Thermal stability of Zr_(55)Al_(10)Ni_5Cu_(30)bulk amorphous alloy during continuous heating and isothermal annealing

1　INTRODUCTIONBulkamorphousalloyspossessalongrangedis orderbutshortrangeorderstructure ,whichresem blesthestructureofliquid .Andthereisasupercooledliquidregionbeforecrystallizationofabulkamor phousalloy .Thisuniquestructureresultsinexcellentpropertiessuchashightensilestrength ,highhard ness,highimpactfractureenergy ,highelasticener gy ,highcorrosionresistance ,highviscousflowabilityandgoodsoftmagnetism[13] .Thesynthesisofmetallicglassesinabulkform (withthickness >1mm )wassuccessfullyachi…     

Crystallization kinetics of bulk Cu58.1Zr35.9Al6 alloy

The crystallization kinetics of the bulk amorphous Cu_58.1Zr_35.9Al₆ alloy was examined by differential scanning calorimetry under continuous heating and isothermal annealing. During continuous heating, the activation energy of crystallization was determined to be 383 kJ/mol by Kissinger method. However, on the isothermal annealing, the activation energy was determined to be 459.2 kJ/mol by the Arrhenius method, which was much larger than that obtained from the Kissinger method. The different temperatures at which crystallization occurs are responsible for the discrepancy in the activation energy. The average Avrami exponent of about 3.5 implies that the crystallization process of the bulk amorphous Cu_58.1Zr_35.9Al₆ alloy is diffusion-controlled with a nucleation rate decreasing with time.     

Structure relaxation and crystallization of Al83Ni10Ce7 metallic glass

Structure relaxation and crystallization of Al₈₃Ni₁₀Ce₇ metallic glass were studied by different scanning calorimetry (DSC) and X-ray diffraction (XRD). According to the DSC scan, it is interesting to find that the second exothermic peak changes with pre-annealing temperatures (below glass transition temperature), suggesting a change in the amorphous structure upon relaxation. Continuous heating crystallization and isothermal crystallization exhibit different crystallization mechanism of the present alloy. fcc-Al and a metastable phase precipitate simultaneously in the first stage crystallization during continuous heating; however, only a metastable phase precipitates during isothermal annealing below glass transition temperature (T_g).     

Applicability of Johnson-Mehl-Avrami model to crystallization kinetics of Zr60Al15Ni25 bulk amorphous alloy

The applicability of Johnson-Mehl-Avrami（JMA） model to the crystallization kinetics of Zr60Al15Ni25 bulk amorphous alloy is investigated by differential scanning calorimetry（DSC） under isochronal and isothermal conditions. A criterion Xm, at which a defined function z（x） exhibits the maximum value, is introduced to check the validity of JMA model to the kinetics analysis. The value Of Xm has a constant of 0.632 for JMA model. It is found that the values Of Xm at different isothermal annealing temperatures （743,748, 753 and 758 K） are almost near 0.632, which indicates that the isothermal crystallization kinetics can be modeled by JMA equation. However, the values Of Xm at different heating rates （10, 20, 30 and 40 K/min） are about 0.52, implying that JMA model is not valid to the isochronal crystallization kinetics. The reason why the JMA model is not valid to the isochronal crystallization kinetics is discussed.     

Crystallization kinetics of amorphous Zr65Cu25Al10 alloy

1　ＩＮＴＲＯＤＵＣＴＩＯＮＴｈｅｄｅｖｅｌｏｐｍｅｎｔｏｆｇｌａｓｓｆｏｒｍｉｎｇ ｍｕｌｔｉｃｏｍｐｏ ｎｅｎｔａｌｌｏｙｓｙｓｔｅｍｓｗｉｔｈｖｅｒｙｌｏｗｃｒｉｔｉｃａｌｃｏｏｌｉｎｇｒａｔｅｓｗｉｔｈｉｎ 1～ 10 0Ｋ/ｓｈａｓｏｆｆｅｒｅｄｆｉｒｓｔ     

Zr57Cu15.4Ni12.6Al10Nb5块体非晶合金晶化行为研究

用示差扫描量热仪（DSC）研究了Zr57Cu15.4Ni12.6Al10Nb5块体非晶合金的匀速升温晶化与等温晶化的晶化行为。在匀速升温晶化方式下，用Kissinger法与Ozawa法获得了块体非晶合金的激活能，对第一晶化峰分别为320．5kJ／mol和316．6kJ／mol，对第二晶化峰分别为324．5kJ／mol和320．5kJ／mol。该非晶合金的晶化表现出明显的动力学效应。在等温晶化方式下，用Johnson-Mehl-Avrami方程获得了晶化的Avrami指数为1．61，表明非晶合金的晶化受原子扩散控制。     

