Oxidation of TiN and Ti(C,N) thin films deposited on titanium substrate

Single-layered TiN and functionally graded Ti(C,N) coatings were magnetron sputtered to a thickness of about 1 μm, and their oxidation behavior was studied. The Ti(C,N) coating oxidized as fast as the TiN coating, forming TiO₂ as an oxide layer. The nitrogen in the TiN and Ti(C,N) coatings tended to escape from the coating via the TiO₂ layer into the air. The carbon in the Ti(C,N) coating also had strong tendency to escape. Even before the complete oxidation of the coatings, the retained coating layer and the Ti-substrate were strongly enriched with oxygen.     

Oxidation Resistance of Ti5Si3 and Ti5Si3Zx at 1000°C (Z = C,N, or O)

The oxidation behavior of Ti₅Si_3+y (y=0 or 0.2) and Ti₅Si₃Z_x (Z=C, N or O, x=0.25 or 0.5) was studied at 1000°C in air or argon–oxygen mixtures for up to 500 h. Ti₅Si₃ has poor oxidation resistance in air because of the formation of an oxide scale rich in rutile and subscale formation of TiN, TiSi, TiSi₂ and Si. In contrast, Ti₅Si_3.2 has excellent oxidation resistance because of the formation of a silica scale. Samples with interstitial oxygen or nitrogen show only slight improvements in the early stages of oxidation, compared to Ti₅Si₃, which is in stark contrast to previous research. However, samples with interstitial carbon displayed excellent oxidation resistance at 1000°C, consistent with previous research.     

Dry sliding wear behavior of PVD TiN,Ti55Al45N,and Ti35Al65N coatings at temperatures up to 600 °C

Three PVD nitride coatings (TiN, Ti₅₅Al₄₅N, and Ti₃₅Al₆₅N) with different Al content were deposited on the cemented carbides by cathode arc-evaporation technique. Microstructural and fundamental properties of these nitride coatings were examined. The friction and wear behavior of these coatings were evaluated at temperatures up to 600 °C. The wear surface features of the test samples were examined by scanning electron microscopy. Results showed that the friction coefficient of these nitride coatings is different depending on the temperature. The friction coefficient of TiN coating increased with the increase of test temperature; while the friction coefficient of Ti₅₅Al₄₅N and Ti₃₅Al₆₅N coatings with the addition of Al decreased with the increase of test temperature. The Ti₅₅Al₄₅N and Ti₃₅Al₆₅N coatings exhibited higher wear resistance over the one without Al (TiN coating). The wear resistance of these nitride coatings at high temperature wear tests is significantly dependent on their tribological oxidation behavior. The Ti₅₅Al₄₅N and Ti₃₅Al₆₅N coatings with the addition of Al exhibited improved wear resistance as compared to the TiN coating, which was attributed to that their tribo-chemically formed Al₂O₃ exhibited better tribological properties than the TiO₂ of the latter.     

Characteristics and machining applications of Ti(Y)N coatings

The Ti(Y)N coatings were successfully deposited onto 18-8 stainless steel substrates by the hollow cathode discharge ion-plating method. The influence of the rare-earth element yttrium on the TiN coating properties was studied. The results show that the adhesion of the coating to the substrate were evidently enhanced by adding a small amount (0.2 wt.%) of the rare-earth element yttrium, showing a critical load of about 390 g which is much higher than that (230 g) of the TiN coating/substrate. Investigation on the corrosion resistance of the Ti(Y)N coating and the TiN coating was performed in 0.5 N Na₂SO₄ + 0.1 N H₂SO₄ + 0.1 N NaCl corrosion media by means of an electrochemical potentiodynamic polarization. The Ti(Y)N coating exhibited much better corrosion resistance than the TiN coating, whose passivity maintaining current is about one order in magnitude smaller than that of the TiN coating.The Ti(Y)N coatings deposited on some HSS-based tools were presented and compared with the TiN coating. The service lifetime of Ti(Y)N coated tools is approximately 36% higher (on the pinion shape cutters) and about 50% higher (on punch side pin) compared to that of TiN coated. The Ti(Y)N coatings showed such excellent performance. It is attributed to that the transition area of Ti(Y)N/substrate consisted of three sublayers which revealed a gradual change of phase structure and composition, so that the adhesion of the coating/substrate was evidently enhanced. Moreover, Ti(Y)N coating showed a preferred orientation with (111) plane which is favorable to improve wear resistance and corrosion resistance of the coating.     

