化学气相沉积钨中氘热脱附特性的定量分析

利用不同升温速率的热脱附谱法(TDS)研究了化学气相沉积钨(CVD-W)经70 eV/D、1.3×10~(25) D/m~2的氘离子辐照后,样品中氘的热脱附特性。结果表明:在该实验条件下,CVD-W中氘滞留总量在10~(19) D/m~2量级;氘的脱附温度区间为400～800 K;脱附总量与升温速率呈负相关,且脱附温度区间会随着升温速率提高而向高温区漂移;CVD-W中氘的主要俘获位为位错或晶界,氘的脱附活化能为0.88 eV,缺陷激活能为0.81 eV。     

钾掺杂钨合金中气相热充氘的热脱附行为

钾(K)掺杂钨(W)合金已经表现了优异的高温力学性能,成为最有希望的PFMs备选材料之一。为评估氢同位素在W-K合金中的滞留情况,采用放电等离子烧结技术(SPS),制备了纯W及K含量82μg/g的W-K合金,通过气相热充法引入氘(D)元素,考察热脱附行为。研究表明,气相热充氘释放温区从600K延伸至1200K,掺杂K后,D脱附活化能从0.86 eV下降到0.68 eV;纯W样品D滞留量在1×10^-6(原子比)左右,掺杂K后有所提高,但依然大大优于商用ITER级纯W。     

金属铈在过量氘气氛下的腐蚀行为研究

采用压力-体积-温度系统(PVT)与热台显微镜(Hot-stage microscope,HSM)相结合的方法,研究了铈(Ce)在过量氘(D2)气氛下的腐蚀行为;采用X射线衍射(XRD)仪和热脱附谱(TDS)方法分别考察了铈-氖反应产物的相组成及热稳定性。结果表明,铈在室温、初始压力43 kPa的氘气氛下,可快速与氘发生反应,形成饱和的铈氘化物CeD3,样品发生严重粉化;对饱和铈氘化物在不同温度下加热,可得到一系列不同氘含量的铈氘化物;所制备的铈氘化物在室温下均具有与金属铈类似的面心立方(fcc)结构,铈形成CeD_2的体胀约为24.3%,但随着氘含量的增加,铈氘化物会发生反常的体积收缩现象;热脱附谱测试表明CeD_3在120℃附近即可发生分解,而CeD_2则可稳定至600℃以上。     

W-Fe-Ni合金中的氘滞留行为

采用气相驱动渗透系统和热脱附试验平台研究了W-Fe-Ni合金中氘的输运行为,获得了氘在合金中的渗透率、扩散系数、溶解度、扩散激活能等参数,进行了合金热充氘及氘热脱附实验,结合微观结构表征及数值模拟,研究了氘在W-Fe-Ni合金中的滞留行为,并建立了氢同位素扩散模型以估算不同形状尺寸的W-Fe-Ni合金中氘滞留量。通过与热脱附实验结果对比,发现使用多物理场数值模拟可以准确地估算W-Fe-Ni合金中氢同位素滞留量。     

W80-Cu20复合材料热变形行为及加工图研究

采用Gleeble-1500热模拟机研究了W80-Cu20(wt.％)复合材料在变形温度为810~970 ℃和应变速率为0.01~10 s_^-1条件下真应变达0.69的热变形行为,基于改进动态材料模型(MDMM)和Malas’s准则建立功率耗散图和热加工图,结合微观组织确定出合理热加工参数,并对材料的损伤方式进行分析。结果表明：W80-Cu20复合材料的应力-应变曲线表现出典型的动态再结晶型特征,峰值应力随变形温度的降低和应变速率的增加而增加;确定出W80-Cu20复合材料的合理热加工区域为：840~885℃、0.2~1.42 s_^-1和885~917℃、0.83~2.05 s_^-1;W80-Cu20复合材料的损伤方式主要有Cu相撕裂、W-Cu界面分离、W-W界面分离以及W颗粒破碎。     

粉末TC4钛合金热压缩动态软化行为分析

通过热模拟压缩实验获得的应力应变曲线表明粉末TC4钛合金在温度为850~950℃,应变速率为0.1~10s_^-1范围内变形时具有加工硬化和连续的动态软化特性,建立了材料本构方程,很好的描述了粉末TC4钛合金的流变行为。进一步对动态软化行为进行了分析,并计算了各种因素对软化的影响程度。结果表明：变形温度越低,应变速率越小,流动软化程度越大;在应变速率为1s_^-1和10s_^-1时,主要是变形热导致流动软化;当应变速率为0.1s_^-1,温度为850℃和900℃时,有变形热、动态相变和α相形态演化三种软化因素,且温度越低,α相形态演化导致的软化占比越大,温度增加,动态相变软化所占比例增加;当应变速率为0.1s_^-1,变形温度为950℃时,有变形热和动态相变两种软化因素,变形量增加,动态相变软化所占比例增大。     

