大块非晶合金的性能、制备及应用

综述了大块非晶合金的性能、制备方法及应用，对比了吸铸法制备的棒状Zr41.2Ti13.8Cu12.5Ni10Be22.5,Zr57Cu20Al10Ni8Ti5,Zr52.5Ti5Cu17.9Ni14.6Al10(原子分数)大块非晶样品的过冷温度区间宽度(△Tx)，给出了3种大块非晶合金系列的热稳定性参数Tg、Tx及△Tx，提出了大块非晶合金领域存在的问题及发展方向．     

Zr基块体非晶合金的成分设计及其性能研究

根据二元共晶混合法设计Zr-Cu-Ni-Al非晶合金成分,利用铜模吸铸法制备Zr-Cu-Ni-Al合金棒材.采用XRD、DSC、SEM及准静态压缩实验研究了所设计合金的非晶形成能力和力学性能.结果表明:所设计的Zr-Cu-Ni-Al合金均为非晶态结构,其过冷液相区(ΔTx)均超过65 K,有较好的非晶形成能力,其中Zr55.7 Cu22.4 Ni7.2 Al14.7合金的ΔTx最宽,达到82 K;合金的塑性变形能力由低到高依次为:Zr57 Cu18.67 Ni8 Al16.33、Zr56.36 Cu20.53-Ni7.6 Al15.51、Zr54.4 Cu26.13 Ni6.4 Al13.07和Zr55.7 Cu22.4 Ni7.2 Al14.7,其中Zr55.7 Cu22.4 Ni7.2 Al14.7的塑性达到5.5％,抗压强度达到1885 MPa,其他三种合金的塑性均不足2％.剪切带的增殖和交互作用与非晶合金的塑性和强度密切相关.合金试样断口中均有熔滴存在,这表明在合金变形过程中,断裂处的合金组织发生了粘性流动,并伴有脉纹产生.合金在塑性变形中均发生了锯齿流变,锯齿流变与自由体积的变化密切相关.     

Zr基大块非晶合金成分的等电子浓度和等原子尺寸判据

制备了6种合金Zr65.5Al5.6Ni6.5Cu22.4,Zr65.3Al6.5Ni8.2Cu20,Zr65Al7.5Ni10Cu7.5,Zr64.8Al8.3Ni11.4Cu5.5,Zr64.5Al9.2Ni13.2Cu13.1和Zr63.8Al11.4Ni17.2Cu7.6,共晶成分位于合金Zr64.5Al9.2Ni13.2Cu13.1和合金Zr63.8Al11.4Ni17.2Cu7.6的成分之间，这6种合金均显示了非晶相的形成和较宽的过冷液相区范围△Tx值，以及较大的约化玻璃转变温度Trg值，除合金Zr63.8Al11.4Ni17.2Cu7.6的△Tx值为87K外，其余5种成分合金的△Tx值均在97K以上，最宽的达105K，表明这6种合金是一个具有大玻璃形成能力和高热稳定性的非晶合金系列，合金Zr63.8Al11.4Ni17.2Cu7.6是6种合金中玻璃表成能力和热稳定性最高的，其Tg，Tx和Trg值最高，Inoue非晶合金Zr65Al7.5Ni10Cu17.5并不是最佳非晶成分，提出以等电子浓度和等原子尺寸规律作为设计大块非晶合金成分的判据。     

微量Al添加对铜基大块非晶合金性能的影响

为了进一步提高铜基大块非晶合金的玻璃形成能力及力学性能,采用添加微量Al元素的方法对块体非晶合金Cu52.5Ti30Zr11.5Ni6进行了成分优化.热分析与X射线衍射结果显示,随着微量Al的添加,液相线温度从非晶合金Cu52.5Ti30Zr11.5Ni6的1150 K逐步降低到Cu50.5Ti30Zr11.5Ni6Al2的1134 K,临界直径相应的从5 mm提高到6 mm.大块非晶Cu50.5Ti30Zr11.5Ni6Al2的压缩断裂强度达到2286 MPa,比经典的铜基非晶合金Cu47Ti34Zr11Ni8提高约100 MPa,表明微量Al的添加在有效提高玻璃形成能力的同时,强度也略有提高.     

TiC颗粒增强非晶钛合金基复合材料的热稳定性

用单辊铜轮旋注法制备了TiC颗粒增强Ti45Zr5Cu25Ni20Sn5非晶合金基复合材料.发现在Ti45Zr5Cu25Ni20Sn5非晶合金中加入TiC颗粒可以提高合金的热稳定性.     

