原位合成TiB和TiC增强钛基复合材料热力学

根据热力学理论编程计算了钛与Ｂ４Ｃ反应的反应生成焓ΔＨ与Ｇｉｂｂｓ自由能ΔＧ以及反应式（ｘ＋５）Ｔｉ＋Ｂ４Ｃ＝ｘＴｉ＋４ＴｉＢ＋ＴｉＣ的绝热温度。计算结果表明：钛与Ｂ４Ｃ反应释放出大量热,反应能自发维持,而过量钛与Ｂ４Ｃ反应更易生成ＴｉＢ和ＴｉＣ增强体。由于钛作为稀释剂吸收热量,随着过剩钛含量的增加,反应的绝热温度逐渐下降,过剩钛完全熔解的初始温度逐渐升高。     

自蔓延高温合成TiC-Ni金属陶瓷的热力学编程计算与分析

根据热力学原理对Ti、C、Ni三元体系进行热力学编程计算,绘出了标准反应自由焓随温度变化的曲线、绝热温度随Ni含量变化的曲线以及绝热温度随预热温度变化的曲线,通过对曲线进行分析认为：Ti、C、Ni三元体系的主反应是Ti C=TiC;体系的绝热温度随Ni含量的增加而下降,当预热温度为600K时,最佳的理论Ni含量约40％;体系的绝热温度随预热温度的升高而升高,当Ni含量过大,体系的绝热温度小于1800K时,可以适当提高预热温度,来确保反应的自发进行。     

添加Nd、Zn、Ti的Mg2Ni基合金微观组织及氢化动力学

为了提高Mg2Ni基合金的储氢动力学性能,通过熔炼方法分别添加金属元素Nd,Zn和Ti来防止镁的氧化和蒸发,将Mg2Ni基合金在有覆盖剂保护的电阻炉中进行熔炼。借助XRD 和 SEM/EDS研究了铸态合金的相组成和微观组织。采用定容法在Sievert’s型PCT测试仪上测试了合金的氢化动力学性能。Nd、Zn和Ti的添加导致了微量相Mg6Ni和Ni3Ti的生成。Nd和Zn溶解在Mg2Ni基合金的α-Mg、Mg2Ni和MgNi2相中。添加Nd元素后,合金的首次吸氢量高于Mg2Ni的,达到2.86%（质量分数）。Mg2Ni基合金的吸氢动力学性能和活化性能均有所提高。在前3次吸放氢循环过程中,添加Zn和Ti的合金吸氢量和吸氢动力学性能均得到提高。采用Hirooka动力学模型分析了合金的氢化动力学性能及反应机制。     

Reactive sintering of TiAl–Ti5Si3 in situ composites

TiAl with between 0 and 20 vol%Ti₅Si₃ was produced by reactive sintering (700 °C for 15 min in vacuum) of cold pressed compacts of elemental Ti, Al and Si powder. The results show that adding Si to Ti and Al reduces the swelling associated with reactive sintering of TiAl, as composites containing more than 5 vol%Ti₅Si₃ densified during reactive sintering. However, composites containing more than 10 vol%Ti₅Si₃ did not retain their shape and the TiAl+20 vol%Ti₅Si₃ composite completely melted during the sintering process. A thermodynamic analysis indicated that the simultaneous formation of TiAl and Ti₅Si₃ increases the adiabatic flame temperature during the reaction between the powders. In fact, the analysis predicted that the maximum temperature of the reaction associated with the formation TiAl+20 vol%Ti₅Si₃ should exceed the melting point of TiAl, and this was observed experimentally. Differential thermal analysis (DTA) revealed that an Al–Si eutectic reaction occurred in mixtures of Ti, Al and Si powders prior to the formation of the TiAl and Ti₅Si₃ phases. There was no such pre-reaction formation of a eutectic liquid in Ti and Al powder mixtures. The formation of the pre-reaction liquid and the increase in adiabatic flame temperature resulted in the melting that occurred and the enhanced densification (minimization of swelling) during reactive sintering of the in situ composites.     