GH2907合金热变形行为及热加工图

通过热模拟压缩实验研究了GH2907合金在变形温度为950~1100℃、应变速率为0.01~10s_^-1、变形量为60%条件下的热变形行为,流变应力随着变形温度的升高或应变速率的降低而显著降低；根据Arrhenius方程和Zener-Hollomon参数,计算了热变形激活能Q,建立了GH2907合金的热变形本构方程；根据动态材料模型,确定了GH2907合金在不同应变下的功率耗散图,功率耗散效率η较高的区域位于温度为1050~1100℃,应变速率为0.01~0.03s_^-1范围,在该变形区域内组织发生了明显的动态再结晶现象；基于Preased失稳判据,绘制了GH2907合金在不同应变下的热加工图,流变失稳区位于高温高应变速率区域,即温度为970~1100℃,应变速率为0.6~10s_^-1范围,在该变形区域内动态再结晶晶粒沿着绝热剪切带和局部流动分布。根据GH2907合金热加工图及微观组织分析得到适宜的加工区域是温度为1050~1100℃,应变速率为0.01~0.03s_^-1范围。     

新型钛合金Ti-555热变形行为及热加工图研究

本文通过高温热压缩试验研究Ti-555钛合金热变形过程中变形温度、应变速率对流变应力的影响,采用Arrhenius双曲正弦函数模型推导出Ti-555本构方程,并依据动态材料模型建立了ε=0.6时的热加工图。结果表明,Ti-555钛合金流变应力对应变速率和变形温度较为敏感,热变形时随变形温度升高或应变速率降低,流变应力下降。根据热加工图确定了两个热加工安全区参数为(1)变形温度为850～950 ℃、应变速率为0.6～10 s_^-1;(2)变形温度为950～1150 ℃、应变速率为0.36～0.9 s_^-1。     

一种新型镍基粉末高温合金的热压缩性能研究

基于Gleeble热压缩模拟试验,研究变形温度和应变速率对一种新型第三代镍基粉末高温合金WZ-A3挤压态试样在变形温度1040~1130 ℃区间,应变速率0.01~0.0025 s_^-1 条件下的热压缩变形行为,分析了合金在不同热压缩条件下的晶粒尺寸及显微组织的变化。试验结果表明：WZ-A3合金挤压棒在1070~1100 ℃温度范围, 0.01~0.005 s_^-1 应变速率范围内热压缩变形后可以获得约4.5 μm细小均匀的晶粒组织,各部位均未出现项链晶及异常晶粒长大的现象。根据以上试验条件成功制备了两件直径190 mm高97 mm的小尺寸热模锻试验盘,验证了WZ-A3合金的热压缩性能。     

Ti60合金的热变形行为及工艺参数优化

在变形温度600～950℃,应变速率0.001～10s_^-1条件下,采用Thermecmaster-Z型热加工模拟试验机对Ti60合金进行等温恒应变速率压缩实验。通过分析流动应力行为,计算应变速率敏感指数m和应变硬化指数n,并综合考虑加工图和变形微观组织来研究该合金的热变形行为,得到优化的工艺参数范围。研究结果表明,Ti60合金的流动应力-应变曲线在不同热力参数条件下分别呈现流动稳态型和流动软化型。应变速率敏感指数m随着变形温度升高和应变速率降低而增大。应变硬化指数n随着变形温度升高而减小；随着应变速率的增加在低应变速率(0.001～0.1s_^-1)区间增大,在高应变速率(1～10s_^-1)区间减小；随着应变的增加在高温段(800～950℃)的低应变速率(0.001～0.1s_^-1)区间较缓慢地减小,在高温段(800～950℃)的高应变速率(1～10s_^-1)区间以及低温段(600～750℃)的所有应变速率(0.001～10s_^-1)区间较明显地减小。Ti60合金存在两个功率耗散效率峰值区域,其对应的热力参数窗口分别为温度725～875℃,应变速率≤0.003s_^-1和温度875～938℃,应变速率≤0.04s_^-1。从流动应力行为、应变速率敏感指数m、应变硬化指数n以及加工图综合考虑,Ti60合金的最佳热加工工艺参数为：温度800～875℃,应变速率0.001～0.003s_^-1,或温度875～938℃,应变速率0.001～0.04s_^-1。     

The poisoning of Pd–Y alloy membranes by carbon monoxide

We have explored the poisoning mechanism of CO on Pd–Y alloy membranes by means of thermal desorption spectroscopy (TDS) and X-ray photoelectron spectroscopy (XPS). TDS results show the total deuterium content sharply decreases and the desorption peak shifts to higher temperature with the increasing concentration of CO (from 0% to 26%) in gaseous deuterium. XPS results show that there are YO_x, carbon, carbonate and adsorbed molecular CO on Pd–Y alloy surfaces after reaction with the mixture of D₂ + 26%CO at 623 K followed by cooling to room temperature. But no carbides and PdO_x are detected.     