具有宽过冷液相区的Fe63Co7NbxZr10—xB20非晶态合金的热稳定性和磁性研究

利用单辊急冷法制备出厚约35μm宽5mm的Fe63Co7NbxZr10-xB20条带，并研究了合金的热稳定性、非晶结构和磁性能。结果表明，含4at%Nb的Fe63Co7Nb4Zr6B20合金过冷液相区ΔTx最宽，达到79K。合金系的饱和比磁化强度σs随着Nb含量的增加而线性减小。合金系经973K退火900s，由于α-Fe等相的析出，使得合金的σs和Hc均迅速升高。     

Cu-Zr-Al-Ti块体非晶合金的制备及腐蚀行为研究

制备出新型Cu46 Zr46 Al4 Ti4块体非晶合金.利用X射线衍射仪和差示扫描量热仪对其非晶态进行表征,采用电化学方法和扫描电子显微镜研究了非晶合金在3.5％ NaCl溶液中的电化学行为.结果表明,Cu46Zr46-Al4 Ti4样品为完全非晶,玻璃转变温度Tg、晶化温度Tx和过冷液相区△Tx都有所降低,断裂强度提高了约11％.Cu46 Zr46 Al4 Ti4的腐蚀电流密度降低了1个数量级,电化学反应电阻R1大大增加.分析表明,Ti通过抑制阴极过程从而降低了非晶合金的腐蚀速度,其机理可能是Ti的加入降低了活性阴极的面积或增加了氧的离子化过电位.     

具有宽过冷液相区的Fe63Co7NbxZr10-xB20非晶态合金的热稳定性和磁性研究

利用单辊急冷法制备出厚约35μm宽5mm的 Fe63Co7NbxZr10-xB20条带,并研究了合金的热稳定性、非晶结构和磁性能.结果表明,含4at%Nb的Fe63Co7Nb4Zr6B20合金过冷液相区Δ Tx最宽,达到79K.合金系的饱和比磁化强度σs随着Nb含量的增加而线性减小.合金系经973K退火900s,由于α\|Fe等相的析出,使得合金的σs和Hc均迅速升高.     

锆基大块非晶在HCl溶液中的耐腐蚀性研究

利用CHI660B型电化学工作站研究了4种不同成分（Zr55Al10Ni5Cu30，Zr60Al15Ni25，Zr65Al10Ni10Cu15，Xr52．5Al0Ni10Cu15Be12．5）的锆基非晶态合金以及其中两种成分（Zr65Al10Ni10Cu15，Zr52．5Al10Ni10Cu15Be12．5）的晶态合金在2．5mol／L的HCl溶液中的腐蚀行为。通过Tafel曲线的测试结果表明，非晶合金的耐腐蚀性能与其成分有很大的关系，这4种非晶合金试样的耐腐蚀性由强到弱的顺序依次为Zr60Al15Ni25〉Zr65Al10Ni10CU15〉Zr52．5Al10Ni10Cu15Be12．5〉Zr55Al10Ni5Cu30。两种成分的非晶态合金与其对应成分的晶态试样相比，非晶态合金具有较低的腐蚀电流，显示出较好的耐腐蚀性。最后，根据电化学腐蚀原理，从合金的微观结构、化学成分以及腐蚀介质的性质3个方面探讨了影响合金耐腐蚀性的因素。     

高能球磨技术制备Fe_(78-x)MxSi_(13)B_9磁性材料

采用高能球磨技术制备Fe78-xMxSi13B9软磁非晶合金粉体,利用X射线衍射仪、差示扫描量热分析仪、扫描电镜和振动样品磁强计分析过渡金属元素M(Zr、Nb、Mo)的添加对合金粉体微观组织结构、热稳定性及软磁性能的影响。结果表明,Zr、Nb的添加有利于Fe-Si-B系合金的非晶转变,其最大过冷液相区ΔTx为70.62 K,玻璃转变温度Tg和开始晶化温度Tx分别为785.05、855.67 K;饱和磁化强度Ms为111 emu/g,矫顽力Hc约为2 028.443 A/m。     

Investigation of mechanical properties and devitrification of Cu-based bulk glass formers alloyed with noble metals