退火对(Nd,Pr)_(12.8)Dy_(0.2)Fe_(77.4)Co_(4.0)B_(5.6)快淬薄带晶化行为的影响

采用高真空高纯氩DSC测量了(Nd,Pr)12.8Dy0.2Fe77.4Co4.0B5.6非晶快淬薄带以及不同温度退火薄带的连续加热曲线,计算了晶化激活能、频率因子、晶化体积分数、晶化速率,研究了预退火前后薄带的晶化动力学和晶化过程。结果表明(Nd,Pr)12.8Dy0.2Fe77.4Co4.0B5.6快淬薄带在30 K/min加热速度时DSC曲线起始晶化温度865.8 K、峰值晶化温度877.2 K、晶化结束温度901.7 K,居里温度转折点581.2 K,富稀土相的初始熔化点1003.6 K。在高于峰值晶化温度或晶化结束温度退火10 min的薄带非晶完全晶化,居里温度处形成吸热峰,而低于803.0 K退火处理的薄带以及快淬薄带在相近温度处只有DSC转折点。相对于快淬薄带直接晶化的特征,在低于起始晶化温度的693.0~743.0 K退火处理的薄带晶化峰形相近;803.0 K退火处理后薄带的晶化峰的温度范围增宽:在10~40 K/min相同加热速度下其起始晶化温度均降低1.4%,晶化结束温度在加热速度20~40 K/min时达到、甚至高于快淬薄带直接晶化结束温度;在低于快淬薄带直接晶化的峰值晶化温度之前存在一个具有相同晶化速率的临界温度,在低于该临界温度时,退火薄带比快淬薄带具有较高的晶化速率、更不稳定;而在高于该临界温度,退火薄带比快淬薄带具有较低的晶化速率。     

Zn38Mg12Ca32Yb18大块金属玻璃的晶化动力学行为

采用差示扫描量热分析仪,研究了Zn38Mg12Ca32Yb18 大块金属玻璃的在等时和等温状态下的晶化动力学行为。在等时条件下,不同的理论模型来分析特征温度的名义激活能。研究结果表明,采用Kissinger模型,Flynn-Wall-Ozawa 模型和Augis-Bennett模型计算的名义激活能相互吻合。再者,采用Johnson-Mehl-Avrami模型分析了等温过程中晶化转变动力学机。The Avrami 指数 n 的分布区间介于 3.25 到 4.12之间. 我们发现,在等温晶化过程中采用Arrhenius 方程计算得到的激活能比在等时晶化过中采用Kissinger 方程的激活能要大,这可能是由于等温退火过程中能垒比等时晶化过程中的要高所引起的。     

HRTEM study of crystallization of Zr–Cu–Ni metallic glass

Employing differential scanning calorimetry (DSC) and high-resolution transmission electron microscopy (HRTEM), the micromechanism for crystallization of Zr₇₀Cu₂₀Ni₁₀ metallic glass under isothermal annealing conditions has been investigated. It is found that the relationship between the annealing temperature and the peak position, incubation time and ending time in the isothermal annealing DSC traces of Zr₇₀Cu₂₀Ni₁₀ metallic glass obeys a first-order exponential function. However, the time–temperature transformation curves of Zr₇₀Cu₂₀Ni₁₀ metallic glass at different crystallized volume fractions can be well fitted by a second-order exponential function. It is observed that at the initial crystallization stage some ordered atomic clusters precipitate first, acting as nucleation sites and facilitating the subsequent crystallization process, and the crystal growth process mainly proceeds through the atomic depositing on the previously formed crystals. This behavior confirms that the new micromechanism for crystallization of amorphous alloys proposed by Lu and Wang can also be applied to the new series of zirconium based amorphous alloys.     

Co基非晶软磁合金的制备与晶化动力学行为研究

采用旋铸急冷工艺在大气环境中制备出Co6.85Fe4Si10B17.5非晶合金带材.XRD分析表明:样品为完全非晶.用DiamondTG/DTA差热分析仪在高纯氩气保护下测量了非晶薄带的等温晶化动力学曲线.采用JMA方程计算出了合金的晶化动力学参数,在不同的晶化温度下,Avrami指数的值在2.11～2.58之间,晶化激活能Ec为113.67 kJ/mol.Co6.85Fe4Si10B17.5非晶合金的晶化方式是初晶型(761、791、803 K)和共晶型晶化(813 K),合金的晶化百分比与退火时间的关系曲线均为S型曲线.     

