CN102418053A - Zr-Cu-Ni-Al amorphous alloy added with trace boron and preparation method thereof - Google Patents

Zr-Cu-Ni-Al amorphous alloy added with trace boron and preparation method thereof Download PDF

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CN102418053A
CN102418053A CN2011104070029A CN201110407002A CN102418053A CN 102418053 A CN102418053 A CN 102418053A CN 2011104070029 A CN2011104070029 A CN 2011104070029A CN 201110407002 A CN201110407002 A CN 201110407002A CN 102418053 A CN102418053 A CN 102418053A
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amorphous
copper mold
amorphous metal
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刘龙飞
颜建辉
刘文辉
杨俊�
蔡春波
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Hunan University of Science and Technology
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Abstract

The invention provides a Zr-Cu-Ni-Al amorphous alloy added with trace boron and a preparation method thereof, wherein the component expression of the amorphous alloy is ZraCubAlcNidBeThe alloy is prepared by arc melting high-purity metal materials of elements into master alloy, cutting the master alloy into a volume weight required by a copper mold, cleaning, placing a master alloy sample in a suction casting crucible, sucking the master alloy sample into the copper mold after melting, filling air, and finally discharging the copper mold. The obtained amorphous alloy has the advantages of low cooling rate, large size, high hardness, good thermal stability, wider supercooled liquid region and good amorphous forming capability.

Description

添加微量硼的Zr-Cu-Ni-Al非晶合金及其制备方法Zr-Cu-Ni-Al amorphous alloy with trace amount of boron added and preparation method thereof

技术领域 technical field

本发明属于非晶合金领域,特别涉及一种添加微量硼的Zr-Cu-Ni-Al非晶合金及其制备方法。 The invention belongs to the field of amorphous alloys, in particular to a Zr-Cu-Ni-Al amorphous alloy added with a trace amount of boron and a preparation method thereof.

