Fe- and Co-based bulk glassy alloys with ultrahigh strength of over 4000 MPa

Since the first synthesis of Fe-based bulk glassy alloys in Fe–(Al,Ga)–(P,C,B,Si) system in 1995, a number of Fe- and Co-based bulk glassy alloys have been developed up to date because their alloys are expected to exhibit high mechanical strength and good soft magnetic properties. The maximum diameter of Fe- and Co-based bulk glassy alloys exhibiting high fracture strength of over 4000 MPa is 5 mm for Fe–Co–B–Si–Nb system and 3 mm for Co–Fe–Ta–B–Mo–Si system. The addition of a small amount of Nb or Ta is essential for the increase in their glass-forming ability through the formation of network-like atomic configurations. The primary crystalline phase from supercooled liquid is a metastable complex FCC Fe₂₃B₆ or Co₂₃B₆ phase and hence the change to the local atomic configurations leading to the precipitation of the metastable Fe₂₃B₆ or Co₂₃B₆-type phase is thought to play an important role in the achievement of high glass-forming ability. The highest fracture strength reached as high as 4250 MPa for Fe–Co–B–Si–Nb alloy and 5545 MPa for Co–Fe–Ta–B–Mo alloy. The fracture strength has a good linear relation with Young's modulus, glass transition temperature or liquidus temperature. It is, therefore, concluded that the origin for the ultrahigh strength is attributed to the strong bonding nature among the constituent elements. Considering that Fe–Si–B amorphous alloy wires developed for several years between 1979 and 1983 have been used as high strength materials for the last two decades, the newly developed high-strength Fe- and Co-based bulk glassy alloys are expected to be used as a new type of ultrahigh strength material by utilizing the advantage points of much higher strength and three-dimensional material form.     

Influence of niobium and yttrium on plastic deformation energy and plasticity of Ti-based amorphous alloys

Many amorphous alloys have been developed to date,but the low plasticity has limited their application.To achieve an amorphous alloy with high plasticity,a series of(Ti₄₀Zr₂₅Cu₉Ni₈ Be₁₈)_100-xTM_x(x=0,1,2,3,4 at.%,TM=Nb,Y)alloys were designed to study the influence of Nb and Y addition on the plasticity.The amorphous samples were prepared using the vacuum melting and copper mold casting process.The microstructures,glass forming ability and mechanical properties of the alloys were investigated by X-ray diffractometry(XRD),scanning electron microscopy(SEM),high-resolution transmission electron microscopy(HRTEM),depth-sensitive nanoindentation,and uniaxial compressive test.The plasticity of different bulk amorphous alloys was investigated by measuring the plastic deformation energy(PDE)during loading.The relationship between the PDE value and plasticity in bulk amorphous alloys was explored.Results show that Nb addition decreases the PDE value and promotes the generation of multiple shear bands,which significantly increases the fracture strength and plasticity,while the addition of Y element reduces the fracture strength and plastic strain of the alloy.     

温度和应变速率对Mg61Cu20.3Ag8.7Er10非晶合金力学行为的影响

采用XRD、SEM等技术分析了Mg61Cu20.3Ag8.7Er10合金的结构和断口形貌,研究了Mg61Cu20.3Ag8.7Er10非晶合金在不同温度和不同应变速率条件下的力学行为。结果表明,室温下非晶合金的断裂强度随应变速率的增加而降低。-100℃时,非晶合金不仅具有较高的强度,同时还表现出一定的塑性行为,此时,应变速率对于非晶合金的强度和塑性几乎没有影响。     

Microstructures and mechanical properties of TiAl alloy prepared by spark plasma sintering

A fine-grained TiAl alloy with a composition of Ti-47%Al(mole fraction) was prepared by double mechanical milling(DMM) and spark plasma sintering(SPS). The relationship among sintering temperature, microstructure and mechanical properties of Ti-47%Al alloy was studied by X-ray diffractometry(XRD), scanning electron microscopy(SEM) and mechanical testing. The results show that the morphology of double mechanical milling powder is regular with size of 20?40 μm. The main phase TiAl and few phases Ti₃Al and Ti₂Al were observed in the SPS bulk samples. For samples sintered at 1000 °C, the equiaxed crystal grain was achieved with size of 100?250 nm. The samples exhibited compressive and bending properties at room temperature with compressive strength of 2013 MPa, compression ratio of 4.6% and bending strength of 896 MPa. For samples sintered at 1100 °C, the size of equiaxed crystal grain was obviously increased. The SPS bulk samples exhibited uniform microstructures, with equiaxed TiAl phase and lamellar Ti₃Al phase were observed. The samples exhibited compressive and bending properties at room temperature with compressive strength of 1990 MPa, compression ratio of 6.0% and bending strength of 705 MPa. The micro-hardness of the SPS bulk samples sintered at 1000 °C is obviously higher than that of the samples sintered at 1100 °C. The compression fracture mode of the SPS TiAl alloy samples is intergranular fracture and the bending fracture mode of the SPS TiAl alloy samples is intergranular rupture and cleavage fracture.     

