Effect of Si addition on the glass-forming ability of a NiTiZrAlCu alloy

The effect of Si addition on the glass-forming ability (GFA) of a NiTiZrAlCu alloy was investigated by using differential scanning calorimetry (DSC), differential thermal analysis (DTA), X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The maximum diameter of glassy rods increased from 0.5 mm for the Ni₄₂Ti₂₀Zr₂₅Al₈Cu₅ alloy (the base alloy) to 2.5 mm for the Ni₄₂Ti₂₀Zr_21.5Al₈Cu₅Si_3.5 alloy and to 3 mm for the Ni₄₂Ti₁₉Zr_22.5Al₈Cu₅Si_3.5 alloy, when prepared by using the copper mould casting. The GFA of the alloys can be assessed by the reduced glass transition temperature T_rg(=T_g/T_l) and a newly proposed parameter, δ(=T_x/T_l − T_g). An addition of a proper amount of Si and a minor substitution of Ti with Zr can enhance the GFA of the base alloy by suppressing the formation of primary Ni(TiZr) and (TiZr)(CuAl)₂ phases and inducing the composition close to eutectic.     

一种具有优异玻璃形成能力的Zr50Ti5Cu27Ni10Al8大块非晶合金的开发

多组元的Zr基非晶合金成分的复杂性对开发具有优异玻璃形成能力的Zr基非晶合金提出巨大的挑战。另外,大部分Zr基非晶合金含有有毒元素Be或者贵金属。因此,采用一种简单有效的方法开发无毒无贵金属元素的多组元Zr基非晶合金十分必要。本文中采用二元共晶比例法和部分元素替代法快速的开发出了一种新的临界尺寸大于10mm的 Zr50Ti5Cu27Ni10Al8非晶合金。这个非晶合金的热稳定性和硬度也通过原位高温X射线衍射和纳米压痕方法测量得出。     

Zr基大块非晶合金在过冷液相区的静液挤压塑性变形研究

通过Gleeble1500热模拟试验,选择纯铁作为挤压包套材料,然后对非晶合金在390℃、应变速率8.9×10-1s-1的条件下进行了静液挤压。Zr非晶合金产生了塑性变形,但没有发生均匀粘滞性流动,而是断裂成两段。样品断口上随机分布着充分与未充分发展的“脉纹”状切变带,并且断面上出现了类似流动熔体凝固后的特征结构。高应变速率变形条件使非晶合金产生的非均匀流变,以及静液挤压时纯铁先于非晶合金的流动变形是造成非晶合金断裂的主要原因。挤压态非晶合金的过冷液相区减小,热稳定性有所降低。     

镁基大块非晶合金在过冷液相区流变行为本构关系

研究了Mg60Cu30Y10大块非晶合金在过冷液相区的流变行为.结果表明:随着温度升高和应变速率增加,平衡态的牛顿流转变为非平衡态的非牛顿流;其流变行为对于温度和应变速率非常敏感.由粘度与应变速率的关系,根据Arrhenius型VFT方程,确定了流动应力、应变速率和温度的关系.Mg60Cu30Y10大块非晶合金在过冷液相区的流变性能依赖于温度与变形速率,其微观机制可由自由体积模型解释,为大块非晶合金流变成形工艺的实现提供理论依据:温度高于玻璃转变温度以后,自由体积的增加使非晶合金变形过程中能够移动的原子数目随之增加,自由体积周围的原子沿外力的作用方向移动,即宏观上的塑性流变行为.应变速率增加,由热激活引起的自由体积增加不能满足更多原子流变所需的空间体积,导致牛顿流向非牛顿流转变.     

Zr基非晶合金在过冷液相区的高应变速率压缩变形行为

利用Gleeble1500热模拟机研究了Zr41.2Ti13.8Cu12.5Ni10Be22.5非晶合金在过冷液相区内633、653和673K,应变速率分别为2×10-2s-1和2×10-1s-1条件下的单向压缩变形行为.结果表明:在673 K时两种应变速率下,该合金都具有很好的塑性,尤其在2×10-2s-1时流变应力只有74 MPa,非常适于进行超塑性加工.对非晶合金的断口进行了观察,得到柱状非晶合金压缩变形时外观和断口形貌随着变形条件的变化规律.采用自由体积模型对非晶合金的形变和断裂的微观机制进行了分析.     

