability is TiAlN〉TiN〉TiAlSiN. At the lower wavelength（102-103 nm）, the power spectral densities have a certain correlation, and the sequence of TiN〉TiAlN〉TiAlSiN, while the correlation is low at the higher wavelength（〉103 nm）.

Influence of Si Content on Properties of Ti1-xSixN Coatings

To investigate the evolution of microstructure and wear behavior of TiSiN coatings with the variation of Si in targets and lays the foundation for its controllable mass production, Ti1-xSixN composite coatings were deposited onto Si(100) and cemented carbide substrates using TiSi targets with different Si content by cathodic arc ion plating. The influences of Si on the microstructure and mechanical properties were studied. Nano-amorphous composite structure appeared in the Ti1-xSixN coatings when Si content in TiSi target was higher than 5 at%. However, further increase of Si content in TiSi target exhibited a negligible effect on the microstructure of Ti1-xSixN coatings. Hardness and deformation resistance were correlated to the content of Si in TiSi targets. Maximum hardness was obtained as the Si content in target increased up to 20 at%. Friction coefficient and wear rate significantly decreased with addition of Si in TiN coating, and then dually increased with the increase of Si content in targets.

The Stress Distribution and Thermal Behavior of TiBN and TiBN TiN Coatings in Milling AISI H13 Work Tool Steel

The FEM model of TiBN and TiBN/TiN coated cutting tool in milling of H13 steel w as developed. Process variables such as temperature and stress in the coating l ayer as well as in the substrate were analyzed. The efficacy of the present FEM analysis was verified by conducting controlled milling experiments on AISI H13 t o collect the relevant tool life and force data.The results show that the stress in a coated tool can significantly be reduced compared to an uncoated cutting t ool,possibly due to surface coatings improving the tribological properties of cu tting tools.Coatings with good thermal properties also help to improve the therm al behavior of cutting tool.