Hydrogen-sorption and thermodynamic characteristics of mechanically grinded TiH1.9 as studied using thermal desorption spectroscopy

Isobaric thermal desorption spectroscopy and X-ray diffraction analysis were used to study the influence of mechanical dispersion during high-energy milling γ-TiH_1.9 hydride upon its hydrogen-sorption characteristics, temperature and enthalpy of the γ → β (TiH_1.9 → Ti[H]_β) phase transition at isobaric heating the sample under hydrogen atmosphere with speed 3°/min. Isobars of hydrogen thermal desorption in the regions of the γ and β phases of the Ti-H₂ system at pressures of 0.1, 0.25, 0.315 and 0.45 MPa of hydrogen in the reactor have been derived. Experimental data obtained for initial titanium hydride and mechanically grinded for 20 min in a planetary ball mill have been used for construction of Van’t Hoff plots and for determination of enthalpy of formation of γ-hydride from solid solution of hydrogen in bcc titanium. Our experimental data reveal that 20 min high-energy influence on titanium hydride powder leads to increasing the specific surface of the samples from 0.13 to 8.58 m²/g and to significant (more than 250°) decreasing the temperature of the beginning of hydrogen release when heating the sample (i.e., to a decrease of thermal stability of mechanically activated TiH_1.9). However, mechanical dispersion does not change the temperature of the γ → β phase transition. It has been established that high-energy milling TiH_1.9 powder causes the effect of a decrease of enthalpy of the formation of γ-hydride from 248 kJ/mole H₂ to 175 kJ/mole H₂.     

Deuterium Storage of Ti39Zr38Ni17Pd6 Icosahedral Quasi- crystal

Ti-Zr-Ni基二十面体准晶是一类特殊的储氢材料,在氢能和核聚变能领域具有较强应用前景。采用XRD、TEM、XPS技术和气固反应系统研究了Ti39Zr38Ni17Pd6二十面体准晶的储氘性能。该合金室温下的饱和吸氘浓度接近 11 mmol·D2/g·M (D2指氘分子,M指金属),超过Zr2Fe和ZrCo 2种合金。在吸放氘循环过程中,没有发现该合金发生相转变。饱和吸氘使得准晶格膨胀了6.37%,并使得Ti与Zr的结合能上升0.2和0.6 eV,反映出氢原子在这种材料中的占位更靠近这2种金属原子。放氘结果显示该合金具有可能较低的坪台压力,350 ℃左右低于1 kPa,这意味着氘原子在该合金中比在ZrCo合金中具有更高的稳定性。以上结果表明,这种准晶有可能替代Zr2Fe和ZrCo合金而在核聚变能领域得到应用。     

Mullite-rich plasma electrolytic oxide coatings for thermal barrier applications

A study has been undertaken of the characteristics exhibited by mullite-rich plasma electrolytic oxide coatings grown on aluminium alloys by using silicate-rich electrolytes. It is found that they can be grown at a higher rate, and to a greater thickness, than alumina PEO coatings on aluminium. The thermal conductivity of these coatings has been measured using a steady-state method. It is shown to be of the order of 0.5 W m^− 1 K^− 1, which may be compared with ∼ 1.5 W m^− 1 K^− 1 for pure alumina PEO coatings and ∼ 10-15 W m^− 1 K^− 1 for dense polycrystalline mullite. Coupled with excellent substrate adhesion and good mechanical properties, this relatively low conductivity makes these coatings attractive for thermal barrier applications. Furthermore, they are shown to exhibit a relatively low global stiffness (∼ 40 GPa), which will reduce the magnitude of thermally-induced stresses and improve the resistance to spallation during temperature changes.     

Hydrogenation of Zr–Cu–Al–Ni–Pd metallic glasses by electrochemical means

Amorphous materials of Zr–Cu–Ni–Al systems have shown attractive electrochemical hydrogen absorption properties. A comparison between Zr₆₀Cu₁₅Al₁₀Ni₁₀Pd₅ and Zr₆₅Cu_17.5Al_7.5Ni₁₀ reveals that the palladium (Pd) increases the hydrogen absorption capacity. Charging melt-spun Zr₆₀Cu₁₅Al₁₀Ni₁₀Pd₅ ribbons electrochemically to different hydrogen-to-metal (H/M) ratios and following the effusion of hydrogen by thermal desorption analysis (TDA) reveals hydrogen desorption from interstitial sites of high energy levels at temperatures below 630 K. Zirconium hydrides are formed above 630 K. At higher temperatures partial desorption of hydrogen occurs. The thermal stability observed with differential scanning calorimetry (DSC) of the amorphous phase has been significantly deteriorated by hydrogen absorption. After hydrogenation, the crystallization behaviour shows suppression of the characteristic quasicrystalline phase and depends on the hydrogen content. Therefore, at low hydrogen concentrations H/M = 0.3, Cu and/or Cu-rich phases are primarily formed while at high hydrogen concentrations H/M ≥ 0.9 Zr-hydride phase(s) are mainly formed.     