The mechanical properties, glass-forming ability, supercooled liquid region and devitrification behaviour of the Cu–Zr–Ti–(Pd, Ag, Pt and Au) bulk glass formers were studied by using a mechanical testing machine, X-ray diffraction, transmission electron microscopy, differential scanning calorimetry and isothermal calorimetry. The bulk glassy alloys of diameter 2 mm were formed in the Cu₅₅Zr₃₀Ti₁₀Pd₅ and Cu₅₅Zr₃₀Ti₁₀Ag₅ alloys while Cu₅₅Zr₃₀Ti₁₀Au₅ bulk alloy showed mixed glassy and crystalline structure. No glassy phase was formed in the Cu₅₅Zr₃₀Ti₁₀Pt₅ bulk alloy whereas the glassy phase was formed in all of the ribbon samples prepared by rapid solidification. The studied alloys except for the Pt-bearing one have slightly increased compressive fracture or yield strength values compared to ternary Cu₆₀Zr₃₀Ti₁₀ glassy alloy. At the same time Pd and Au addition significantly expand the supercooled liquid region of Cu–Zr–Ti glassy alloy and increase Young’s modulus. A nanoicosahedral phase is primarily formed in the Cu₅₅Zr₃₀Ti₁₀(Pd,Au)₅ glassy alloys in the initial stage of the devitrification process by nucleation and three-dimensional diffusion-controlled growth. Nearly the same quasilattice constant obtained in the Cu₅₅Zr₃₀Ti₁₀(Pd,Au)₅ alloys illustrates the same type of the icosahedral phase in these alloys. However, no icosahedral phase was found in the Cu₅₅Zr₃₀Ti₁₀(Ag,Pt)₅ alloys.     

Fabrication and nano-imprintabilities of Zr-, Pd- and Cu-based glassy alloy thin films

With the aim of investigating nano-imprintability of glassy alloys in a film form, Zr(49)Al(11)Ni(8)Cu(32), Pd(39)Cu(29)Ni(13)P(19) and Cu(38)Zr(47)Al(9)Ag(6) glassy alloy thin films were fabricated on Si substrate by a magnetron sputtering method. These films exhibit a very smooth surface, a distinct glass transition phenomenon and a large supercooled liquid region of about 80 K, which are suitable for imprinting materials. Moreover, thermal nano-imprintability of these obtained films is demonstrated by using a dot array mold with a dot diameter of 90 nm. Surface observations revealed that periodic nano-hole arrays with a hole diameter of 90 nm were successfully imprinted on the surface of these films. Among them, Pd-based glassy alloy thin film indicated more precise pattern imprintability, namely, flatter residual surface plane and sharper hole edge. It is said that these glassy alloy thin films, especially Pd-based glassy alloy thin film, are one of the promising materials for fabricating micro-machines and nano-devices by thermal imprinting.     

Investigation of mechanical properties and devitrification of Cu-based bulk glass formers alloyed with noble metals

The mechanical properties, glass-forming ability, supercooled liquid region and devitrification behaviour of the Cu–Zr–Ti–(Pd, Ag, Pt and Au) bulk glass formers were studied by using a mechanical testing machine, X-ray diffraction, transmission electron microscopy, differential scanning calorimetry and isothermal calorimetry. The bulk glassy alloys of diameter 2 mm were formed in the Cu₅₅Zr₃₀Ti₁₀Pd₅ and Cu₅₅Zr₃₀Ti₁₀Ag₅ alloys while Cu₅₅Zr₃₀Ti₁₀Au₅ bulk alloy showed mixed glassy and crystalline structure. No glassy phase was formed in the Cu₅₅Zr₃₀Ti₁₀Pt₅ bulk alloy whereas the glassy phase was formed in all of the ribbon samples prepared by rapid solidification. The studied alloys except for the Pt-bearing one have slightly increased compressive fracture or yield strength values compared to ternary Cu₆₀Zr₃₀Ti₁₀ glassy alloy. At the same time Pd and Au addition significantly expand the supercooled liquid region of Cu–Zr–Ti glassy alloy and increase Young's modulus. A nanoicosahedral phase is primarily formed in the Cu₅₅Zr₃₀Ti₁₀(Pd,Au)₅ glassy alloys in the initial stage of the devitrification process by nucleation and three-dimensional diffusion-controlled growth. Nearly the same quasilattice constant obtained in the Cu₅₅Zr₃₀Ti₁₀(Pd,Au)₅ alloys illustrates the same type of the icosahedral phase in these alloys. However, no icosahedral phase was found in the Cu₅₅Zr₃₀Ti₁₀(Ag,Pt)₅ alloys.     

Gibbs Free Energy and Activation Energy of ZrTiAlNiCuSn Bulk Glass Forming Alloys

The Gibbs free energy differences between the supercooled liquid and the crystalline mixture for the (Zr_(52.5)Ti_5Al_(10)-Ni_(14.6)Cu_(17.9))_((100-x)/100)Sn_x (x=0, 1, 2, 3, 4 and 5) glass forming alloys are estimated by introducing the equationproposed by Thompson, Spaepen and Turnbull. It can be seen that the Gibbs free energy differences decrease firstas the increases of Sn addition smaller than 3, then followed by a decrease due to the successive addition of Snlarger than 3, indicating that the thermal stabilities of these glass forming alloys increase first and then followed by adecrease owing to the excessive addition of Sn. Furthermore, the activation energy of Zr_(52.5)Ti_5Al_(10)Ni_(14.6)Cu_(17.9) and(Zr_(52.5)Ti_5Al_(10)Ni_(14.6)Cu_(17.9))_(0.97)Sn_3 was evaluated by Kissinger equation. It is noted that the Sn addition increases theactivation energies for glass transition and crystallization, implying that the higher thermal stability can be obtainedby appropriate addition of Sn.     