On the nature of anomalously high plasticity of high-strength titanium nickelide alloys with shape-memory effects: I. Initial structure and mechanical properties

This work presents the results of studies of the Ti_49.4Ni_50.6 alloy of enhanced purity with shapememory effects in an ordinary coarse-grained state with an average grain size of 20–30 μm or in a submicrocrystalline state with an average grain size of 0.2–0.3 μm. In this alloy the initial structure, phase composition, martensitic transformations, mechanical properties, and character of fracture have been investigated in a wide temperature range. It has been shown that upon cooling and mechanical tests at room temperature, the alloy exhibits highly reversible thermoelastic martensitic transformations. It has been established that the alloy exhibits high values of the strength and plastic properties and strain-hardening coefficients.     

多孔SiC陶瓷/Zr基非晶合金复合材料动态压缩性能研究

通过压力-浸渗法制备多孔SiC陶瓷/Zr基非晶合金复合材料。利用分离式霍普金森压杆装置(SHPB)、S-4800场发射扫描电镜等测试分析手段,探究复合材料制备保温时间和多孔碳化硅性能对多孔SiC陶瓷/Zr基非晶合金复合材料动态压缩性能的影响,并揭示了其变形机制。结果表明:保温时间和多孔碳化硅性能对多孔SiC陶瓷/Zr基非晶合金复合材料的动态抗压强度都有较大影响,当多孔碳化硅孔隙率为23.77%,平均孔径尺寸为26.72μm时,在复合材料制备浸渗温度为860℃,浸渗后保温6.0 min时,复合材料具有最高的动态抗压强度,为1757 MPa。多孔SiC陶瓷/Zr基非晶合金复合材料动态压缩断裂为脆性断裂,断口微观形貌特征包括SiC陶瓷相上形成具有不同特征的解理台阶,Zr基非晶合金相形成不同形态的脉状花样,非晶相保持相对完整。Zr基非晶合金相能有效阻碍裂纹的扩展,导致非晶相周围的碳化硅碎裂并挤压非晶相整体运动,从而提高了多孔SiC陶瓷/Zr基非晶合金复合材料动态抗压强度。     

Influence of thermal treatment on structure and microhardness of Fe75Ni2Si8B13C2 amorphous alloy

Correlation between hardness of amorphous Fe₇₅Ni₂Si₈B₁₃C₂ alloy and thermally induced structural transformations has been investigated by measuring microhardness in a series of samples heated at different temperatures from 25 to 1000 °C. The alloy has a relatively high hardness in the amorphous state, due to its chemical composition involving silicon, boron and carbon. As the alloy begins to crystallize, microhardness increased and reached a plateau in 500–650 °C temperature region, due to formation composite structure involving the small nanocrystals of α-Fe(Si) and Fe₂B phases dispersed in the amorphous matrix. After treatment at higher temperatures, the nanocomposite structure is replaced by a more granulated structure, leading to decline in microhardness.     

Designing a toxic-element-free Ti-based amorphous alloy with remarkable supercooled liquid region for biomedical application

A series of toxic-element-free Ti–Zr–Ta–Si amorphous alloy ribbons have been successfully prepared by melt-spinning. The differential scanning carlorimetry (DSC), X-ray diffraction analysis, bending test and microhardness test are conducted for studying the thermal and mechanical properties. The results show that the Ti₄₂Zr₄₀Ta₃Si₁₅ metallic glass ribbon present excellent ductile behavior by the bending testing, without any fracture cracking after bending over 180 degree. In addition, this amorphous alloy possesses a very high glass transition and crystallization temperature of 799 and 898 K, respectively, as well as a very wide supercooled liquid region of 99 K. This amorphous alloy exhibits promising thermal stability during isothermal annealing at the middle temperature of its supercooled region, with more than 3000 s incubation time for isothermal annealing at 823 K (550 °C). This amorphous alloy also shows much lower value of corrosion current density (2.27 × 10⁻⁹ A/m²) than the 304 stainless steel in the 0.3 mass% sodium cloride solutions. This Ti₄₂Zr₄₀Ta₃Si₁₅ alloy is believed to be a promising based alloy for fabricating the bulk metallic glass foam by the spacer technique in the application of biomedical implants.     