Microstructure and properties of CVD coated Ti(C,N)-based cermets with varying WC additions

In this paper, multilayer coatings of TiN/TiCN/Al₂O₃/TiN are deposited on the Ti(C, N)-based cermets containing WC, and the effect of WC on the growth and adhesion strength as well as the mechanical properties of the coating are investigated. The multilayer coatings deposited by chemical vapor deposition (CVD) are uniform and dense. TiN coating exhibits a dense fine-grained structures and the Ti (C,N) on TiN coating shows dense columnar structure. The α-Al₂O₃ layer deposited on transition coating presents coarse grains with limited voids. The grain size of the columnar crystals deposited on the substrates gradually decreases with WC addition. The Al₂O₃ layer shows a preferred growth orientation of (104) plane. For TiN/TiCN phase, a change in orientation from (111) to (200) is observed. Generally, the (200) preferred orientation enhances and (111) preferred orientation diminishes with increasing WC addition. Strong adhesion of the CVD coating is obtained due to a sufficient amount of chemical elements, especially tungsten, diffusing from the substrate to the interfacial layer. Scratch tests show that the adhesion strength of TiN/TiCN/Al₂O₃/TiN films gradually increases firstly, and then decreases. With the addition of WC, the hardness, elastic modulus and plasticity index increase at the beginning, and then decrease. The change in nanohardness and elastic modulus is related to the grain size, elemental diffusion, and preferred orientation of the coating.     

Structure and mechanical properties of TiAlCrSiN coatings deposited on Ti(C,N)-NbC-Ni cermets with varied Mo2C contents

TiAlCrSiN coatings were deposited on Ti(C,N)-NbC-Ni cermets with varied Mo₂C contents by medium frequency reactive magnetron sputtering, and their structure, phases, mechanical and frictional properties were investigated in the present work. The results indicated that both the Mo diffusion to the coating and the Al diffusion to the substrate resulted in the decreased lattice parameter of TiAlCrSiN phase in the coating. When increasing Mo₂C contents in the substrate, the columnar crystal grains in the coating were refined, whereas the adhesion of the coating to the substrate was degraded as a result of the coating thickening and the inner stress in the coating. Apart from being influenced by grain size, the coating's hardness was also linked to the crystal plane orientation, and it declined with a decrease of relative intensity ratio of I₍₁₁₁₎/I₍₂₀₀₎ in the TiAlCrSiN coating. The elasticity modulus of the coating decreased slightly due to the grain refinement in the coating. The average friction coefficient of TiAlCrSiN coating was reduced by oxidation of the Mo diffused from the substrate, while the friction coefficient was not the predominant indicator influencing wear rate of the coated Ti(C,N)-NbC-Ni cermet.     

Mechanical Properties and Oxidation Behavior of a Graded (Ti,Al)N Coating Deposited by Arc-Ion Plating

A graded (Ti,Al)N coating was deposited on 1Cr–11Ni–2W–2Mo–V stainless steel for aero-engine compressor blades by arc-ion plating(AIP). The microstructure and the morphology of the graded coating were investigated using electron-probe microanalysis (EPMA), X-ray diffraction and scanning-electron microscopy. The mechanical properties of the graded coating were investigated and it was found that the microhardness and the wear resistance were similar to those of the monolithic (Ti,Al)N coating, but much better than those of a homogenous TiN coating. In addition, the adhesive strength and the thermal-shock resistance of the graded (Ti,Al)N coating were much better than those of the monolithic TiN and (Ti,Al)N coatings. The oxidation tests were performed at 600 and 700°C in air for 500 hr, and corrosion tests were carried out at 600°C under the synergistic effect of water vapor and NaCl for 20 hr. Compared to pure TiN, it was found that due to the incorporation of aluminum, a protective layer rich in alumina was formed on top of the graded (Ti,Al)N coating, which greatly improved the oxidation resistance and corrosion resistance of the coating.     