背景技术 Background technique

非晶合金是指固态时其原子的三维空间是拓扑无序排列,并在一定温度范围内保持这种状态相对稳定的合金,又称金属玻璃(Metallic Glass)。由于超急冷凝固,合金凝固时原子来不及有序排列结晶,没有晶态合金的晶粒、晶界及位错缺陷的存在,因而呈现出优异的综合物理、化学和力学性能。人们最早使用的金属和合金都是晶态材料,1937年德国物理学家 Kramer 利用蒸发沉积法首先制备出非晶态 Sb 薄膜,1950年 Brenner 等用电沉积法制备出了Ni-P 非晶态合金。50年代末期,美国哈佛大学 Turnbull 教授首次提出利用熔体深过冷的方法制备非晶态合金的设想。60年代初,美国加州理工学院的 Duwez 教授发明了喷枪及活塞装置,并首次用过冷熔体急冷法(冷速可达105K/s)制得 Au75Si25非晶态合金薄膜。从此非晶态合金引起了人们的广泛关注,从60年代初到80年代末近30年的时间里,由于受冷却速率制约,制备的非晶态合金只限为薄带、细丝、或粉末状,因而限制了非晶态合金的应用,特别是作为工程结构材料的应用。1974年,Chen 利用真空吸铸法制备出 Pd-Cu-Si 三元非晶合金,尺寸达到毫米级,临界冷速低于 103K/s。从此块体非晶(Bulk Metallic Glass)时代到来,所谓块体非晶合金是指具有较高的非晶形成能力(GFA)和低临界冷速 Rc的非晶态合金,它的三维空间尺寸均大于 1mm。1982年,Turnbull 利用氧化硼包裹法避免异质形核,成功制备出直径达 10mm 的 Pd-Ni-P 块体非晶合金,临界冷速在 10K/s 范围内,但制备的块体非晶合金仅限于 Pd 等贵金属体系。80年代末期,日本的 Inoue 通过多组元合金化的方法突破了冷速的限制,制备出由非贵金属组成的块体非晶合金(如:La-Al-Ni 和 La-Al-Cu[10])。1993年美国的Johnson 成功地制备出玻璃形成能力很大的Zr-Ti-Cu-Ni-Be 块体非晶合金,临界尺寸达到 14mm。随后Inoue 教授利用水淬法制备出临界直径为 72mm的Pd-Ni-Cu-P 块体非晶合金,临界冷速达到0.1K/s。从此块体非晶合金备受材料领域和凝聚态物理领域研究的关注,许多新型合金的深过冷块体非晶合金被制备出来,如:Ti基,Hf基,Fe基,Pd-Fe基,Co基,Cu基,Zr基等。块体非晶合金的形成能力、结构、性能、稳定性和应用等方面的研究都取得了很大进展。 Amorphous alloy refers to an alloy in which the three-dimensional space of its atoms is topologically disordered in a solid state and maintains this state relatively stable within a certain temperature range, also known as metallic glass (Metallic Glass). Due to ultra-rapid solidification, when the alloy is solidified, the atoms have no time to arrange and crystallize in an orderly manner, and there are no grains, grain boundaries and dislocation defects of the crystalline alloy, so it presents excellent comprehensive physical, chemical and mechanical properties. The earliest metals and alloys used by people are crystalline materials. In 1937, German physicist Kramer first prepared amorphous Sb thin film by evaporation deposition method. In 1950, Brenner et al. prepared Ni-P amorphous state by electrodeposition method. alloy. In the late 1950s, Professor Turnbull of Harvard University in the United States first proposed the idea of using the method of deep supercooling of the melt to prepare amorphous alloys. In the early 1960s, Professor Duwez of the California Institute of Technology invented the spray gun and the piston device, and for the first time used the supercooled melt quenching method (cooling rate up to 105K/s) to prepare the Au75Si25 amorphous alloy film. Since then, amorphous alloys have attracted widespread attention. During the nearly 30 years from the early 1960s to the end of the 1980s, due to the restriction of the cooling rate, the prepared amorphous alloys were limited to thin strips, filaments, or powders. shape, thus limiting the application of amorphous alloys, especially as engineering structural materials. In 1974, Chen used the vacuum suction casting method to prepare a Pd-Cu-Si ternary amorphous alloy with a size of millimeters and a critical cooling rate lower than 103K/s. Since then, the era of bulk amorphous (Bulk Metallic Glass) has come. The so-called bulk amorphous alloy refers to an amorphous alloy with high amorphous forming ability (GFA) and low critical cooling rate Rc. Its three-dimensional space size is uniform Greater than 1mm. In 1982, Turnbull used the boron oxide wrapping method to avoid heterogeneous nucleation, and successfully prepared a Pd-Ni-P bulk amorphous alloy with a diameter of 10mm. The critical cooling rate was in the range of 10K/s, but the prepared bulk amorphous alloy Alloys are limited to noble metal systems such as Pd. In the late 1980s, Japan's Inoue broke through the limitation of cooling rate through the method of multi-element alloying, and prepared bulk amorphous alloys composed of non-noble metals (such as: La-Al-Ni and La-Al-Cu[10 ]). In 1993, Johnson in the United States successfully prepared a Zr-Ti-Cu-Ni-Be bulk amorphous alloy with a high glass forming ability, and the critical size reached 14mm. Subsequently, Professor Inoue used the water quenching method to prepare a Pd-Ni-Cu-P bulk amorphous alloy with a critical diameter of 72mm, and the critical cooling rate reached 0.1K/s. Since then, bulk amorphous alloys have attracted much attention in the field of materials and condensed matter physics. Many new alloys of deep supercooled bulk amorphous alloys have been prepared, such as: Ti-based, Hf-based, Fe-based, Pd-Fe-based , Co-based, Cu-based, Zr-based, etc. Great progress has been made in researches on the formation ability, structure, performance, stability and application of bulk amorphous alloys.

自Inoue等总结出获取块体非晶合金的三条原则之后,块体非晶合金的制备及其性能研究有了突破性的进展。大块非晶合金在冷却时,发生形核的原因主要有三个:(1)从原材料中带入的杂质作为非均质形核的核心;(2)合金在熔炼及浇注过程中与周围的氧化性气氛发生反应形成的氧化物夹杂;(3)冷却速度不够大而导致初生晶核乃至晶粒的形成。因此,在大块非晶合金的制备过程中,关键是在冷却过程中抑制合金的非均质形核以及尽可能地提高冷却速度以减少均质晶核的孕育时间。为了减少非晶合金发生形核,对金属的熔炼要进行严格的惰性气体保护。熔体中的杂质和容器的内表面会起到非均质形核的作用,因此熔炼时的提纯和造渣也极为重要。按照Inoue提出的获得高的非晶形成能力的合金系的原则,决定非晶形成能力的将主要是合金的组成。通过选择适当的合金系,在较低冷却速率下即可获得非晶态合金。但是对于同一合金系,选择适当的制备方法将获得尺寸更大的样品。 Since Inoue et al. summed up three principles for obtaining bulk amorphous alloys, breakthroughs have been made in the preparation and performance research of bulk amorphous alloys. There are three main reasons for the nucleation of large amorphous alloys when they are cooled: (1) the impurities brought in from the raw materials serve as the core of heterogeneous nucleation; The oxide inclusions formed by the reaction in the oxidizing atmosphere; (3) The cooling rate is not large enough to cause the formation of primary crystal nuclei and even grains. Therefore, in the preparation of bulk amorphous alloys, the key is to suppress the heterogeneous nucleation of the alloy during cooling and to increase the cooling rate as much as possible to reduce the incubation time of homogeneous nuclei. In order to reduce the nucleation of amorphous alloys, strict inert gas protection is required for the melting of metals. Impurities in the melt and the inner surface of the container will play a role in heterogeneous nucleation, so purification and slagging during smelting are also extremely important. According to the principle proposed by Inoue to obtain an alloy system with high amorphous forming ability, the composition of the alloy will mainly determine the amorphous forming ability. By choosing an appropriate alloy system, amorphous alloys can be obtained at lower cooling rates. But for the same alloy system, choosing an appropriate preparation method will obtain larger samples.