高强高韧Mg60Cu16Ni10Nd14块体非晶合金的研究

采用铜模铸造法制备了直径为5mm的Mg60Cu16Ni10Nd14块体非晶合金,利用扫描电镜(SEM)、透射电镜(TEM)X射线衍射(XRD)和差示扫描量热仪(DSC)研究了其组织、相结构和热稳定性。结果表明:合金为完全的非晶结构,且出现了相分离;玻璃转变温度Tg、晶化温度Tx分别为431和488K,过冷液相区△Tx为57K,表明该合金具有较大的玻璃形成能力。压缩试验表明:合金的压缩断裂强度为653MPa,断口出现的大量韧窝是合金塑性变形量达到2.5%的主要原因。     

Structure and magnetic characterization of amorphous and crystalline Nd–Fe–Al alloys

Glass formation has been studied in Nd₆₀Fe₃₀Al₁₀ alloy produced by melt-spinning, water quenching and copper mold chill casting. Partially amorphous alloys were obtained by melt-spinning at low wheel speeds of 5 to 15 m/s and by water quenching of a 1-mm diameter rod, while fully amorphous alloys were obtained by melt-spinning at higher wheel speeds of 20 and 30 m/s and chill casting of a 1-mm diameter rod. A high coercivity was observed in the partially amorphous ribbon melt-spun at 5 m/s and water quenched rod, and in the fully amorphous chill cast rod, while low values of coercivity were obtained in fully amorphous ribbons melt-spun at high speeds of 20 and 30 m/s. Crystallization of water quenched and chill cast samples after heat treatment at high temperature resulted in a substantial reduction of the high coercivity. Results of X-ray diffraction indicate that formation of Nd and a ternary Fe–Nd–Al phase with an unknown crystal structure were present after crystallization. TEM results and a magnetic study of the heat treated samples indicate that as long as there is an amorphous phase produced by low cooling rate, the high coercivity remains. The high coercivity of bulk amorphous samples is discussed. The unknown ternary Fe–Nd–Al phase is antiferromagnetic with a Neel temperature at about 260 K.     

Cu含量对钛镍基非晶复合材料的组织和力学性能的影响

采用铜模吸铸法成功制备Cu含量不同但直径相同的TiNi基非晶复合材料试样(Ti0.5Ni0.5)100-XCuX,研究Cu含量在(X=0,10,15,20,25,30,35,40)情况下对TiNi基非晶复合材料组织和力学性能的影响。试验结果表明,在铜的含量x=20时,合金断裂强度和塑性应变都很高,此时合金具有最优良的综合性能。随着x值的增大,(Ti0.5Ni0.5)100-XCuX合金的非晶形成能力呈现一个从上升、降低再到上升的波形变化,但总体呈现降低趋势。Cu元素在TiNi基复合材料中的适量添加(x=25左右时)可以提高Ti基非晶材料的塑性,但添加量较多(x>30)时,既不能提高合金的非晶形成能力又不能提高合金的强度。在x=15时,合金有最高的断裂强度2440MPa,达到了1471MPa的较高的屈服强度值,且其产生了17.15%塑性应变,在X=25时,合金塑性应变有所提高,塑性变形达到了21.35%。     

High-pressure-torsion deformation of melt-spun Nd<Subscript>9</Subscript>Fe<Subscript>85</Subscript>B<Subscript>6</Subscript> alloy