Microstructure evolution in nanocrystalline NiTi alloy produced by HPT

A slightly Ni-rich nano-NiTi alloy, deformed by high-pressure torsion (HPT) was investigated. By HPT, almost complete amorphization of initial B2 NiTi is obtained. Crystallization and microstructure evolution during isothermal treatment were investigated by differential scanning calorimetry (DSC) and transmission electron microscopy.The DSC signals observed during continuous heating experiments indicate an unusually large separation between the crystallization and the growth stages. A detailed analysis of the evolution of the enthalpy release upon annealing reveals reproducibly non-monotonous trends with annealing time that cannot be explained solely by growth of crystalline volume fractions. The size of nanocrystals increases dramatically after annealing for 5 h. The effective activation enthalpies for stress relaxation (along with crystallization) and grain growth were estimated at 115 and 289 kJ/mol, respectively. The results are discussed with respect to the intricate interdependencies between synthesis and thermal processing pathways and the evolution of the nanoscale microstructure.     

Formation and crystallization of Zr-Ni-Ti metallic glass

The metallic Zr65 Ni25 Ti10 (mole fraction, ％) glass has been fabricated by a single roller melt-spinning method. The glass forming ability(GFA) and thermal stability of the Zr65 Ni25 Ti10 melt-spun ribbons were investigated by using X-ray diffraction(XRD) and differential scanning calorimetry(DSC) in the mode of continuous heating. It is shown that the reduced glass transition temperature (Trg) is 0. 506 and the supercooled liquid region (△Tx) is 30 K. Two exothermic peaks were observed in the DSC curves of the as-quenched ribbon, which indicates that the crystallization process undergoes two different stages. The phase transformation during the isothermal annealing was investigated by X-ray diffraction(XRD) and transmission electronic microscope(TEM). It is observed that the metastable FCC Zr2 Ni(Fd3m, a= 12.27 A) precipitated while annealing in the suppercooled region(615 K) and the stable BCT Zr2Ni(I4/mcm, a= 6.499 A, c= 5.270 A) precipitated while annealing at higher temperature(673 K or 723 K). The crystallines are on nanoscale, with grain size of 15-30 nm. The reason for the precipitation of the different structural Zr2 Ni from the glassy matrix under different annealing conditions was discussed based on the concept of multi-component chemical short range order(MCSRO).     

高温变形对(Cu50Zr50)92Al8等温晶化行为及其力学性能的影响

研究了(Cu50Zr50)92Al8非晶合金在过冷液相区中,经过牛顿流变和非牛顿流变后的等温晶化行为及其对该合金力学性能的影响。结果表明,牛顿型流变对(Cu50Zr50)92Al8非晶合金的结构没有明显的影响;而非牛顿流变对该非晶的显微结构及其等温晶化行为有显著影响:非牛顿流变促进了(Cu50Zr50)92Al8非晶合金的晶化,其主要晶化相为体心立方结构的CuZr相(B2相)和CuZr马氏体相;经非牛顿流变及真空热处理试样,在室温压缩过程中,应力诱发了部分B2相的马氏体相变,从而使其在室温下表现出超弹性,当预塑性应变量为8%时,其总可回复应变为5%左右。     

20CrMoH钢锻件带状组织的消除及其硬度控制

分析了20CrMoH钢锻件带状组织形成的原因及其对力学性能和切削性能的影响；介绍了消除带状组织和控制锻件硬度的等温退火工艺；当加热规范、等温温度一定时，20CrMoH钢锻件的退火硬度主要决定於风温和风冷时间。     

Structure and crystallization kinetics of a Cu50Zr45Ti5 glassy alloy

The crystallization kinetics and structure changes in a melt-spun Cu₅₀Zr₄₅Ti₅ glassy alloy on heating were investigated by X-ray diffractometry, transmission electron microscopy, differential scanning calorimetry and differential isothermal calorimetry. The glassy phase in the Cu₅₀Zr₄₅Ti₅ alloy was crystallized forming Cu₁₀Zr₇ and CuZr₂ phases upon thermal annealing. The activation energy for crystallization obtained by the Arrhenius equation was 435 kJ/mol. The crystallization process took place by nucleation and growth mechanism, and an Avrami exponent of about 3.3 may indicate a three-dimensional interface-controlled growth of nuclei with a decreasing nucleation rate.     

