Oxidation behaviours of Nb–22Ti–15Si–2Al–2Hf–2V–(2, 14)Cr alloys with Al and Y modified silicide coatings prepared by pack cementation

Al and Y modified silicide coatings on the Nb-15Si-22Ti-(2,14)Cr-2Al-2Hf-2V alloys(where the alloy with 2 at%Cr or 14 at%Cr is hereafter referred to as 2Cr and 14 Cr alloy,respectively) was prepared by pack cementation.The microstructural evolution and the oxidation behaviours of the coating 2Cr and 14 Cr samples at 1250 ℃ were studied.The 2Cr alloy consists of Nb solid solution(Nb_(SS)) and α-Nb_5Si_3 silicide,while the Laves C15-Cr_2Nb phase arised in the 14 Cr alloy.The coating structure of the coating 2Cr sample contained the outer(Nb,X)Si_2+(Nb,X)_5Si_3 layer,the middle(Nb,X)_5Si_3 layer and the inner undeveloped intermetallic(Nb,Ti)_3(Al,X) layer,the structure of the coating 14 Cr sample consisted of the outer single(Nb,X)Si_2 layer,the middle(Nb,X)_5Si_3 layer,the transition(Nb,Ti)(Cr,Al) layer and the inner(Cr,Al)_2(Nb,Ti) layer.The coating 14 Cr sample exhibited better oxidation resistance than the coating 2Cr sample.With an outer single(Nb,X)Si_2 layer,a compact oxide scale consisting of SiO_2 and TiO_2 formed on the coating14 Cr sample,which can efficiently prevent the substrate from oxidising.For the coating 2Cr sample with an outer(Nb,X)Si_2 +(Nb,X)_5Si_3 layer,the oxide scale of the SiO_2,TiO_2,Nb_2O_5 and CrNbO_4 mixture generated,and the scale spalled out from the surface of the sample,resulting in disastrous failure.     

Microstructure and growth kinetics of Ce and Y jointly modified silicide coatings for Nb–Ti–Si based ultrahigh temperature alloy

In order to protect Nb-Ti-Si based ultrahigh temperature alloy from oxidation, pack cementation processes were utilized to prepare Ce and Y jointly modified silicide coatings. The Ce and Y jointly modified silicide coating has a double-layer structure: a relatively thick (Nb, X)Si2 (X represents Ti, Cr and Hf elements) outer layer and a thin (Ti, Nb)5Si4 transitional layer. The pack cementation experiments at 1150 ℃ for 8 h proved that the addition of certain amounts of CeO2 and Y2O3 powders in the packs distinctly influenced the coating thickness, the contents of Si, Ce and Y in the (Nb, X)Si2 outer layers, and the density of cavities in the coatings. In order to study the effects of Ce and Y joint modification in the silicide coatings, both only Ce and only Y modified silicide coatings were also prepared for comparison. The mechanisms of the beneficial effects of Ce and Y are discussed. A pack mixture containing 1.5CeO2-0.75Y2O3 (wt%) powders was employed to investigate the growth kinetics of the Ce and Y jointly modified silicide coating at 1050, 1150 and 1250 ℃. It has been found that the growth kinetics obeyed parabolic laws and the parabolic rate constants were 109.20 mm2/h at 1050 ℃, 366.75 mm2/h at 1150 ℃ and 569.78 mm2/h at 1250 ℃, and the activation energy for the growth of the Ce and Y jointly modified silicide coating was 197.53 kJ/mol.     

Effect of Y_2O_3 content in the pack mixtures on microstructure and oxidation resistance of B–Y modified silicide coating

B–Y modified silicide coatings were prepared on Nb–Si based alloy by pack cementation at 1300 ℃ for 10 h. The effect of Y_2O_3 content in the pack mixtures on microstructure and oxidation resistance of the coatings was investigated. The results show that the four coatings have similar structures, which possess a(Nb,X)Si_2 outer layer and a(Nb,X)_5Si_3 transitional layer. Y_2O_3 content in the pack mixtures has an obvious effect on the Si content in the coating. The mass gains of the coatings prepared with 0.5, 1, 2 and 3 wt% Y_2O_3 in pack mixtures are 2.33, 1.96, 2.05 and 2.86 mg/cm~2 after oxidation at 1250 ℃ for 100 h, respectively. The coating prepared with 1 wt% Y_2O_3 exhibits the best oxidation resistance due to the formation of a dense glass-like borosilicate scale.     