The effect of severe plastic deformation by high-pressure torsion (HPT) at room temperature and subsequent annealing on the magnetic properties and structural transformations of the melt-spun alloy (MSA) Nd₉Fe₈₅B₆ is studied. The melt-spun ribbons in three structural states, such as nanocrystalline, mixed amorphous-nanocrystalline, and quasi-amorphous, have been subjected to deformation. In the nanocrystalline alloy, HPT leads to the decomposition of part of the Nd₂Fe₁₄B phase into the amorphous phase and α-Fe nanocrystals. The deformation of the alloy in the quasi-amorphous state leads also to the precipitation of a great amount of α-Fe nanocrystals; in this case, the amorphous matrix is depleted of iron. During the HPT of the MSA in the mixed amorphous + nanocrystaline state, both structural transformations occur. The annealing of deformed samples at above 500°C restores the two-phase (Nd₂Fe₁₄B + α-Fe) nanocrystalline state. This is accompanied by increasing magnetic hysteretic properties. The HPT has been found to suppress the formation of nonequilibrium magnetically soft phases, such as NdFe₇ and Nd₂Fe₂₃B₃, that precipitate upon annealing of the melt-spun amorphous alloy. This promotes the formation of an optimum nanocrystalline structure of the α-Fe/Nd₂Fe₁₄B composite material and an increase in its magnetic hysteretic properties because of enhancement of the intergranular exchange interaction. Compact micromagnets 6–15 mm in diameter and 0.2 mm thick, which were prepared from the Nd₉Fe₈₅B₆ alloy using HPT and subsequent annealing, exhibit the following characteristics: B _r = 11.4 kG, H _c = 5.4 kOe, and (BH)_max = 17.1 MG Oe.     

Liquid phase separation and microstructure characterization in a designed Al-based amorphous matrix composite with spherical crystalline particles

The solidification process of the immiscible alloys exhibit a unique opportunity in designing the composites with the spherical crystalline particles dispersed in the amorphous metal matrix. The typical Al–Pb immiscible alloy and the additional elements Ni, Y and Co were selected, and the Al_82.87Pb_2.5Ni_4.88Y_7.8Co_1.95 multicomponent immiscible alloy has been designed. The ribbon samples of the multicomponent alloy were prepared by using the melt spinning technique. The ribbons were characterized by the scanning electron microscopy (SEM). The phase constitution and transformation were studied by the X-ray diffraction (XRD) and the differential scanning calorimeter (DSC). It was revealed in the as-quenched ribbons the Al-based metallic glass matrix is embedded by the spherical crystalline Pb-rich particles. The microstructure evolution, the glass formation and the thermal stability of the as-prepared composite have been discussed in detail. A method has been developed based on the mechanism of the liquid–liquid phase transformation in the miscibility gap of the multicomponent immiscible alloy to produce the spherical crystalline particles in the amorphous matrix.     

高强韧Mo-0.1Zr合金的制备、性能及组织

采用球磨制备Mo-0.1Zr粉末,经压制成型、预烧、高温烧结和真空热处理后,制备抗拉强度超过650 MPa、伸长率大于30%的高强韧Mo-0.1Zr合金,研究真空热处理对合金性能与显微组织的影响。结果表明:经高温烧结后,Mo-0.1Zr合金与纯Mo相比性能提高不明显,断口形貌呈明显的沿晶脆性断裂特征;但经真空热处理后,Mo-0.1Zr合金的性能显著提高,抗拉强度提高了40%、伸长率从7.3%提高到31.2%,合金断口也由沿晶脆性断裂转变为穿晶韧性断裂,且部分晶粒呈韧性撕裂特征。真空热处理温度对合金性能的影响很大,真空热处理温度过高容易使晶粒长大,导致性能提高程度下降;而真空热处理温度过低难以起到消除晶体缺陷的作用,对合金性能提高有限。     

Al0.1CoCrFeNi高熵合金力学性能的分子动力学研究

通过分子动力学方法研究了Al_0.1CoCrFeNi单晶高熵合金在室温（300 K）下沿轴向拉伸后的组织和力学性能变化。通过改变模拟应变速率和温度,分析了单晶高熵合金的拉伸性能;通过模拟室温拉伸实验,研究了含表面小裂纹单晶的显微组织和抗拉伸性能。结果表明,当应变速率在一定范围内时,抗拉伸强度随应变速率增大而增大;当应变速率为10¹⁰ s^-1时,杨氏模量和抗拉伸强度随温度降低而增大。表面有贯穿小裂纹的单晶高熵合金在拉伸一段时间后出现颈缩现象,随着大量滑移位错的快速发展,裂纹尖端出现应力集中,导致快速断裂。     

