Corrosion behavior of select MAX phases in NaOH, HCl and H2SO4

In this paper we report on the electrochemical corrosion of select MAX phases, namely Ti₂AlC, (Ti,Nb)₂AlC, V₂AlC, V₂GeC, Cr₂AlC, Ti₂AlN, Ti₄AlN₃, Ti₃SiC₂ and Ti₃GeC₂ in 1 M NaOH, 1 M HCl and 1 M H₂SO₄ solutions. Polarization characteristics recorded in 1 M NaOH show that V₂AlC, V₂GeC and Cr₂AlC undergo active dissolution at potentials more positive than the corrosion potential, while Ti₂AlC, (Ti,Nb)₂AlC, Ti₃SiC₂ and Ti₃GeC₂ passivate. In the 1 M HCl solutions, Ti₂AlC, V₂AlC and V₂GeC actively dissolve; Ti₃SiC₂ and Ti₃GeC₂ passivate. Depending on potential, (Ti,Nb)₂AlC and Cr₂AlC showed trans-passive behavior. In 1 M H₂SO₄ solutions, Ti₂AlC, (Ti,Nb)₂AlC, Ti₃SiC₂ and Ti₃GeC₂ passivate, V₂AlC and V₂GeC show active dissolution, while Cr₂AlC exhibits trans-passive behavior. Ti₂AlN and Ti₄AlN₃ were passive in all solutions except in 1 M HCl, where Ti₂AlN showed trans-passive behavior. Given that the corrosion behavior of (Ti,Nb)₂AlC is unlike either Ti or Nb, the behavior of the former cannot be predicted from that of the latter.     

Preparation of Ti3AlC2 by mechanically activated sintering with Sn aids

The mechanically activated sintering process was adapted to synthesize Ti₃AlC₂ using 3Ti/Al/2C/0.05Sn powder mixtures. The result showed that the powders containing TiC, Ti₃AlC₂ and Ti₂AlC were obtained by mechanical alloying (MA) 3Ti/Al/2C powders. Addition of appropriate Sn reduced the content of Ti₂AlC and enhanced the synthesis of Ti₃AlC₂ significantly. The powders with highest content of Ti₃AlC₂ were obtained by MA 3Ti/Al/2C/0.05Sn powders. Through pressureless sintering the mechanical alloyed powders at 900–1100 °C for 2 h, the high purity Ti₃AlC₂ material with fine organization was produced.     

Microstructure of carbide precipitates in L12−Ni3Al and L10−TiAl

The crystallographic structures of carbide formed in Ni₃Al- and TiAl-based intermetallics containing carbon are investigated in this study using transmission electron microscopy. In an L1₂-ordered Ni₃Al alloy with 4 mol.% of chromium and 0.2 mol.% to 3.0 mol.% of carbon, fine octahedral precipitates of M₂₃C₆ type carbide were formed in the matrix by aging at temperatures around 973 K after solution annealing at 1423 K. TEM examination revealed that the M₂₃C₆ phase and the matrix lattices have a cube-cube orientation relationship and maintain partial atomic matching at the {111} interface. After prolonged aging or by aging at higher temperatures, the M₂₃C₆ precipitates adopt a rod-like morphology elongated parallel to the <100> directions. In L1₀-ordered TiAl containing from 0.1 mol.% to 2.0 mol.% carbon, TEM observations reveal that needle-like precipitates, which lie only in one direction parallel to the [001] axis of the L1₀ matrix appear in the matrix mainly at dislocations. Selected-area electron diffraction (SAED) patterns analyses showed that the needle-shaped precipitate is perovskite-type Ti₃AlC. The orientation relationship between the Ti₃AlC and the L1₀ matrix was found to be (001)_Ti3AlC//(001)_{L10 matrix} and [010]_Ti3AlC//[010]_{L10 matrix}. By aging at higher temperatures or for a longer period at 1073 K, plate-like precipitates of Ti₂AlC with a hexagonal structure form on the {111} planes of the L1₀ matrix. The orientation relationship between the Ti₂AlC and the L1₀ matrix is (0001)_Ti2AlC//(111)_{L10 matrix} and Ti2AlC//L10 matrix.     