9Cr?5Si?3Al铁素体耐热钢的高温氧化行为

To improve the oxidation properties of ferritic heat-resistant steels, an Al-bearing 9Cr?5Si?3Al ferritic heat-resistant steel was designed. We then conducted cyclic oxidation tests to investigate the high-temperature oxidation behavior of 9Cr?5Si and 9Cr?5Si?3Al ferritic heat-resistant steels at 900 and 1000°C. The characteristics of the oxide layer were analyzed by X-ray diffraction, scanning electron microscopy, and energy dispersive spectroscopy. The results show that the oxidation kinetics curves of the two tested steels follow the parabolic law, with the parabolic rate constant k_p of 9Cr?5Si?3Al steel being much lower than that of 9Cr?5Si steel at both 900 and 1000°C. The oxide film on the surface of the 9Cr?5Si alloy exhibits Cr₂MnO₄ and Cr₂O₃ phases in the outer layer after oxidation at 900 and 1000°C. However, at oxidation temperatures of 900 and 1000°C, the oxide film of the 9Cr?5Si?3Al alloy consists only of Al₂O₃ and its oxide layer is thinner than that of the 9Cr?5Si alloy. These results indicate that the addition of Al to the 9Cr?5Si steel can improve its high-temperature oxidation resistance, which can be attributed to the formation of a continuous and compact Al₂O₃ film on the surface of the steel.     

Microstructure characteristics of Ni/WC composite cladding coatings

A multilayer tungsten carbide particle (WCp)-reinforced Ni-based alloy coating was fabricated on a steel substrate using vacuum cladding technology. The morphology, microstructure, and formation mechanism of the coating were studied and discussed in different zones. The microstructure morphology and phase composition were investigated by scanning electron microscopy, optical microscopy, X-ray diffraction, and energy-dispersive X-ray spectroscopy. In the results, the coating presents a dense and homogeneous microstructure with few pores and is free from cracks. The whole coating shows a multilayer structure, including composite, transition, fusion, and diffusion-affected layers. Metallurgical bonding was achieved between the coating and substrate because of the formation of the fusion and diffusion-affected layers. The Ni-based alloy is mainly composed of γ-Ni solid solution with finely dispersed Cr₇C₃/Cr₂₃C₆, CrB, and Ni+Ni₃Si. WC particles in the composite layer distribute evenly in areas among initial Ni-based alloying particles, forming a special three-dimensional reticular microstructure. The macrohardness of the coating is HRC 55, which is remarkably improved compared to that of the substrate. The microhardness increases gradually from the substrate to the composite zone, whereas the microhardness remains almost unchanged in the transition and composite zones.     

Ti4+在铁酸钙/钛酸钙扩散偶中的扩散系数

This study investigated the interdiffusion of calcium ferrite/calcium titanate system in the time range of 0–120 min by the diffusion couple method in a CO/N₂ reducing atmosphere at 700°C. The results show that after the diffusion reaction occurred, no longitudinal agglomerations were present on the substrate surface on the calcium titanate side. When the diffusion time was increased to 105 min, a net vacancy flow from calcium titanate to calcium ferrite might have occurred, causing the surface of the calcium ferrite substrate to collapse. The thickness of the diffusion layer of the calcium ferrite/calcium titanate system was about 17–48 μm, which conforms to the parabolic law of diffusion. The diffusion coefficient and the Ti4+ concentration in the calcium ferrite/calcium titanate system are related. This shows an increase in the diffusion coefficient with the increase of Ti4+ concentration, and the diffusion coefficient value was in the range of 10?12–10?11 cm2·s?1.     