Ti—13Al—29Nb—2.5Mo合金ISM熔炼过程中多组元挥发损失

在基于活度系数计算模型的基础上，计算了ISM熔炼过程中不同熔炼温度下Ti-13Al-29Nb-2.5Mo(ω/%)熔体中Ti,Al,Nb元素的饱和蒸气压，计算结果表明，在熔炼温度范围内，Al元素的饱和蒸气压分别比Ti,Nb元素的饱和蒸气压大17倍和3070倍左右。在熔炼温度范围内对熔体中Al,Ti,Nb元素的挥发损失速率的计算表明，Al元素在损失速率比Ti,Nb的损失速率分别大43倍和144倍左右，在此基础上计算了Ti,Al,Nb元素的挥发损失量以及合金在熔炼后的化学成分，结果表明由于合金中各组元的挥发损失速率大小不一，使得熔炼前后合金的成分出现了变化。分析表明合理降低熔炼温度及增加真空室中压力可以减小成分的变化。本结果为ISM熔炼实践中合金成分控制提供有价值的理论指导。     

镁对铜锌合金α→β相转变的影响

采用熔炼法制备了CuZn_((40-x))Mg_x合金,借助光学金相显微镜、差热分析仪以及X射线衍射仪,研究了Mg含量对铜锌合金熔点、相转变温度及相变过程微观组织演变的影响.结果表明,当Mg含量大于4 %时,CuZn_((40-x))Mg_x合金析出Cu_2Mg相;CuZn_((40-x))Mg_x合金相转变温度随Mg含量的增加而降低;随着Mg含量的增加,CuZn_((40-x))Mg_x合金熔点降低.     

Investigating the influence of Ti powder purity on phase evolution during NiTi sintering using in-situ neutron diffraction

The influence of Ti powder purity on phase evolution during the reactive sintering of elemental Ni and Ti powders to form NiTi was studied using differential scanning calorimetry (DSC) and in-situ neutron diffraction. Reaction between the Ni and Ti is not significant until 600 °C. From 600 to 700 °C, Ti₂Ni forms in mixtures made from high (HP) and low purity (LP) Ti powder. The Ni₃Ti phase also grows in this temperature range in the LP mixture. The most significant phase evolution takes place between 700 and 920 °C. The α to β phase transformation in (Ti) begins at the eutectoid temperature (765 °C) and ends at 820 °C. The highest growth rates for all three intermetallic phases, including NiTi, and the decay rate of the elemental Ni occur in this temperature range. At approximately 1000 °C, all reactants are consumed and homogenization occurs, with NiTi continuing to grow at the expense of the other intermetallic phases. The Ti rich intermetallic phase persists above its melting point, due to the formation of a solid-solution with oxygen (i.e. Ti₂Ni(O)). From 1100 to 1200 °C, the microstructure becomes a stable mixture of NiTi with a small fraction of Ti₂Ni(O). The phase evolution is similar in the LP and HP mixtures. However, the rate of reaction is higher in the LP mixture due to the influence of impurities (O, Fe and Ni) on the diffusivities in the many phases involved.     

Thermodynamics of the Mg Recycling Process

With the increasing demand of Mg alloys, their recycling will become an important issue in the near future. In the current study, the chemical reactions involved during the recycling process are investigated using thermodynamic calculations. It is found that the melting temperature, density, and MgO solubility of conventional refining fluxes composed of MgCl₂-NaCl-KCl-CaF₂ salts are very sensitive to the flux composition. According to chemical reaction calculations, the solubility of MgO in the refining flux is much lower than the MgO impurity level in molten Mg. Therefore, the refining of Mg alloy, and in particular the removal of MgO by submersing molten flux, seems to be mainly achieved by physical attachment rather than chemical reaction. As a result, it is suggested that the liquidus temperature and density of the molten flux are important physicochemical properties to be considered in the selection of a proper refining flux for a given Mg alloy. In addition, calculations show that expensive and reactive alloying elements such as Ca, Sr, and rare-earth elements can be easily consumed by the molten flux during the refining process, which limits current refining fluxes. All thermodynamic calculations were performed using the FactSage thermochemical software.     