INFLECTION OF COERCIVITY DURING LOCAL CRYSTALLIZATION OF Fe-Si-B AMORPHOUS ALLOYS

An inflection hehaviour was revealed during isothermal annealing under the observation oftransition of the coercivity of Fe-Si-B amorphous alloys during local crystallization.It maybe interpreted by the transition of α-Fe grain precipitated from single to multiple domain,Thus,the theoretical expression of H_0-t_a may be derived.The plot of expression H_0-t_a calcu-lated well represents the feature of the experimental curve.     

大块非晶合金淬态相等温长大过程

利用石英管水淬法制备了ZR41.2Ti13.8Cu12.5Ni10Be22.5大块非晶合金,在真空度不小于10-3Pa和原材料纯度99.9%的情况下,当制备样品直径大于10mm时,经常发现非晶基体中含有一定数量的淬态相,该相的数量不在X衍射仪检测范围内,同时DSC分析表明,这些淬态相对非晶合金的过冷液相区、晶化温度和玻璃转变温度影响也较小.非晶合金过冷液相区内的等温晶化过程表明,晶化初期淬态相具有优先长大的趋势,并有亚稳过渡相的生成.而在晶化的后期,形核和长大同步进行.利用经典形核和长大理论分析了非晶合金的形核和长大过程.     

Microstructure evolution during batch annealing

Design of industrial annealing cycles requires recrystallization and grain growth studies, which are typically carried out under isothermal laboratory condition. The kinetics coefficients of these phase transformations are obtained from such studies, which are subsequently used in designing the industrial nonisothermal cycles using the additivity principles. However, the strong heating rate effects on the grain growth kinetics necessitate such kinetics studies using industrial thermal profiles. In the present work, the hot and cold spot cycles of an industrial batch annealing cycle for AIK grade steel have been simulated in a programmable laboratory furnace. Subsequently, the effect of annealing temperature, soaking time, and heating rate on the microstructural features, such as grain size distribution, grain shape anisotropy, and grain orientation, have been investigated through extensive quantitative microscopy. The implications of these results on the design of industrial batch annealing cycles have been discussed.     

热处理对Hf-基非晶合金力学性能的影响

采用铜模浇铸法制备Hf44.5Cu27Ni13.5Ti5Al10块体非晶合金,并对其进行等温退火处理。利用X射线衍射仪（XRD）和透射电镜（TEM）对非晶合金的晶化行为进行了分析,并通过MTS810实验机及场发射扫描电子显微镜（FESEM）研究了等温退火对合金力学性能的影响。结果表明,该非晶合金等温退火相转变进程为：非晶→非晶＋Al16 Hf6Ni7→非晶＋Al16 Hf6Ni7＋CuTi2→CuHf2＋CuTi2。合金断裂强度随退火温度的升高先增大后减小。743 K等温退火后,合金断裂强度达到最大值2400 MPa,弹性应变为3.0%。在Hf44.5Cu27Ni13.5Ti5Al10块体非晶合金压缩断口上观察到纳米级韧窝及周期性条纹结构。随着退火温度的升高,周期性条纹间距逐渐减小直至消失,断口形貌呈现为脆性解理断裂的河流状花样。     

Zr-Ti-Cu-Ni-Be大块非晶合金等温晶化过程相分离研究

利用差示扫描量热法(DSC)和透射电镜(TEM)对Zr41.2Ti13.8Cu12.5Ni10Be22.5(at％)大块非晶合金的等温晶化过程和析出相进行了研究。结果表明，大块非晶合金在等温晶化过程中表现出多阶段相析出行为，并且在不同的晶化阶段，析出相也有所不同。在第1个晶化阶段，析出相主要是体心四方(b.c．t)结构的Zr2Cu相；而在晶化的第2个阶段，晶化相主要为简单六方结构的ZrBe2相。从一定程度上证实了Zr41.2Ti13.8Cu12.5Ni10Be22.5大块非晶合金在发生晶化时会形成富Zr区和富Be区，即有相分离的趋势。XRD测试的结果也证实了非晶合金在发生完全晶化时，主要的晶化产物为Zr2Cu和ZrBe2相。