液-固扩散焊复合连接Ti(C,N)与40Cr的界面行为与接头强度

通过预置Ti/Cu非对称中间层对Ti(C,N)基金属陶瓷与40Cr钢进行了液-固扩散焊复合连接试验,重点研究了界面组织、接头强度及其影响因素.结果表明,通过预置Ti/Cu非对称中间层液-固扩散焊,能够分别实现Ti(C,N)基金属陶瓷与铜箔,以及铜箔与40Cr钢之间的冶金结合;Ti(C,N)基金属陶瓷界面物相呈梯度分布,形成Ti(C,N)基金属陶瓷/TiAl₂/Ti₂Cu/TiCu/铜箔结构;Ti(C,N)基金属陶瓷一侧靠近界面区域存在较大的焊接残余拉应力,以及脆弱的TiAl₂金属间化合物层,是制约焊接接头强度的关键因素;单纯以铜箔为中间层,采用常规固相扩散焊连接Ti(C,N)基金属陶瓷,即使在加热温度1223 K、压力20 MPa条件下,也难以实现Ti(C,N)基金属陶瓷与铜箔的有效连接.     

The Effect of Hf on the Oxidation and Corrosion Behavior of Ti0.7Al0.3N Coating Prepared by Arc-Ion Plating

Ti_0.7Al_0.3N and Ti_0.68Al_0.30Hf_0.02N coatings were deposited on 1Cr–11Ni–2W–2Mo–V stainless steel by arc-ion plating (AIP), and their oxidation and corrosion performance were characterized using TGA, TEM, SEM/EDS, EPMA and XRD. The oxidation behavior of the coatings at 800 °C for up to 100 h was investigated, and the results showed that the introduction of hafnium into the Ti_0.7Al_0.3N coating dramatically improved the oxidation-resistance of the coating in air. Compared to the Ti_0.7Al_0.3N coating, the presence of Hf in the nitride coating promoted the outward diffusion of Al, and suppressed the outward diffusion of Ti and inward diffusion of O. The Ti_0.7Al_0.3N coating was completely oxidized and formed a layered scale after oxidation at 800 °C for 20 h in air. Meanwhile, local serious oxidation of the substrate occurred. Corrosion tests of the coatings with a NaCl deposit in wet oxygen at 650 °C for 10 h were also conducted, and the results showed that the Ti_0.7Al_0.3N coating suffered serious local corrosion, while a thin and dense scale formed on the surface of the Ti_0.68Al_0.30Hf_0.02N coating, and its anti-corrosion performance was remarkably enhanced.     

Thermal and thermo-mechanical properties of Ti–Al–N and Cr–Al–N coatings

Metastable Ti–Al–N and Cr–Al–N coatings have been proven to be an effective wear protection due to their outstanding mechanical and thermal properties. Here, a comparative investigation of mechanical and thermal properties, for Ti–Al–N and Cr–Al–N coatings deposited by cathodic arc evaporation with the compositions (c-Ti_0.52Al_0.48N, c/w-Ti_0.34Al_0.66N and c-Cr_0.32Al_0.68N) widely used in industry, has been performed in detail. The hardness of Ti_0.52Al_0.48N and Ti_0.34Al_0.66N coatings during thermal annealing, after initially increasing to the maximum value of ~ 34.1 and 38.7 GPa with T_a up to 900 °C due to the precipitation of cubic Al-rich and Ti-rich domains, decreases with further elevated T_a, as the formation of w-AlN and coarsening of precipitated phases. A transformation to Cr₂N and finally Cr via N-loss in addition to w-AlN formation during annealing of the Cr_0.32Al_0.68N coating occurs, and thus results in a continuous decrease in hardness. Among our coatings, the mixed cubic-wurtzite Ti_0.34Al_0.66N coating exhibits the highest thermal hardness, but the worst oxidation resistance. The Cr_0.32Al_0.68N coating shows the best oxidation resistance due to the formation of dense protective α-Al₂O₃-rich and Cr₂O₃-rich layers, with only ~ 1.4 μm oxide scale thickness, after thermal exposure for 10 h at 1050 °C in ambient air, whereas Ti–Al–N coatings are already completely oxidized at 950 °C.     