ORDERING TRANSFORMATION OF γ TO γ1 IN TiAl+Nb SYSTEM

A series of TiAl+Nb alloys with various Nb contents has been employed to explore phase relationship and the evolution of microstructure.A new ordered γ derivative (γ₁) has been observed in the alloy containing 20 at% Nb.The additional diffraction spots added to the diffraction pattern of L1₀ (TiAl) structure have been found in the alloy containing Nb up to 11 at% in terms of further ordering.The transformation from L1₀ (TiAl) structure to the further ordering phase,γ₁,is a continuous ordering process with the substitution of Nb atoms for Ti atoms in alloys with over-stoichiometric Al content of TiAl.The possible transformtion characterzation has been discussed.     

Formation mechanism of an aluminium-based chemical conversion coating on AZ91D magnesium alloy

An environmentally clean aluminium-based conversion coating on AZ91D magnesium alloy was studied in aluminium nitrate solutions. The morphology, composition, structure, and formation mechanism of the coating were investigated in detail using scanning electron microscopy/energy dispersion spectrometry, X-ray diffraction, transmission electron microscopy, and electrochemical corrosion tests. The results show that the conversion coating is composed of magnesium, aluminium, and oxygen, and shows an amorphous structure. In the initial stage of coating formation, the grain-like nucleus is composed of Al₁₀O₁₅·xH₂O, (Al₂O₃)_5.333, Al₂O₃, AlO(OH), MgAl₂O₄, (Mg_0.88Al_0.12)(Al_0.94Mg_0.06)₂O₄, and (Mg_0.68Al_0.32)(Al_0.84Mg_0.16)₂O₄. The conversion coating formed in the 0.01 mol/L aluminium nitrate solution for 15 min can improve the corrosion resistance of the magnesium alloy greatly. The discussion reveals that the possible formation mechanism for the aluminium-based conversion coating is the reduction reaction on micro-cathodic sites due to the electrochemically heterogeneous magnesium alloy substrate.     

PTA clad (Cr,Fe)7C3/γ-Fe in situ ceramal composite coating

A wear-resistant (Cr, Fe)₇C₃/γ-Fe in situ ceramal composite coating was fabricated on the substrate of 0.45wt%C carbon steel by a plasma-transferred arc cladding process using the Fe-Cr-C elemental powder blends. The microstructure, microhardness, and dry-sliding wear resistance of the coating were evaluated. The results indicate that the microstructure of the coating, which was composed of (Cr, Fe)₇C₃ primary phase uniformly distributed in the γ-Fe, and the (Cr, Fe)₇C₃ eutectic matrix was metallurgically bonded to the 0.45wt%C carbon steel substrate. From substrate to coating, the microstructure of the coating exhibited an evident epitaxial growth character. The coating, indehiscent and tack-free, had high hardness and appropriate gradient. It had excellent wear resistance under the dry sliding wear test condition.     

Isothermal oxidation behavior and mechanism of a nickel-based superalloy at 1000℃

The oxidation behavior of a nickel-based superalloy at 1000℃ in air was investigated through X-ray diffraction, scanning electron microscopy, and energy-dispersive spectroscopy analysis. A series of oxides, including external oxide scales (Cr₂O₃, (TiO₂ + MnCr₂O₄)) and internal oxides (Al₂O₃,TiN), were formed on the surface or sub-surface of the substrate at 1000℃ in experimental still air. The oxidation resistance of the alloy was dependent on the stability of the surface oxide layer. The continuity and density of the protective Cr₂O₃ scale were affected by minor alloying elements such as Ti and Mn. The outermost oxide scale was composed of TiO₂ rutile and MnCr₂O₄ spinel, and the growth of TiO₂ particles was controlled by the outer diffusion of Ti ions through the pre-existing oxide layer. Severe internal oxidation occurred beneath the external oxide scale, consuming Al and Ti of the strength phase γ' (Ni₃(Al,Ti)) and thereby severely deteriorating the surface mechanical properties. The depth of the internal oxidation region was approximately 35 μm after exposure to experimental air at 1000℃ for 80 h.     