等温热处理对Zr57Cu15．4Ni12．6Al10Nb5块体非晶合金的组织结构与压缩性能的影响

对Zr57Cu15．4Ni12．6Al10Nb5块体非晶合金进行了等温热处理，用X射线衍射仪、扫描电镜、显微硬度计与压缩试验机研究了不同温度下的等温热处理后合金的组织结构变化、硬度变化与压缩性能变化。该非晶合金出现晶化的温度随热处理时间的增长而降低。在热处理时间相同的条件下，随热处理温度升高，合金的显微硬度有增大趋势。当非晶合金出现相分离或晶化时，其抗压缩强度将急剧下降，断裂方式由非晶态的断裂方式向晶态的断裂方式转变。     

Development of High Strength Ni–Cu–Zr–Ti–Si–Sn In-Situ Bulk Metallic Glass Composites Reinforced by Hard B2 Phase

In the present study, the influence of atomic ratio of Zr to Ti on the microstructure and mechanical properties of Ni–Cu–Zr–Ti–Si–Sn alloys is investigated. The alloys were designed by fine replacement of Ti for Zr from Ni₃₉Cu₂₀Zr_36?xTi_xSi₂Sn₃. The increase of Ti content enhances glass forming ability of the alloy by suppression of formation of (Ni, Cu)₁₀(Zr, Ti)₇ phase during solidification. With further increasing Ti content up to 24 at.%, the B2 phase is introduced in the amorphous matrix with a small amount of B19′ phase from alloy melt. The bulk metallic glass composite containing B2 phase with a volume fraction of ~ 10 vol% exhibits higher fracture strength (~ 2.5 GPa) than that of monolithic bulk metallic glass (~ 2.3 GPa). This improvement is associated to the individual mechanical characteristics of the B2 phase and amorphous matrix. The B2 phase exhibits higher hardness and modulus than those of amorphous matrix as well as effective stress accommodation up to the higher stress level than the yield strength of amorphous matrix. The large stress accommodation capacity of the hard B2 phase plays an important factor to improve the mechanical properties of in situ Ni-based bulk metallic glass composites.     

EFFECT OF Gd ADDITION ON THE GLASS FORMING ABILITY AND MECHANICAL PROPERTIES IN A Zr–BASED BULK AMORPHOUS ALLOY

适量的Gd掺杂可提高Zr_50.7Cu₂₈Ni₉Al_12.3块体非晶合金的玻璃形成能力, 当Gd元素掺杂量 (原子分数) 为1%时, 即(Zr_50.7Cu₂₈Ni₉Al_12.3)₉₉Gd₁, 柱状非晶合金直径可达16 mm (不掺杂时为14 mm). 稀土Gd掺杂降低了锆基块体非晶合金的断裂强度与塑性 变形能力. 随着Gd含量的增加, 其断裂方式由单一的剪切断裂转变为剪切断裂与破碎断裂的复合形式, 且含Gd元素掺杂的非晶合金断口呈现了脉状纹络与纳米周期性条纹共存的特征.     

Effect of γ-(Fe,Ni) crystal-size stabilization in Fe–Ni–B amorphous ribbon

The effect of stabilizing crystal size in a melt-quenched amorphous Fe₅₀Ni₃₃B₁₇ ribbon is described upon crystallization in a temperature range of 360–400°С. The shape, size, volume fraction, and volume density have been investigated by transmission electron microscopy and X-ray diffraction methods. The formation of an amorphous layer of the Fe₅₀Ni₂₉B₂₁ compound was found by means of atomic-probe tomography at the boundary of the crystallite–amorphous phase. The stabilization of crystal sizes during annealing is due to the formation of a barrier amorphous layer that has a crystallization temperature that exceeds the crystallization temperature of the matrix amorphous alloy.     

Zr-基块体非晶合金近玻璃转变温度热处理后的组织与性能

选择在非晶合金的玻璃转变温度与晶化起始温度间的较低温度对Zr57Cu15.4Ni12.6Al10Nb5块体非晶合金进行了等温热处理，用X射线衍射、扫描电镜、显微硬度计与压缩试验，研究了等温热过程中非晶合金的组织结构变化及其对显微硬度与压缩性能的影响。结果表明，在近晶化温度下，一定时间的热处理会引起非晶合金的晶化。而在近玻璃转变温度下，较长时间的热处理也不会引起非晶合金出现明显的晶化和组织变化；但随着热处理时间的增长，合金的显微硬度有增大趋势，合金的压缩强度明显下降，断口形貌变化显著，断裂方式也逐渐由非晶态的断裂方式向晶态的断裂方式转变。