Early high temperature oxidation behaviour of Ti(C,N)-based cermets in air

Isothermal oxidation behaviour of two Ti(C,N)-based cermets (TiC-10TiN-16Mo-6.5WC-0.8C-0.6Cr₃C₂-(32-x)Ni-xCr, x = 0 and 6.4 wt%) was investigated in air at 800-1100 °C up to 2 h. Mass gains exhibited neither linear nor parabolic law during isothermal oxidation. The oxide scales formed at 800-1100 °C were multi-layered, consisting of NiO outerlayer, NiTiO₃ interlayer and TiO₂-based innerlayer. The internal oxidation zones formed at 1000-1100 °C consisted of Ti-based, Ni-based and Mo-based complex oxides. Cermet with 6.4 wt% Cr exhibited superior oxidation resistance, due to the presences of Cr_0.17Mo_0.83O₂ in TiO₂-based innerlayer of the oxide scale and Cr-rich Ti-based complex oxide in the internal oxidation zone.     

Effect of C2H2 gas flow rate on synthesis and characteristics of Ti–Si–C–N coating by cathodic arc plasma evaporation

The influences of C₂H₂ gas flow rate on the synthesis, microstructure, and mechanical properties of the Ti–Si–C–N films were investigated. Quaternary Ti–Si–C–N coatings were deposited on WC-Co substrates using Ti and TiSi (80:20 at.%) alloy target on a dual cathodic arc plasma evaporation system. The Ti–Si–C–N coatings were designed with Ti/TiN/TiSiN as an interlayer to enhance the adhesion strength between the top coating and substrate. The Ti–Si–C–N coatings were deposited under the mixture flow of N₂ and C₂H₂. Composition analysis showed that as the C₂H₂ gas flow increased, the Ti, Si and N contents decreased and the carbon content increased in the coatings. The results showed the maximum nanohardness of approximately 40 GPa with a friction coefficient of 0.7 was obtained at the carbon content of 28 at.% (C₂H₂ = 15 sccm). However, as the C₂H₂ gas flow rate increased from 15 to 40 sccm (carbon content from 25.2 to 56.3 at.%), both the hardness and friction coefficient reduced to 20 GPa and 0.3, respectively. Raman analysis indicated the microstructure of the deposited coating transformed from Ti–Si–C–N film to TiSi-containing diamond-like carbon films structure, which was strongly influenced by the C₂H₂ flow rate and is demarcated at a C₂H₂ flow of 20 sccm. The TiSi-containing diamond-like carbon films reveal low-friction and wear-resistant nature with an average friction coefficient between 0.3 and 0.4, lower than both TiSiN and Ti–Si–C–N films.     

碳氮比对Ti(C,N)粉末抗氧化性的影响

本文对不同碳氮比Ti(C,N)固溶体粉末分别进行了等温氧化和非等温氧化,通过TG-DSC热分析、氧化动力学分析和物相分析,研究了碳氮原子比对Ti(C,N)粉末氧化行为的影响。Ti(C,N)粉末在O2气流中从室温加热至1 000~1 200℃的非等温氧化,以及在650℃的静置空气中的等温氧化。结果表明,Ti(C,N)粉末在非等温氧化过程中,氧化过程可分为2个阶段或3个阶段,第1氧化阶段氧化脱氮占主导地位,第2氧化阶段氧化脱碳占主导地位,Ti(C0.5,N0.5)粉末表现出最优的抗氧化性能。在650℃的等温氧化中,Ti(C,N)粉末氧化遵循随机形核动力学模型,Ti(C0.7,N0.3)具有最小的一阶速率常数,表现出最优的抗氧化性能。初始氧化固体产物为锐钛矿结构TiO2,随氧化时间延长,逐渐向金红石结构TiO2转变。     

NiCoCrAlY coatings with and without an Al2O3/Al interlayer on an orthorhombic Ti2AlNb-based alloy: Oxidation and interdiffusion behaviors