Ag和Fe元素添加对Cu-Zr-Al系非晶形成能力和力学性能的影响

以Cu-Zr-Al三元系为基础,研究Ag和Fe合金组元添加对块体金属玻璃(BMG)及BMG基复合材料的非晶形成能力和力学性能的影响.在Cu-Zr-Al三元合金体系中,Cu50Zr42Al8系BMG的△Tx=61 K,Trg=0.624,γ=0.416.适量添加Ag元素能显著地提高非晶形成能力:在Cu-Zr-Al-Ag四元合金体系中,Cu43Zr45Al8Ag4、Cu45Zr42Al8Ag5、Cu40Zr44Al10Ag6、Cu43Zr41Al8A98和Cu36Zr48Al8Ag8的Trg分别为0.618、0.625、0.618、0.628和0.598,γ值分别为0.424、0.427、0.424、0.432和0.433,△TX分别为77、76、78、84和108 K.在(Cu0.36Zr0.48-Al0.08Ag0.08)100-XFex(x-=0,3,5,10,15,20)五元体系中,Fe的添加明显影响合金的非晶形成能力;尽管△TX和Trg呈下降趋势,但(Cu0.36Zr0.48Al0.08Ag0.08)97Fe3块体非晶合金仍具有较高的非晶形成能力,其△TX=103 K,Trg=566,γ=0.424:Fe的适量加入可显著提高合金的力学性能,其中(Cu0.36Zr0.48Al0.08Ag0.08)95Fe5合金的强度和塑性应变分别提高至2 249 MPa和4.9%.Fe元素的存在导致Cu36Zr48Al8Ag8合金中产生明显的相分离,使(Cu0.36Zr0.48Al0.08Ag0.08)100-xFex合金得到增强增韧.     

Evolution of microstructure and non-equilibrium phases in electron beam treated Zr55Cu30Al10Ni5 bulk amorphous alloy

Electron beam (EB) is becoming very popular for the modification of the surfaces as it involves localized melting and fast cooling which helps in achieving the non-equilibrium phases as well as fine microstructure. Surface modification of Zr-based amorphous alloy Zr₅₅Cu₃₀Al₁₀Ni₅ has been carried out by EB melting. Differential scanning calorimetry (DSC) was employed to determine the supercooled liquid region and activation energy of crystallization. The as-cast and modified surfaces of amorphous alloy at different beam conditions were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) techniques. Various phases like NiZr₂, CuZr₂ and Cu₁₀Zr₇ were identified which resulted in the enhancement of hardness of the modified alloy surface.     

A Cu-based amorphous alloy with a simultaneous improvement in its glass forming ability and plasticity

An amorphous alloy, Cu₄₃Zr₄₃Al₇Be₇, was synthesized. The alloy showed a large supercooled liquid region (115 °C), a significant glass forming ability (Φ12 mm) and considerable strain to fracture (8–9%), which collectively have not been observed in other Cu-based amorphous alloys. The alloy has a unique microstructure characterized by atomic-scale phase separation, which most likely resulted from the large difference in the mixing enthalpy between the binary pairs. This study discusses a possible mechanism underlying the simultaneous enhancement in the GFA and plasticity by considering the atomic packing state and atomic-scale compositional separation resulting from Al and Be.     

A thermodynamic approach to assess glass-forming ability of bulk metallic glasses

According to the Gibbs free energy difference between liquid and crystal, a thermodynamic glass-forming ability(GFA) parameter related to characteristic temperatures, onset crystallization temperature(T_x) and liquidus temperature(T_l), was proposed for evaluating the GFA of bulk metallic glasses(BMGs). The new parameter defined as ω=T_l(T_l+T_x)/(T_x(T_l−T_x)) has good correlation with the critical section thickness(Z_c) of Ca-Mg-Cu BMGs. Being verified by the glasses data, including oxide glasses, which were used to validate the former GFA parameters, ω is one of the most reliable and applicable GFA parameters among T_rg (=T_g/T_l), γ(=T_x/(T_l+T_g)), α (=T_x/T_l), δ (=T_x/(T_l−T_g), and so on. Finally, predicting GFA of Cu-Ag-Zr-Ti and Cu-Zr-Ti-Al BMGs using ω was compared with the experimental results.     