Ti-Zr-Be-Cu-Co块体非晶合金在NaCl溶液中的冲刷腐蚀行为

为评价Ti基块体非晶合金的耐蚀性,以期今后在工业生产中的应用,采用失重法研究了Ti35Zr30Be2 4Cu7.5Co3.5块体非晶合金及其对应晶体成分在质量分数6%Na Cl溶液中0.2、0.4、0.6 m/s流速下的冲刷腐蚀行为.利用X射线分析(XRD)、扫描电镜(SEM)研究了Ti35Zr30Be2 4Cu7.5Co3.5块体非晶合金及其对应晶体成分的相结构、微观腐蚀形貌,并利用电化学极化试验测试2种合金冲刷腐蚀后的耐蚀性.结果表明:随着流速的增加,2种合金的腐蚀速度均升高,其中非晶合金出现最大腐蚀速度峰值的时间由无冲刷状态的32 h缩短到流速为0.6 m/s下的10 h,Ti35Zr30Be2 4Cu7.5Co3.5块体非晶合金腐蚀速度较对应晶体成分小;Ti35Zr30Be2 4Cu7.5Co3.5块体非晶合金较对应晶体成分在质量分数6%NaCl溶液中具有更好的耐蚀性.     

Impurity-driven nanocrystallization of Zr-based bulk amorphous alloys

The effect of oxygen content and Ti addition on the glass forming ability (GFA) and crystallization kinetic of Zr-based bulk glass forming alloys have been studied by means of thermal analysis and X-ray diffraction techniques. Presence of oxygen triggers the formation of a nanocrystalline metastable f.c.c. Zr2 Ni-type phase which can act as heterogenous nucleation sites for the formation of dendrites during solidification. An increase in oxygen content changes the crystallization behaviour from a single- to a double-step process and triggers the crystallization of stable Zr2(Cu,Al) besides metastable Zr2 Ni-type phase. Oxygen-triggered nucleation of a nanocrystalline metastable Zr2 Ni-type phase is found to be the initial step of crystallization. The important parameters of GFA such as glass transition temperatures, Tg, the crystallization temperatures, Tx, and crystallization enthalpies, deltaH, were determined by using DSC. It was observed that the presence of oxygen, even in a very small amount, and Ti addition cause a drastic reduction of the supercooled liquid region, deltaTx, accompanied by a change of the crystallization kinetic. This leads to the decrease in stability of the supercooled liquid, consequently results in a deterioration of the glass forming ability of the alloy.     

Complete Composition Tunability of Cu(Ni)-Ti-Zr Alloys for Bulk Metallic Glass Formation

In the Cu-Zr-Ti ternary system, a new composition zone of bulk metallic glasses (BMGs) formation was discovered, locating at the 55-57 at. Pct Cu, 30-31 at. Pct Ti and 13-14 at. Pct Zr, and near Cu-Ti binary subsystem rather than the Cu-Zr binary. For these alloys, BMG rods of 2 mm in diameter can be fabricated by using copper mould casting. It is expected that these BMG-forming alloys correlate with (L→CuTi+Cu2TiZr+Cu61Zr14) eutectic reaction that the undercooled melt undergoes during solidification. Adopting "3D pinpointing ap-proach", compositional dependence of glass-forming ability (GFA) in Cu(Ni)-Ti-Zr pseudo ternary system was revisited. Optimized BMG-forming composition is located at Cu50.4Ni5.6Ti31Zr13, with a critical diameter of 6 mm for complete BMG formation. Its GFA is significantly superior to Vit 101 (Cu47Ni8Ti34Zr11) previously developed by Caltech group. The effect that the GFA of the ternary base alloy was improved by substitution of Ni for Cu is attributed to a role of retarding the crystallization of Cu51Zr14 intermetallics.     

大块非晶合金Zr55Cu30Al10Ni5的电子结构特征及电击穿行为

测定了大块非晶合金Zr55Cu30Al10Ni5晶化前后的费米能级和各元素的电子结合能，研究了非品合金的电子结构特征和电击穿行为．测试并讨论了非晶材料场发射能力和耐电压强度的关系．结果表明，对于Zr基合金，非品态比品态合金具有更大的功函数．比较了Zr55Cu30Al10Ni5合金非晶态与晶态的耐电压强度数值，发现非晶态合金的耐电压强度数值比较分散，品化合金的耐电压强度相对比较集中．耐电压强度平均值表明，Zr基合金非晶态具有更好的耐电压能力．