The mechanism of oxidation protection of NiCoCrAlY overlay coatings on the orthorhombic Ti₂AlNb-based alloy (O alloy) Ti–22Al–26Nb (at.%) is described. While the bare alloy exhibited poor oxidation resistance at 800 °C, adding NiCoCrAlY coatings significantly improved the oxidation resistance. However, serious interdiffusion between the coatings and the substrate resulted in rapid degradation of the coating system. Several reaction layers were formed at the coating/substrate interface by interdiffusion, and non-protective scales mainly of Cr₂O₃ and TiO₂ were formed due to the degradation of the coating. In order to solve this problem, an Al₂O₃/Al interlayer was sandwiched into the coating system as a diffusion barrier. The isothermal and cyclic oxidation protection of the multilayer coating system on the Ti–22Al–26Nb substrate was evaluated at 800 and 900 °C. The results indicated that the interdiffusion was much suppressed, and the duplex coating system demonstrated improved oxidation resistance on the Ti–22Al–26Nb substrate, with a thin and adherent protective α-Al₂O₃ scale forming on the surface.     

Effect of SI Content on the Oxidation Resistance of Ti3Al1-x Si x C2 (x⩽ 0.25) Solid Solutions at 1000–1400°C in Air

The oxidation behavior of Ti₃Al_1-x Si _x C₂ (x ⩽ 0.25) solid solutions was investigated in flowing air at 1000–1400°C for up to 20 hrs. Similar to Ti₃AlC₂, Ti₃Al_1-x Si _x C₂ (x⩽ 0.15) solid solutions display excellent oxidation resistance at all temperatures because of the formation of the continuous α-Al₂O₃ protective layers. However, Al₂(SiO₄)O formed during oxidation of Ti₃Al_1-x Si _x C₂ (x=0.2 and 0.25) solid solutions at and above 1100°C, which is believed to be responsible for the deterioration of oxidation resistance of Ti₃Al_0.75Si_0.25C₂ at 1300°C. Additionally, Ti₅Si₃ was also found in the oxidized samples. This implies that Ti₅Si₃ precipitated from Ti₃Al_1-x Si _x C₂ solid solutions during oxidation. But it has been proven that Ti₅Si₃ has little effect on the oxidation resistance of the material, which is attributed to an interstitial carbon effect.     

SiO2–Al2O3–glass composite coating on Ti–6Al–4V alloy: Oxidation and interfacial reaction behavior

A SiO₂–Al₂O₃–glass composite coating was prepared on Ti–6Al–4V alloy by air spraying and subsequent firing. The oxidation behavior of the specimens at 800 °C and 900 °C for 100 h was studied. The thermal shock resistance of the coating was tested by heating up to 900 °C and then quenching in water. The composite coating acted as an oxygen migration barrier and exhibited good resistance against high temperature oxidation, thermal shock, and oxygen permeation on the Ti–6Al–4V alloy. Coating/alloy interfacial reaction occurred, forming a Ti₅Si₃/Ti₃Al bilayer structure. A thin Al₂O₃ rich layer formed beneath the composite coating during oxidation at 900 °C.     

Reaction diffusion in continuous SiC fiber reinforced Ti matrix composite

SiC continuous fiber-reinforced pure Ti(TA1)matrix composites were fabricated by a vacuum hot pressing(VHP)methodand then heat-treated in vacuum under different conditions.The interfacial reaction and the formation of interfacial phases werestudied by using SEM,EDS and XRD.The results show that there exists reaction diffusion at the interface of SiC fibers and Timatrix,and the concentration fluctuation of reaction elements such as C,Ti and Si appears in interfacial reaction layer.The interfacialreaction products are identified as Ti3SiC2,TiCx and Ti5Si3Cx.At the beginning of interfacial reaction,the interfacial reactionproducts are TiCx and Ti5Si3Cx.Along with the interfacial reaction diffusion,Ti3SiC2 and Ti5Si3Cx single-phase zones come forth inturn adjacent to SiC fibers,and the TiC Ti5Si3Cx double-phase zone appears adjacent to Ti matrix,which forms discontinuousconcentric rings by turns around the fibers.The formed interfacial phases are to be Ti3SiC2,Ti5Si3Cx and TiCx Ti5Si3Cx from SiCfiber to Ti matrix.The interfacial reaction layer growth is controlled by diffusion and follows a role of parabolic rate,and theactivation energy(Qk)and(k0)of SiC/TA1 are 252.163 kJ/mol and 7.34×10?3m/s1/2,respectively.     