Zr基非晶合金在过冷液相区静液挤压的变形行为及结构

研究了Zr41.2Ti13.8Cu12.5Ni10Be22.5非晶合金在过冷液相区内静液挤压的变形行为以及结构变化。结果表明:非晶合金在高应变速率下产生了明显的塑性变形,直径从16 mm变为12 mm,断裂为4段,且样品断口上随机分布着充分发展与未充分发展的脉纹式切变带,由此可看出非晶合金的变形为非牛顿体变形行为;挤压后的样品约有3%的非晶相发生晶化,在非晶基体上析出10~20 nm的纳米晶粒,导致挤压后非晶合金的热稳定性降低;静液挤压高应变速率变形条件使非晶合金产生非均匀流变,是造成非晶合金断裂的主要原因。     

Anomalous packing state in Ce-Ga-Cu bulk metallic glasses

Formation mechanism of bulk metallic glasses (BMGs) with high glass-forming ability (GFA) has been a long-standing subject in the field of solid state physics. To highlight the GFA-associated local atomic structure, element-specific positron annihilation spectroscopy was conducted for recently discovered ternary Ce₇₀Ga_xCu_30-x (x = 6–13; at.%) BMGs. We succeeded in identifying the packing structure under the condition of ambient pressure, in which Ce atoms are concentrated more than that in Ce crystal. This anomalous glassy state is most efficiently formed at the Ga concentration of ∼10%, where the best glass-forming ability (GFA) is experimentally observed. First-principles computer simulation results suggest that this anomalous packing structure is associated with Ce-4f electron delocalization in the Ce-Ga-Cu BMGs. The findings provide unambiguous evidence for the relationship between the packing-efficient local structure and the GFA.     

Zr-Co(Cu)-Al bulk metallic glasses with optimal glass-forming ability and their compressive properties

The formation of bulk metallic glasses (BMGs) in the ternary Zr₅₆Co₂₈Al₁₆ and quaternary Zr₅₆Co_28–xCu_xAl₁₆ (x=2, 4, 5, 6, 7, mole fraction, %) glassy alloys was investigated via the copper mold suction casting method. The main purpose of this work was to locate the optimal BMG-forming composition for the quaternary ZrCo(Cu)Al alloys and to improve the plasticity of the parent alloy. The X-ray diffractometry (XRD), transmission electron microscopy (TEM) and differential scanning calorimetry (DSC) were used to investigate the glassy alloys structure and their glass forming ability (GFA). In addition, the compression test, microhardness, nano-indentation and scanning electron microscopy (SEM) were utilized to discuss the possible mechanisms involved in the enhanced plasticity achievement. The highest GFA among Cu-containing alloys was found for the Zr₅₆Co₂₂Cu₆Al₁₆ alloy, which was similar to that of the base alloy. Furthermore, the plasticity of the base alloy increased significantly from 3.3% to 6% for the Zr₅₆Co₂₂Cu₆Al₁₆ BMG. The variations in the plasticity and GFA of the alloys were discussed by considering the positive heat of mixing within Cu and Co elements.     

Zr基块体非晶合金超塑性微挤压成形数值模拟

利用压缩实验数据建立了Zr55Cu30Ni5Al10大块非晶合金在过冷温度区域内的流动应力模型,并选用DE-FORM-3D软件对杯形非晶合金零件超塑性微挤压成形过程进行了模拟,得到了挤压过程中坯料的速度场、应变速率场和应力场的分布规律。分析发现在挤压过程中材料的应变速率极不均匀,因此,对材料的流动变形过程进行了合理分区,分析各区域的形状、大小及变化历程。在此基础上,利用反挤压工艺成功挤出了外径为2.2 mm、壁厚为0.05 mm的杯形零件。SEM显示,该成形件壁厚均匀,尺寸和几何形状满足设计要求。     

Glass forming ability and crystallization of Zr-Cu-Ag-Al-Be bulk metallic glasses

The glass forming ability of Zr₄₆Cu_37.64−xAg_8.36Al₈Be_x (x = 0, 6 and 10 at.%) bulk metallic glasses (BMGs) were significantly improved by Be addition. The critical size of amorphous rods can be over 35 mm diameter. The high GFA achieved is mainly due to the decrease of melting point and liquidus temperature, and suppression of the formation of crystalline phases during solidification from liquid state. The high stabilization with supercooled liquid regime of 115 K was found for the BMG with x = 10 at.%. Two independent exothermic events happen in x = 0 and 6 at.% BMGs, corresponding to the formation of primary crystalline phases Cu₁₀Zr₇ and AgZr, then transforming to final stable crystalline phases Zr₂Cu and AlCu₂Zr. However, in the x = 10 at.% BMG, the precipitation of primary phases and transformation to final stable phases are within the first exothermic event and the AlCu₂Zr phase is totally suppressed.     