Ti3AlC2掺杂SPS法制备Ti2AlC/TiAl复合材料的研究

通过2TiC-Ti-1.2Al体系的原位热压反应制备了Ti₃AlC₂陶瓷,然后以59.2Ti-30.8Al-10Ti₃AlC₂(wt%)为反应体系,采用放电等离子烧结技术制备出Ti₂AlC/TiAl基复合材料。借助XRD、SEM分析了产物的相组成和微观结构,并测量了其室温力学性能。结果表明：原位热压烧结产物由Ti₃AlC₂和TiC相组成,Ti₃AlC₂呈典型的层状结构,TiC颗粒分布在其间。SPS法制备的Ti₂AlC/TiAl基复合材料主要由TiAl、Ti₃Al和Ti₂AlC相组成,Ti₂AlC增强相主要分布于基体晶界处,表现为晶界/晶内强化作用。力学性能测试表明：Ti₂AlC/TiAl基复合材料的密度、维氏硬度、断裂韧性和抗弯强度分别为3.85 g/cm₃、5.37 GPa、7.17 MPa?m_1/2和494.85 MPa。     

Effects of TiC and Al4C3 addition on combustion synthesis of Ti2AlC

Preparation of the ternary carbide Ti₂AlC was conducted by combustion synthesis in the mode of self-propagating high-temperature synthesis (SHS) from the elemental powder compacts of Ti:Al:C = 2:1:1, TiC-containing samples with TiC of 6.67–14.3 mol%, and Al₄C₃-containing samples with Al₄C₃ of 1.96–10 mol%. Effects of TiC and Al₄C₃ addition were studied on combustion characteristics and the degree of phase conversion. Due to the growth of laminated Ti₂AlC grains, the reactant compact was subjected to an axial elongation during the SHS process. Because the addition of TiC and Al₄C₃ led to a decrease in the reaction temperature, the flame-front propagation velocity was correspondingly reduced for the TiC- and Al₄C₃-containing samples when compared with the elemental reactants. Based upon the XRD analysis, formation of Ti₂AlC along with a secondary phase TiC was identified in the synthesized products. The grains of Ti₂AlC are typically plate-like with a size of 10–20 μm and several laminated Ti₂AlC grains form a layered structure. The content of Ti₂AlC yielded from the elemental powder compacts is about 85 wt%. The addition of TiC was found to facilitate the formation mechanism and therefore to enhance the extent of Ti₂AlC conversion approaching 90 wt%. As a result of the reduced exothermicity of the reaction, however, the content of Ti₂AlC decreased slightly in the products synthesized from the Al₄C₃-added samples.     

部分MAX相在NaOH、H2SO4和HCl中的电化学性质

用热压的方法合成了若干MAX相化合物,包括相（Ti₂AlC和Ti₂AlN）和312相（Ti₃SiC₂和Ti3AlC2）;研究了它们在1 mol/L HCl、1 mol/L NaOH和1 mol/L H₂SO₄中的电化学性质及其结构与其稳定性的关系.结果表明:在所有溶液中,312型MAX相比211相更稳定;Ti₃SiC₂ 和Ti₃AlC₂几乎在所有溶液里都发生钝化,而Ti₂AlC和Ti₂AlN在1 mol/L HCl中活跃地溶解,还伴有大量气泡产生;Ti₃SiC₂比Ti₂AlC、Ti₂AlN 和Ti₃AlC₂更稳定.     