Nanolayer (Ti,Cr)N coatings for hard particle erosion resistance

This paper discusses the synthesis and characterization of titanium chromium nitride ((Ti,Cr)N) thin films deposited onto AM355 stainless steel by multi-source cathodic arc physical vapor deposition (PVD) for improved erosion resistance. The effect of Cr evaporator current and substrate bias on the erosion resistance of the (Ti,Cr)N coating were investigated. The coatings were characterized using X-ray diffraction, scanning electron microscopy, electron probe microanalysis, scanning transmission electron microscopy, scratch adhesion testing and erosion testing. The (Ti,Cr)N coatings deposited using multisource mode were determined to be nanolayered structures consisting of TiN rich and CrN rich layers. EPMA showed that the atomic percentage of Cr within the coating increased (increased Cr:Ti ratio) with increasing Cr evaporator current and that the (Ti,Cr)N chemical composition did not appear to change with varying bias. Using XRD and STEM, it was determined that all nanolayer (Ti,Cr)N coatings were multi-phased consisting of a B1 NaCl crystal structure. XRD also revealed that as the Cr evaporator current was increased, there was an increase in the CrN phase volume. Macroparticle incorporation increased with an increase in Cr evaporator current and decreased with an increase in bias. The nanolayer (Ti,Cr)N coatings ranged in Vickers hardness from 1700 to 2800 VHN_0.050. Coating adhesion increased as Cr:Ti ratio increased. In regards to erosion, (Ti,Cr)N coatings with a high number of TiN/CrN interfaces performed poorly against alumina media. As the Cr evaporator current was varied, the coating deposited with the highest Cr:Ti ratio (evaporator current of 85 A) and when bias was varied, the lowest substrate bias of - 50 V had the best erosion performance.     

Synthesis of ultrafine (Ti, W, Mo, V)(C, N)–Ni composite powders by low-energy milling and subsequent carbothermal reduction–nitridation reaction

Ultrafine (Ti, W, Mo, V)(C, N)–Ni composite powders with globular-like particles of 50–300 nm were synthesized at static nitrogen pressure from oxides by a simple and cost-effective route which combines traditional low-energy milling plus carbothermal reduction–nitridation (CRN) techniques. Reaction path of the (Ti, W, Mo, V)(C, N)–Ni system was discussed by X-ray diffraction (XRD) and thermogravimetry–differential scanning calorimetry (TG–DSC), and microstructure of the milled powders and final products was studied by scanning electron microscopy (SEM) and transmission electron microscope (TEM), respectively. The results show that CRN reaction has been enhanced by nano-TiO₂ and nano-carbon powders. Thus, the preparation of (Ti, 15W, 5Mo, 0.2V)(C, N)–20Ni is at only 1300 °C for 1 h. During synthesizing reaction, Ni solid solution phase forms at about 700 °C and reduction–carbonization of WO₂ and MoO₂ occurs below 900 °C. The reactions of TiO₂ → Ti₃O₅, Ti₃O₅ → Ti(C, O) and Ti(C, O) → Ti(C, N) take place at about 930 °C, 1203 °C and 1244 °C, respectively.     

Erosion-corrosion behavior of Ti(C,N)-based cermets containing different secondary carbides

The present work investigated the effects of secondary carbides (Mo₂C\WC\TaC\NbC) on the erosion-corrosion behavior of Ti(C,N)-based cermets. The results indicate that the erosion-corrosion resistance of Ti(C,N)-based cermets is enhanced in the order of NbC, TaC, WC and Mo2C addition. The contribution of erosion to the erosion-corrosion of Ti(C,N)-based cermets is much more significant than that of corrosion, and it increases with the decreased mechanical properties. The synergistic effect plays a dominant role in the degradation of Ti(C,N)-based cermets in erosion-corrosion conditions. There are two modes to ceramic phase degradation in erosion conditions: large ceramic grains are prone to deterioration through crack initiation and propagation → grain fracture → fragment removal; finer ceramic grains trend to be pulled out after the deterioration of binder and interface. The binder loss is determined by the corrosion resistance of binder, the erosion resistance of binder and the erosion resistance of ceramic phase.