High-flux plasma exposure of ultra-fine grain tungsten

In this work, we examine the response of an ultra-fine grained (UFG) tungsten material to high-flux deuterium plasma exposure. UFG tungsten has received considerable interest as a possible plasma-facing material in magnetic confinement fusion devices, in large part because of its improved resistance to neutron damage. However, optimization of the material in this manner may lead to trade-offs in other properties. We address two aspects of the problem in this work: (a) how high-flux plasmas modify the structure of the exposed surface, and (b) how hydrogen isotopes become trapped within the material. The specific UFG tungsten considered here contains 100 nm-width Ti dispersoids (1 wt%) that limit the growth of the W grains to a median size of 960 nm. Metal impurities (Fe, Cr) as well as O were identified within the dispersoids; these species were absent from the W matrix. To simulate relevant particle bombardment conditions, we exposed specimens of the W-Ti material to low energy (100 eV), high-flux (> 10²² m^− 2 s^− 1) deuterium plasmas in the PISCES-A facility at the University of California, San Diego. To explore different temperature-dependent trapping mechanisms, we considered a range of exposure temperatures between 200 °C and 500 °C. For comparison, we also exposed reference specimens of conventional powder metallurgy warm-rolled and ITER-grade tungsten at 300 °C. Post-mortem focused ion beam profiling and atomic force microscopy of the UFG tungsten revealed no evidence of near-surface bubbles containing high pressure D₂ gas, a common surface degradation mechanism associated with plasma exposure. Thermal desorption spectrometry indicated moderately higher trapping of D in the material compared with the reference specimens, though still within the spread of values for different tungsten grades found in the literature database. For the criteria considered here, these results do not indicate any significant obstacles to the potential use of UFG tungsten as a plasma-facing material, although further experimental work is needed to assess material response to transient events and high plasma fluence.     

Thickness effect on interdiffusion of Fe/Pt multilayers

The effect of thickness on interdiffusion in Fe/Pt multilayer thin films was studied using rapid thermal annealing. [Fe(1 nm)/Pt(1 nm)]₂₀ and [Fe(3 nm)/Pt(3 nm)]₁₀ multilayers were prepared via DC magnetron sputtering and subsequently annealed at temperatures of 523 K to 603 K in an argon atmosphere in an infrared lamp furnace for a very short time. X-ray diffraction yielded the interdiffusion coefficients from the slopes of the satellite peak versus annealing time. The temperature dependence of interdiffusion in the range of 523 K to 603 K can be described by D(t)=3.42×10⁻¹⁵ exp(−0.83 eV/k_BT) (m²/s) for [Fe(1 nm)/Pt(1 nm)]₂₀ and D(t) =7.85×10⁻¹⁶ exp(−0.62 eV/k_BT) (m²/s) for [Fe(3 nm)/Pt(3 nm)]₁₀. The activation energy Q=0.83 eV for [Fe(1 nm)/Pt(1 nm)]₂₀ is higher than that of Q=0.62 eV for [Fe(3 nm)/Pt(3 nm)]₁₀. This phenomenon suggests that the atoms in the thicker film can move more easily in the interface and the lattice, which results in lower activation energy and higher diffusivity.     

Modeling of nitrogen penetration in polycrystalline AISI 316L austenitic stainless steel during plasma nitriding

The nitrogen depth profile in polycrystalline AISI 316L austenitic stainless steel after plasma nitriding at temperatures around 400 °C is analyzed by the “trapping-detrapping” model. This model considers the diffusion of nitrogen under the influence of trap sites formed by local chromium atoms. Nitrogen depth profiles in polycrystalline AISI 316L steel simulated on the basis of this model are in good agreement with experimental nitrogen profiles. The enhanced nitrogen diffusivity as well as a plateau-type shape of nitrogen depth profile can be explained. The nitrogen diffusion coefficient at 400 °C is found to be D = 4.81 × 10⁻¹² cm²/s and the diffusion pre-exponential factor D₀ (0.837 × 10⁻³ cm²/s) and detrapping activation energy E_B (0.28 eV) were deduced from fitting experimental data. It is known that the nitrogen penetration depth (and nitrogen diffusivity) depends on the crystalline orientation and a tentative to take into account this anisotropy effect and describe nitrogen depth profiles in polycrystalline AISI 316L steel is proposed by using different diffusion coefficients characteristic for each crystallite orientation.