Formation of TiC/Ti2AlC and α2+γ in in-situ TiAl composites with different solidification paths

In order to improve the mechanical properties of TiAl alloys, TiAl composites with different solidification paths were synthesized by metallurgical method. Results show the TiC disappears and Ti₂AlC increases when the Al content is more than 42% (at.%, similarly hereinafter). Small TiC particles are located in Ti₂AlC grains with irregular shapes when the Al content is 40%, and they translate into clubbed Ti₂AlC with increasing of Al. This metallurgy method can solve the defects of the Al lacking and the residual TiC. The γ phase increases between lamellar colonies with the increasing of Al. When the Al content is 48%, the fully lamellar structure transforms into a duplex microstructure and there are small Ti₂AlC phases in γ phases, because the forming of Ti₂AlC phase must consume Al. The compressive strength increases up to 1678.68 MPa as Al content is 46 at.%, and then decrease to 1460.22 MPa, the compressive strain increases and then keeps stabilization with the increasing Al. The maximum strength improves 38.82% and the maximum strain improves 121.37%. The Ti₂AlC/TiAl composites fracture behaviors are load transferring behavior, crack deflection, trans-lamellar cracking and extraction of carbide reinforcements. The Ti₂AlC phase and the fully lamellar structure improve the mechanical properties.     

Precipitation behavior of (Al,Ag)3Ti and Ti3AlC in L10-TiAl in Ti-Al-Ag system

A transmission electron microscopy (TEM) investigation has been performed on the morphologies of L1₂-(Al,Ag)₃Ti and Ti₃AlC precipitates in L1₀-ordered TiAl(Ag). During aging at temperatures around 1073 K after quenching from 1273 K, TiAl(Ag) hardens by the precipitation of (Al,Ag)₃Ti and Ti₃AlC. TEM observations revealed that plate-like (Al,Ag)₃Ti precipitates lie on {001} planes of TiAl(Ag) matrix in the short aging period and the habit plane changed from {001} to {hhl} after a long period aging or high-temperature aging and finally to {112} of the matrix lattice. At the same time needle-like precipitates Ti₃AlC, which lie only in one direction parallel to the [001] direction of the TiAl(Ag) matrix, appear after long period aging or high-temperature aging. The anisotropic misfits between TiAl(Ag) matrix and L1₂-(Al,Ag)₃Ti and Ti₃AlC are considered to explain the morphologies of L1₂-(Al,Ag)₃Ti and Ti₃AlC precipitates.     

Formation of TiAl–Ti2AlC in situ composites by combustion synthesis

Preparation of TiAl–Ti₂AlC in situ composites with a broad range of composition was conducted by self-propagating high-temperature synthesis (SHS) with compressed samples from the mixture of elemental powders. When compared with SHS formation of monolithic TiAl, the addition of carbon particles to the Ti–Al powder mixture enhances the sustainability of the reaction. It was found that no prior heating was required for the samples prepared to produce the composites containing more than 20 mol% Ti₂AlC, in contrast to the need of preheating at 200 °C for single-phase TiAl formation. This is attributed to the fact that formation of Ti₂AlC is more exothermic than that of TiAl. As a result, the combustion temperature and combustion wave velocity increase with the content of Ti₂AlC formed in the TiAl–Ti₂AlC composite, and approach the values associated with formation of single-phase Ti₂AlC when considerable amounts of Ti₂AlC are yielded. The XRD analysis of the end products confirms formation of TiAl–Ti₂AlC in situ composites. Moreover, simultaneous formation of Ti₂AlC promotes the phase evolution of the aluminide compounds. That is, the secondary aluminide phase, Ti₃Al, was no longer detected in the TiAl–matrix composites containing Ti₂AlC of 30 mol% or above.     

High-Temperature Oxidation Behavior of Ti2AlC in Air

The isothermal oxidation behavior of bulk Ti₂AlC in air has been investigated in temperature range 1000–1300°C for exposure time up to 20 hr by TGA, XRD, and SEM/EDS. The results demonstrated that Ti₂AlC had excellent oxidation resistance. The oxidation of Ti₂AlC obeyed a cubic law with cubic rate constants, k_c, increasing from 2.38×10^-12 to 2.13×10^-10 kg³/m⁶/sec as the temperature increased from 1000 to 1300°C. As revealed by X-ray diffraction (XRD) and SEM/EDS results, scales consisting of a continuous inner -Al₂O₃ layer and a discontinuous outer TiO₂ (rutile) layer formed on the Ti₂AlC substrate. A possible mechanism for the selective oxidation of Al to form protective alumina is proposed in comparison with the oxidation of Ti–Al alloys. In addition, the scales had good adhesion to the Ti₂AlC substrate during thermal cycling.     