Effect of hydrostatic pressure on the decomposition behavior of Cu54Zr22Ti18Ni6 bulk metallic glass alloy in supercooled liquid region

The effect that hydrostatic pressure has on the decomposition behavior in Cu₅₄Ni₆Zr₂₂Ti₁₈ bulk metallic glass (BMG) alloy was assessed using samples, which were isothermally annealed in the supercooled liquid region (SLR) with and without application of hydrostatic pressure. During subsequent annealing for the thermal analysis, the samples annealed under hydrostatic pressure displayed a slower crystallization process in the SLR, which is attributed to a retarded compositional decomposition of the BMG alloy under pressure.     

Nd对块体Mg-Cu-Y-Nd非晶合金玻璃形成能力的影响

在非真空熔炼条件下采用工业纯原材料和负压铜模吸铸法制备Mg65Cu25Y10-xNdx(x=0,2,4,6,8,10)棒状试样,利用差示扫描量热(DSC)和X射线衍射(XRD)等方法分析Nd对Mg-Cu-Y-Nd非晶合金玻璃形成能力的影响。结果表明:Nd的含量(x)为0,4,6成分的合金试样具有完全非晶态组织,且x=4时具有最大的玻璃形成能力,其约化玻璃转变温度(Trg)为0.592,过冷液相区宽度(ΔTx)高达66 K;当x为2,8,10时,由于合金成分明显偏离共晶成分,玻璃形成能力降低,试样只含有少量非晶,且主要呈晶体组织特征。     

Preparation, thermal stability, and magnetic properties of Fe---Co---Zr---Mo---W---B bulk metallic glass

A bulk metallic glass (BMG) cylinder of Fe₆₀Co₈Zr₁₀Mo₅W₂B₁₅ with a diameter of 1.5 mm was prepared by copper mould casting of industrial raw materials. The amorphous state and the crystallization behavior were investigated by X-ray diffraction (XRD). The thermal stability parameters, such as glass transition temperature (T_g), crystallization temperature (T_x), supercooled liquid region (ΔT_x) between T_g and T_x, and reduced glass transition temperature T_rg (T_g/T_m) were measured by differential scanning calorimetry (DSC) to be 891, 950, 59 K, and 0.62, respectively. The crystallization process took place through a single stage, and involved crystallization of the phases -Fe, ZrFe₂, Fe₃B, MoB₂, Mo₂FeB₂, and an unknown phase, as determined by X-ray analysis of the sample annealed for 1.5 ks at 1023 K, 50 K above the DSC peak temperature of crystallization. Mössbauer spectroscopy was studied for this alloy. The spectra exhibit a broadened and asymmetric doublet-like structure that indicated paramagnetic behavior and a fully amorphous structure. -Fe was found in the amorphous matrix for a cylinder with a diameter of 2.5 mm. The success of synthesis of the Fe-based bulk metallic glass from industrial materials is important for the future progress in research and practical application of new bulk metallic glasses.     

过冷液态Zr48Cu36Ag8Al8块体非晶合金的相分离及组织演变

本文通过x射线衍射(XRD)、差示扫描量热法(DSC)和透射电子显微镜(TEM)研究了退火温度对Zr₄₈Cu₃₆Ag₈Al₈金属玻璃微观结构演化的影响。结果表明,快速凝固获得的样品为典型的非晶态结构。当样品在703K保温20分钟时,均一的非晶基体相分离成两种非晶合金,即,发生相分离。由于相分离结构与非晶基体在等温退火过程是竞争的关系,这个结构很容易向晶化态进行转变,形成AlZr₂ AlAg₃相。Zr₄₈Cu₃₆Ag₈Al₈金属玻璃的微观结构在过冷液相区等温退火过程中经历了的局部结构转变,相分离以及纳米晶转变,这个过程意味着Zr₄₈Cu₃₆Ag₈Al₈金属玻璃的微观结构对退火温度十分敏感。此外,相分离的形成可以加速纳米晶的形成。     

Zr_(55)Al_(10)Ni_5Cu_(30)大块非晶合金在过冷液相区内虚拟应力模型的改进

针对描述非晶合金在过冷液相区流动行为的虚拟应力模型虽然能定性分析应力-应变关系,但定量计算误差很大的问题,以Zr55Al10Ni5Cu30为例,采用MATLAB遗传算法优化弹性模量、最大应力和最大松弛时间,提高了模型对应力峰值及稳态应力值的计算精度;提出时间调整因子概念,可提高对应力变化历史描述的准确度;改进后的虚拟应力模型与Zr55Al10Ni5Cu30大块非晶合金单轴压缩实验的结果吻合较好。