TiB-Ti基金属陶瓷的燃烧合成

通过自蔓延高温燃烧合成 ,结合准热等静压工艺 (SHS/PHIP)制备了相对密度超过 94%的TiB xTi基金属陶瓷复合材料 ,研究了金属Ti含量对燃烧合成TiB Ti基金属陶瓷复合材料的影响。研究结果表明 :随着Ti含量的增加 ,绝热温度、燃烧温度和燃烧速度均降低 ,反应产物主要由TiB和Ti两相组成 ,部分产物还有TiB2 相存在 ,产物组织中 ,TiB相主要有针状、棒状和片状等形态 ,增强相的尺寸随Ti含量的增加而减小 ;随Ti含量的增加 ,产物的抗弯强度、抗拉强度、抗压强度和断裂韧性提高 ,且在Ti含量为 40 % (质量分数 )时达到最大值     

Oxidation resistance of decorative (Ti,Mg)N coatings deposited by hybrid cathodic arc evaporation-magnetron sputtering process

Titanium-magnesium nitride coatings (Ti,Mg)N were deposited on steels and silicon substrates by hybrid reactive arc evaporation-magnetron sputtering process from cathodic Ti and sputter Mg targets in an argon/nitrogen gas mixture. X-ray diffraction analyses (XRD) of as-deposited coatings with various Mg/Ti atomic ratios gave evidence of a fcc TiN-like structure strongly oriented in the [111] direction. The TiN lattice parameter increases with the addition of Mg resulting from the substitution of Ti atoms by Mg ones. Optical investigations by spectrophotometry revealed that Mg addition to TiN leads to a change in colour from golden through coppery and violet to grey. Nanoindentation measurements showed that increasing Mg content does not alter the hardness of coatings. As-deposited films were annealed in air from 450 to 750 °C with a 100 °C step. XRD and Raman analyses revealed the formation of rutile TiO₂ and MgTiO₃ phases. Secondary neutral mass spectrometry measurements were performed to study the elemental depth profiles after air annealing. A diffusion of Mg atoms towards the film surface was evidenced above 650 °C, leading to the formation of the MgTiO₃ phase. However, thermogravimetric measurements showed that this oxide phase did not protect the films against high temperature oxidation. On the contrary, below 650 °C Mg affords to TiN a beneficial protective effect, able to reduce the oxidation kinetics by half.     

Thermal Reactivity of Nanostructure Al0.8Mg0.2 Alloy Powder Used in Thermites

采用双向球磨法,通过控制球磨时间和助磨剂的添加量,制备了具有纳米级晶粒度的Al-Mg合金,该合金很有希望应用为冲击引发含能材料中的固体燃料。结构表征表明,机械合金化处理后得到的 Al0.8Mg0.2呈粒状,且其表面存在大量尺寸约为15～30nm的纳米结构。另外,球磨后材料的晶粒度从原料Al的>100nm降低到Al0.8Mg0.2的 22.7 nm。热分析结果表明,Al0.8Mg0.2合金粒子具有很高的热反应活性。在空气中,Al0.8Mg0.2合金于熔化前就发生了明显的氧化还原反应,而这种固-气相反应在原料 Al 的 DSC 图谱中却没有出现,且Al0.8Mg0.2-O2体系的高温反应放热峰较Al-O2体系提前了33 ℃。从TG 图谱中可以看出,当加热温度达到1100 ℃后,有69.13%的 Al0.8Mg0.2被空气中的 O2氧化,而在相同的条件下原料 Al 只有 15.52%被氧化,可见原料 Al 的氧化效率远低于Al0.8Mg0.2。另外,对于Al0.8Mg0.2-Fe2O3铝热体系,其在合金熔化前也发生了显著的固-固相反应,该反应的活化能比随后的液-固相反应降低了331.664 kJ.mol-1,这表明由 Al-Mg 合金组成的铝热剂应具有优异的点火性能。     

Effect of CaO composition on oxidation and burning behaviors of AM50 Mg alloy

Oxidation and burning behaviors were studied for CaO added AM50 Mg composites which were manufactured by conventional melting and casting processes without SF₆ protective gas. CaO added AM50 Mg composites show the stable oxidation resistance, while AM50 Mg alloys show the poor oxidation resistance. The effects of CaO addition on the burning resistance under ambient, nitrogen and dry air atmospheres were examined for CaO added AM50 Mg composites. With increasing CaO addition, the burning temperature increases under ambient, nitrogen and dry air atmospheres. The burning temperatures of small test specimen under all conditions greatly increase even by 0.3% CaO (mass fraction) addition into AM50 Mg alloys.     