Microstructure and Residual Stress of Alumina Scale Formed on Ti2AlC at High Temperature in Air

Ti₂AlC ternary carbide is being explored for various high temperature applications due to its strength at high temperatures, excellent thermal-shock resistance, and high electrical conductivity. A potential advantage of Ti₂AlC over conventional Al₂O₃-forming materials is the near-identical coefficient of thermal expansion (CTE) of Ti₂AlC and α-Al₂O₃, which could result in superior spallation resistance and make Ti₂AlC a promising option for applications ranging from bondcoats for thermal barrier coatings to furnace heating elements. In this study, isothermal and cyclic oxidation were performed in air to examine the oxidation behavior of Ti₂AlC. Isothermal oxidation was performed at 1000, 1200 and 1400 °C for up to 25 h and cyclic oxidation consisted of 1,000 1-hour cycles at 1200 °C. Characteristics of the oxide scale developed in air, including mass change, residual stress in the α-Al₂O₃ scale, phase constituents and microstructure, were examined as functions of time and temperature by thermogravimetry, photostimulated luminescence, x-ray diffraction, scanning electron microscopy, and transmission electron microscopy via focused ion beam in situ lift-out. Above a continuous and adherent α-Al₂O₃ layer, a discontinuous-transient rutile-TiO₂ scale was identified in the oxide scale developed at 1000 and 1200 °C, while a discontinuous-transient Al₂TiO₅ scale was identified at 1400 °C. The continuous α-Al₂O₃scale thickened to more than 15 μm after 25 h of isothermal oxidation at 1400 °C, and after 1,000 1-hour cycles at 1200 °C, yet remained adherent and protective. The compressive residual stress determined by photoluminescence for the α-Al₂O₃ scale remained under 0.65 GPa for the specimens oxidized up to 1400°C for 25 hours. The small magnitude of the compressive residual stress may be responsible the high spallation-resistance of the protective α-Al₂O₃ scale developed on Ti₂AlC, despite the absence of reactive element additions.     

Summary of constitutional data on the Aluminum-Carbon-Titanium system

The constitution of the titanium-aluminum-carbon ternary system has been investigated combining critical evaluation of literature data with new experimental results. Three ternary phases occur in this system: Ti₃AlC, Ti₂AlC, and newly discovered Ti₃AlC₂. As analyzed by wet chemistry methods, all three phases are carbon deficient with respect to their “ideal≓ stoichiometry, which is based on the crystal structure formula. Ti₂AlC and Ti₃AlC melt incongruently at 1625 ± 10 ‡ and 1580 ± 10 ‡, respectively. Ti₃AlC₂ decomposes in the solid state. The two isothermal sections at 1000 and 1300 ‡ investigated experimentally are corroborated by thermochemical calculations. A projection of the liquidus surface is given, and a reaction scheme linking this liquidus projection with the isothermal sections observed is proposed.     

两相连续网络结构Ti2AlC/TiAl复合材料的制备及力学性能

采用热压工艺制备不同体积分数的Ti2AlC/TiAl复合材料,并研究其增强结构特征及力学性能.当增强相体积分数达到20％时,复合材料形成两相三维互贯通的结构;当增强相体积分数高于20％,复合材料中Ti2AlC相聚集长大并形成粗大的骨骼网络.Ti2AlC相的微观塑性变形行为(如扭折和层裂)能改善复合材料的断裂韧性,均匀细...     