CrN/Cr涂层对Ti22Al26Nb合金的高温防护研究

采用电弧离子镀技术在O相Ti22Al26Nb合金表面镀覆CrN以及CrN/Cr涂层并研究了其在800和900℃空气中的等温氧化行为,结果显示O相钛合金表面施加单一的CrN涂层后,涂层表面在氧化时形成了保护性的氧化膜Cr2O3层,因此合金受到了良好的高温防护,但是涂层和基体合金之间发生了明显的互扩散;在CrN涂层和钛合金基体之间施加纯Cr扩散障层后形成的CrN/Cr涂层,其表面除了象单一CrN涂层那样氧化后形成了一层连续、致密、结合良好的保护性氧化膜Cr2O3层外,还能有效的抑制涂层与基体合金之间的互扩散,此外扩散障Cr层的存在使得靠近其基体的晶粒也出现了长大现象。     

Effects of alloying and high-temperature heat treatment on the microstructure of Nb–Ti–Si based ultrahigh temperatur e alloys

The phase co mpositions, microstructure and especi ally phase i nterfaces in the as-cast and heat-treated Nb– Ti–Si based ultrahigh temperature alloys have been investigated. It is shown that β(Nb,X)5Si3 and γ(Nb,X)5Si3 are the primary p hase s in the Nb–22Ti–16Si–5Cr–5Al (S1) (at%) and Nb–20Ti–16Si–6C r–4Al–5Hf–2B–0.06Y (S2) (at% ) alloys, respectively. The Nb solid solution (Nbss) is the primary phase in Nb–22Ti–14Si–5Hf–3Al–1. 5B –0.0 6Y (S3) (at%) alloy . An orientation relationship between Nbss and γ(Nb,X)5Si3 was determine d to be (1-10)Nb//(101-0)γ and [111]Nb//[0001]γ in the as-cast S2 and S3 alloys. Some original β(Nb,X)5Si3 transfor med into α(Nb,X)5Si3 because Al and Cr diffused from the β(Nb,X)5Si3 to Nbss during heattreatment at 1500 °C for 50 h in the S1 alloy. Mean while, Ti diffused from Nbss to β(Nb,X)5Si3, which induced a Ti to generate near the interface between Nbss and Ti-rich β(Nb,X)5Si3. The orientation relationship between the newl y-formed a Ti and previous Nbss was (110 )Nb//(1-10-1) αTi and [001]Nb//(12-3-1)αTi. Among the ( Nb,X)5Si3 phases , the contents o f Cr and Al in β(Nb,X)5Si3 are n earl y the same as those in γ(Nb,X)5Si3 but obviously hi gher than those in the α(Nb,X)5Si3, where as the content of Si in α(Nb,X)5Si3 is nearly the same a s that in γ(Nb,X)5Si3 but higher than that in the β(Nb,X)5Si3     

Vapor phase codeposition of Cr and Si on Nb-base in situ composites by pack cementation process

In order to identify suitable halide activators and pack compositions for codepositing Cr and Si to form diffusion coatings on Nb-base in situ composites by the pack cementation process, thermochemical calculation was taken to analyze the vapor pressure of halide species generated at high temperatures. NH4Cl, NaF and CrCl3·6H2O were selected as the halide salts. The results of thermochemical calculations suggested that the pack powder mixtures, which contained Cr, Si, halide salts and Al2O3, may be activated by NH4Cl and NaF. According to the thermochemical calculations, the pack powder mixture of 12Cr-6Si-5NH4Cl-77Al2O3 (wt%) activated by NH4Cl was formulated and coating deposition experiments were carried out at 1200 and 1300℃. With adequate control of pack compositions and deposition conditions, it was found that codeposition of Cr and Si could indeed be achieved at these temperatures. The coating has a three-layer structure, of which was mainly composed of Cr2(Nb,X) (X represents Ti and Hf elements), Nb5Si3 and (Nb,Cr)3Si. Then the kinetics of coating growth process affected by temperature was studied. The experimental results of the oxidation showed that the coating can efficiently prevent substrate from oxidizing.     

High-throughput synthesis of oxidation-resistant Nb–Si based alloy thin film by magnetron co-sputtering

A high-throughput method was applied to study oxidation behavior of Nb–Si based alloy using composition spread alloy film as combinatorial libraries. An extended range of composition gradients of Nb–Si based alloy film was deposited by (multi)magnetron co-sputtering. The as-deposited film was composed of amorphous phase. Cr₂Nb, Nb₅Si₃ and Nb_ss could be detected after annealing treatment. After oxidation at 1250 ?°C for 10 ?min and 20 ?min, the film composition space was divided into three regions of the distinct oxide scales. The compositions for establishment of the different oxides on Nb–Si based alloy was defined efficiently across the entire composition space by the combinatorial libraries.     