TiAl与Ni基合金接触反应钎焊接头界面组织及性能

以Ti为中间层实现了TiAl与Ni基合金的接触反应钎焊。采用扫描电镜和电子探针等手段对钎焊接头的界面结构及生成相进行分析,并对接头剪切强度进行测试。结果表明:当钎焊温度为960℃时,钎缝主要由Tiss和Ti2Ni组成;当钎焊温度从960℃升高到1000℃时,钎缝中生成Ti-Al及Al-Ni-Ti化合物,典型界面结构为:GH99/(Ni,Cr)ss/Ti2Ni+AlNi2Ti+TiNi/Ti3Al+Al3NiTi2/Ti3Al+Al3NiTi2/TiAl;钎焊温度继续升高,Ti3Al和Al3NiTi2变得粗大,导致接头性能下降。当钎焊温度为1000℃,保温10min时,接头剪切强度达到最大值233MPa。随钎焊温度的升高,钎缝厚度先增加后减小。     

Hydrogen Storage Properties of Ti_(1.2)Fe xCa Hydrogen Storage Alloys

Intermetallic compound TiFe has been apromising candidate fOr hydrogen storage sinceReilly and Wiswa1l fOund its hydrogen absorp-tion capacity[l ]. However, due to its poor acti-vation characteristics, its large-scaIe commer-cia1 use is very hard. For binary TFe, high-temperature heat treatment is required to acti-vate TiFe specimens to absorb hydrogen atroom temperature. In this case, it may take aday or more and high pressure (5.0 MPa ormore) fOr complete activation[2].In the past year…     

Improvement of hydrogen-storage properties of MgH2 by addition of Ni and Ti via reactive mechanical grinding and a rate-controlling step in its dehydriding reaction

In a shift from prior work, MgH₂, instead of Mg, was used as a starting material in this work. A sample with a composition of 86 wt% MgH₂-10 wt% Ni-4 wt% Ti was prepared by reactive mechanical grinding. Activation of the sample was completed after the first hydriding cycle. The effects of reactive mechanical grinding of Mg with Ni and Ti were discussed. The formation of Mg₂Ni increased the hydriding and dehydriding rates of the sample. The addition of Ti increased the hydriding rate and greatly increased the dehydriding rate of the sample. The titanium hydride, TiH_1.924, was formed during reactive mechanical grinding. This titanium hydride, which is brittle, is thought to help the mixture pulverized by being pulverized during reactive mechanical grinding and further to prevent agglomeration of the magnesium by staying as a hydride among Mg particles. A rate-controlling step for the dehydriding reaction of the hydrided MgH₂-10Ni-4Ti was analyzed by using a spherical moving boundary model on an assumption that particles have a spherical shape with a uniform diameter.     

A numerical study of solidification of n-hexadecane based on the enthalpy formulation

A numerical study is described in this paper on the investigation of the solidification of a pure n-hexadecane inside a rectangular enclosure based on an enthalpy formulation of the energy equation. A vertical wall of the enclosure is maintained at a constant temperature below the melting temperature of the n-hexadecane while all other sides are adiabatic. The effects of the cold wall temperature, initial liquid superheat and aspect ratio of the enclosure are studied in terms of the solid fraction and the shape of the solid–liquid phase front. It has been found that a lower wall temperature and a smaller initial liquid superheat result in a larger solid fraction. The solidification process is more affected by the natural convection at the early stage of the solidification than at the later stage. This is inferred by the reduction in the phase front’s slope with time as the temperature in the liquid becomes more uniform. At the early stage of the solidification where natural convection is more dominant in the liquid, a lower wall temperature and a larger liquid superheat result in a larger slope on the phase front, indicating strong natural convection in the liquid. The aspect ratio of the enclosure has some effect on the shape of the phase front, but has only a weak effect on the solid fraction.     