保温时间对瞬时液相扩散连接的Ti3Al /Ti2AlNb接头微观结构及力学性能的影响

采用Ni-Ti复合箔片作为中间层,在990 ℃、低连接压力（0.1 MPa）下,通过瞬时液相（TLP）扩散连接制备了Ti₃Al/Ti₂AlNb异种合金接头。分析了保温时间（10~90 min）对Ti₃Al/Ti₂AlNb接头微观结构及力学性能的影响,并研究了TLP扩散连接接头的界面演变和形成机制。结果表明,Ti₃Al/Ti₂AlNb接头具有典型的“Ti₃Al | Al_0.5Nb_0.5Ti₃ | 残余 Ni | NiTi | NiTi₂ | 残余 Ti | Al_0.5Nb_0.5Ti₃ | Ti₂AlNb”多层梯度结构。随着保温时间的延长,接头的抗剪切强度先增大后减小,当保温时间达到60 min时,Ti₃Al/Ti₂AlNb接头的抗剪切强度最大,达到167±12 MPa。另外,接头的断裂主要发生在Ti₂AlNb/Ti附近的NiTi₂层,并向Ti层延伸,呈现出脆性断裂的特征。     

Microstructure and some properties of TiAl-Ti2AlC composites produced by reactive processing

The TiAl–Ti₂AlC composites with and without impurities, Ni, Cl and P, were prepared by combustion reaction from the elemental powders and cast after arc melting. The resulting composites had about 18 vol% Ti₂AlC in the lamellar matrix consisting of γ-TiAl and Ti₃Al (α₂). In the homogenized specimens, the α₂ phase decomposed to γ-TiAl and Ti₂AlC. The composite material had a high strength both at ambient and elevated (1173 K) temperatures; about 800 and 400 MPa, respectively, with an ambient temperature ductility of 0.7% at bending test. The fracture toughness test also proved that the homogenized composite has higher toughness than the as cast one. The toughness value reached to 17.8 MPa m^1/2. The zigzag cracks propagated in the homogenized composite and the reinforcement Ti₂AlC particles and the finely precipitated Ti₂AlC particles were main obstacles to the crack propagation. The composite with impurities showed a marginal improvement in the oxidation resistance over the composites without impurities.     

Processing and characterization of porous Ti2AlC with controlled porosity and pore size

In this work, we demonstrate a simple and inexpensive way to fabricate porous Ti₂AlC, one of the best studied materials from the MAX phase family, with controlled porosity and pore size. This was achieved by using NaCl as the pore former, which was dissolved after cold pressing but before pressureless sintering at 1400 °C. Porous Ti₂AlC with samples a volume fraction of porosity ranging from ～10 to ～71 vol.% and different pore size ranges, i.e. 42–83, 77–276 and 167–545 μm, were successfully fabricated. Fabricated samples were systematically characterized to determine their phase composition, morphology and porosity. Room temperature elastic moduli, compressive strength and thermal conductivity were determined as a function of porosity and/or pore size. For comparison, several samples pressureless-sintered without NaCl pore former, or fabricated by spark plasma sintering, were also characterized. The effects of porosity and/or pore size on the room temperature elastic moduli, compressive strength and thermal conductivity of porous Ti₂AlC are reported and discussed in this work. It follows that porosity can be a useful microstructural parameter to tune mechanical and thermal properties of Ti₂AlC.     

Ti活度对Al2O3/AgCuTi/Fe-Ni-Co钎焊接头机械性能和微观组织结构的影响

采用AgCuTi钎料实现了Al₂O₃陶瓷与Fe-Co-Ni合金的钎焊连接,并调查了不同钛含量的钎料对Al₂O₃/AgCuTi/Fe-Ni-Co钎焊接头机械性能和微观组织结构的影响。扫描电子显微镜(SEM), X射线能量色散光谱仪(EDS), X射线衍射仪(XRD)及电子万能试验机用于分析钎焊接头的机械性能和微观组织结构,结果表明:钛含量的增加明显提高AgCuTi钎料与Al₂O₃陶瓷的相互作用,在Al₂O₃/Ag-Cu-Ti界面生成一层由Ti-Al 和 Ti-O化合物组成的反应层。Al₂O₃/AgCuTi/Fe-Ni-Co钎焊接头的抗拉强度随钛含量的增加而增加,当钛含量提高到8wt.%时,抗拉强度达到最大值78Mpa。通过微观组织结构分析发现,采用AgCu4Ti在890℃保温5min的条件下可以获得较好的钎焊接头,典型接头的微观组织结构为Al₂O₃/TiAl+Ti₃O₅/NiTi+Cu₃Ti+Ag(s,s)/Ag(s,s)+Cu(s,s)+(Cu,Ni)/Fe-Ni-Co。采用AgCu8Ti获得的钎焊接头的界面反应层与AgCu4Ti差异不大,但反应层稍微增厚,并伴有TiO和Ti3Al在Al₂O₃/Ag-Cu-Ti界面生成。     