Rapid directionally solidified microstructure characteristic and fracture behaviour of laser melting deposited Nb–Si–Ti alloy

Aiming at achieving fine and directionally-solidified microstructure of Nb-Si based alloy,Nb,Si and Ti powder particles were utilized as the raw materials,and laser melting deposition(LMD) experiments were conducted with1500 W and 2000 W laser power,respectively.The microstructure characteristic,micro-hardness,and indentation fracture toughness were examined by scanning electron microscope(SEM),X-ray energy dispersive spectrometer(XEDS) and X-ray diffraction(XRD).The results showed that the two kinds of as-deposited Nb-17 Si-23 Ti alloy samples were mainly composed of Nbss,(Nb,Ti)3 Si and Ti-rich Nbss,and the microstructure presents rapid directionally-solidified characteristic,in which the 100 crystallographic direction of Nbss and 110 crystallographic direction of(Nb,Ti)3 Si tend to be parallel to the LMD building direction.With the laser power increasing from 1500 W to 2000 W,the microstructure became more oriented and homogeneous.For the sample at 2000 W,the dendrite spacing was only about 1-2 μm,and Nbss and(Nb,Ti)3 Si couples grow alternately and they are parallel to the building direction strictly.In the meantime the micro-hardness and indentation fracture toughness reached 1075 HV and 20.3 MPa·m~(1/2),respectively,indicating significant improvement by the directional growth of fine Nbss and(Nb,Ti)3 Si phases,and the dimple fracture mode of the Nbss dendrites.     

在钛合金表面制备Al-Si涂层的方法及其高温抗氧化性

采用低氧压高温快速熔结技术在Ti-6Al-4V合金表面成功地制备出具有抗高温氧化能力的Al-Si熔结涂层. 与其他工艺相比,这种工艺相对简单,且不需要经过长时间的加热处理就能在合金的表面形成一层足够厚度的Al-Si熔结涂层,不仅省时节能,且涂层中的抗氧化元素铝、硅的浓度可通过调整涂层粉末的混合比例来进行控制. XRD检测表明涂层主要由Al、Si、Ti5Si3和TiAl3相组成. 在1 073 K空气中循环氧化105 h的实验结果表明:未经过处理的钛合金试样的氧化增重一直保持着较高的增长速率;而对带有低氧压熔结Al-Si涂层的试样来说,其氧化增重近似呈抛物线规律,显著地提高了钛合金的抗氧化能力.     

Microstructure and mechanical properties of TiAl/TiAl joints brazed with a newly developed Ti–Ni–Nb–Zr quaternary filler alloy

A novel Ti-Ni-Nb-Zr quaternary filler alloy with the composition of Ti-(19～25)Ni-(15～25)(Nb+Zr)(wt.%) was designed.The filler alloy was composed of(Ti,Nb)ss,(Ti,Zr,Nb)ss+(Ti,Zr)₂Ni,α-Ti and Ti₂Ni phases.It was fabricated into filler foil with a thickness of about 45 μm by a rapid solidification technique.The results indicate that the liquidus temperature of the Ti-Ni-Nb-Zr brazing alloy was about 978℃,and the brazing alloy presented excellent wettability on TiAl substrate.T...     

高温均匀化对Nb-Ti-Si-Cr基超高温合金组织和成分分布的影响

研究了不同均匀化温度对Nb-Ti-Si-Cr基超高温合金组织和元素分布的影响;结果发现随着高温均匀化处理温度的升高,硅化物的组织形貌由共晶首先转变为细长条状,随后长大为长条状,Laves相Cr_2Nb的形貌由针状转变为粗大的不规则形貌,最后溶解。随着高温均匀化温度的升高,Ti在初生相Nbss中的含量呈现升高的趋势,而Cr在初生相Nbss中的含量呈现先升高后降低的趋势。