基于Ti中间层的B4C复合陶瓷扩散连接接头界面微观组织与力学性能

碳化硼(B₄C)复合陶瓷以其高硬度、高熔点、良好的耐磨性以及吸收中子能力的特性,广泛应用于制造防弹装甲材料,原子反应堆控制以及耐磨耐高温结构材料等领域.文中采用中间层Ti箔对碳化硼复合陶瓷(B₄C-SiC-TiB₂)进行扩散连接,研究了连接温度对连接界面组织及接头力学性能的影响.结果表明,在连接温度1300 ~ 1450 ℃下成功扩散连接了B₄C-SiC-TiB₂复合陶瓷,Ti与B₄C反应生成TiB₂和TiC.随着连接温度的升高,反应层变厚,而过厚的反应层会对接头的性能造成不利影响.在连接温度1300 ℃时,反应层的平均厚度约为5 μm,此时获得较高的接头抗剪强度100 MPa;在连接温度1450 ℃时连接层基本为TiB₂和TiC陶瓷相,此时扩散连接接头可以获得较高硬度(25.4 GPa).     

Effect of the magnesium content on the mechanochemical behavior in ternary system Mg–B2O3–C

The influence of Mg content in Mg–B₂O₃–C mixture on the MgO–B₄C composite formation and mechanism of reactions during ball milling process was investigated. In keeping with this aim, a mixture of boron oxide powder along with different amounts of Mg (4–10 mol) and C (1–3 mol) was activated in a ball mill. Thermodynamic calculations and differential thermal analysis (DTA) results revealed that Mg value played a main role, thereby; overall reaction enthalpy and adiabatic temperature (T_ad) changed by variation of magnesium content. T_ad enhanced with the increase in the Mg content and found maximum value (2852 °C) at stoichiometric ratio (Mg = 6 mol). DTA results showed that increasing the activation time to 5.5 h could decrease the temperature of combustion reaction to 530°C before magnesium melting. According to experimental findings, in the mixture of powder with 4 mol Mg, magnesiothermic reaction occurred in MSR mode and no carbothermal reaction took place. However, when the Mg content reached within a range of 9/2–6 mol, the magnesiothermic reaction occurred in MSR mode and activated the carbothermal reaction. Further enhancement in Mg content (10 mol Mg), as a diluent agent, led to MSR magnesiothermic reaction and no carbothermal reduction occurred.     

Surface modification of TC4 Ti alloy by laser cladding with TiC+Ti powders

Laser surface cladding was applied on a TC4 Ti alloy to improve its surface properties.Mixed TiC and Ti powders with a TiC-to-Ti mass ratio of 1:3 were put onto the TC4 Ti alloy and subsequently treated by laser beam.The microstructure and composition modifications in the surface layer were carefully investigated by using SEM,EDX and XRD.Due to melting,liquid state mixing followed by rapid solidification and cooling,a layer with graded microstructures and compositions formed.The TiC powders were completely dissolved into the melted layer during melting and segregated as fine dendrites when solidified.The inter-dendritic areas were filled with fine α' phase lamellae enrich in Al.Mainly due to the reduced TiC volume fraction with increasing depth,the hardness decreases with increasing depth in the laser clad layer with a maximum value of HV1400,about 4.5 times of the initial one.     

Kinetics and numerical simulation of self-propagating high-temperature synthesis in Ti–Cr–Al–C systems

In this paper, Ti–Cr–Al–C materials were investigated by self-propagating high-temperature synthesis（SHS） according to the experimental study and numerical simulation results. The highest adiabatic combustion temperature Tadof 2,467.45 K indicates that the2Ti–0Cr–Al–C is the highest exothermic reaction system in the Ti–Cr–Al–C system. The adiabatic combustion temperature decreases with the increase of the Cr content. And a higher exothermal reaction would result in higher porosity which is induced by the high temperature and pressure of C reducing atmosphere and Al vapor. Combustion characterization of the products shows that the geometrical alternating layers result in the high exothermal reaction and flame-front propagating velocity. The higher the Tadis, the thinner the layer is. To demonstrate the process of the microscopic characterization and show the detailed combustion process closed to the experimental observations, the flame-front propagating velocity and temperature distribution were simulated numerically.