Cf/SiC复合材料与钛合金(Ti-Zr-Cu-Ni)+W复合钎焊分析

在适当的工艺参数下,用(Ti-Zr-Cu-Ni)+W复合钎料真空钎焊Cf/SiC复合材料与钛合金,采用SEM,EDS和XRD分析接头组织结构,利用剪切试验检测接头的力学性能.结果表明,钎焊时复合钎料中的钛、锆与Cf/SiC复合材料反应,在Cf/SiC复合材料与连接层界面生成Ti3SiC2,Ti5Si3和少量TiC(ZrC)化合物的混合反应层,在连接层与钛合金界面形成Ti-Cu化合物扩散层.增强相钨粉能有效缓解接头的残余热应力,提高接头力学性能,在连接温度930℃,保温时间20 min的工艺条件下,增强相钨粉含量为15%(体积分数)时,接头抗剪强度最高为166 MPa.     

Ag-Cu+WC复合钎料钎焊ZrO2陶瓷和TC4合金

采用新型Ag-Cu+WC复合钎料进行ZrO₂陶瓷和TC4合金钎焊连接,探究了接头界面组织及形成机制,分析了钎焊温度对接头界面结构和力学性能的影响. 结果表明,接头界面典型结构为ZrO₂/TiO+Cu₃Ti₃O/TiCu+TiC+W+Ag_(s,s)+Cu_(s,s)/TiCu₂/TiCu/Ti₂Cu/TC4. 钎焊过程中,WC颗粒与Ti发生反应,原位生成TiC和W增强相,为Ti-Cu金属间化合物、Ag基和Cu基固溶体提供了形核质点,同时抑制了脆性Ti-Cu金属间化合物的生长,优化了接头的微观组织和力学性能. 随钎焊温度的升高,接头反应层的厚度逐渐增加,WC颗粒与Ti的反应程度增强. 当钎焊温度890 ℃、保温10 min时,复合钎料所得接头抗剪强度达到最高值82.1 MPa,对比Ag-Cu钎料所得接头抗剪强度提高了57.3%.     

HiPIMS复合热处理制备高纯Ti2AlC MAX相涂层

Ti₂AlC MAX相涂层是一类兼具金属和陶瓷特性的具有密排六方结构的高性能陶瓷涂层,在电接触、高温防护、宽温域摩擦等领域具有广阔的应用前景。然而MAX相涂层的成相成分窗口窄,性能受杂质相影响大,实现高纯、致密Ti₂AlC MAX相涂层的制备目前仍存在挑战。考虑沉积气压与溅射等离子体能量密切相关,采用高功率脉冲复合直流磁控溅射技术在钛合金基体上制备了TiAl/Ti-Al-C涂层,经后续热处理退火得到高纯Ti₂AlC MAX相涂层,重点研究不同沉积气压对涂层退火前后的成分、微观结构以及力学性能的影响和作用机制。结果表明,随着气压不断增大,沉积态涂层厚度先增加后减少。其中低沉积气压下沉积态涂层退火后,结构中除了Ti₂AlC MAX相外,还含有一定量杂质相;而在高气压下沉积态涂层退火后几乎全部转变为Ti₂AlC MAX相,呈现高纯、表面光滑致密的MAX相涂层特征。相较于沉积态涂层,退火后的涂层硬度变化不大,但由于生成了Ti₂AlC MAX相,涂层弹性模量有所提高...