目前,大块非晶合金的制备方法可分为直接凝固法和粉末固结成形法。直接凝固法主要包括:水淬法,铜模铸造法,吸入铸造法,粉末冶金技术,氩弧炉熔炼法,单向熔化法等。 At present, the preparation methods of bulk amorphous alloys can be divided into direct solidification method and powder consolidation forming method. The direct solidification method mainly includes: water quenching method, copper mold casting method, suction casting method, powder metallurgy technology, argon arc furnace melting method, one-way melting method, etc.

水淬法是将大块非晶合金的配料密封在抽成真空的石英管中,加热后水淬冷却,获得大块非晶合金。如果合金中有高熔点组成,可先在氩弧炉中混料制成合金后再封装到石英管中。此法的优点是设备投资小,封装石英管的部门很容易找到,且易得到尺寸较大的圆柱形大块非晶棒。缺点是每制备一次非晶样品均须封一次石英管,且淬火时石英管要被破坏。 The water quenching method is to seal the ingredients of the bulk amorphous alloy in a vacuumed quartz tube, and then water quench and cool after heating to obtain a bulk amorphous alloy. If there is a high melting point composition in the alloy, it can be mixed in an argon arc furnace to form an alloy and then packaged into a quartz tube. The advantage of this method is that the equipment investment is small, the department that encapsulates the quartz tube is easy to find, and it is easy to obtain a large cylindrical bulk amorphous rod. The disadvantage is that the quartz tube must be sealed every time an amorphous sample is prepared, and the quartz tube will be destroyed during quenching.

氩弧炉熔炼法是将各组分混合后利用氩弧炉直接炼制非晶制品。此法只能炼制尺寸较小的非晶样品,且非晶样品的形状一般为纽扣状,不易加工成型。另外此法对合金体系的非晶形成能力要求高,否则样品或样品的心部不能形成非晶,样品和坩埚直接接触的底部有时未完全熔化,可成为结晶相与成的核心,也易出现结晶相。 The argon arc furnace smelting method is to directly smelt amorphous products by using an argon arc furnace after mixing the components. This method can only refine amorphous samples with small size, and the shape of amorphous samples is generally button-shaped, which is not easy to process and shape. In addition, this method has high requirements on the amorphous forming ability of the alloy system, otherwise the sample or the center of the sample cannot form amorphous, and sometimes the bottom of the sample and the crucible in direct contact with the crucible is not completely melted, which can become the core of the crystal phase and formation, and is also prone to occur. crystalline phase.

    粉末冶金法利用非晶态固体在过冷液相区ΔTx 内有效粘度大幅度下降的特性,施加一定的压力使材料发生均匀流变,从而复合为块体。用粉末冶金制备出的大块非晶合金,不仅要满足密实,而且要避免晶化。所制设备的块体材料在纯度、致密度、尺寸和成形等方面受到很大限制。 The powder metallurgy method utilizes the characteristic that the effective viscosity of the amorphous solid decreases significantly in the supercooled liquid phase region ΔT x , and a certain pressure is applied to make the material undergo uniform rheology, thereby recombining into a block. The bulk amorphous alloy prepared by powder metallurgy should not only be dense, but also avoid crystallization. The bulk materials of fabricated devices are very limited in terms of purity, density, size and shape.

发明内容 Contents of the invention

为解决上述技术问题,本发明提供一种添加微量硼的Zr-Cu-Ni-Al非晶合金及其制备方法,其非晶合金冷却速率低,尺寸大,硬度高,热稳定性好,具有较宽的过冷液相区,非晶形成能力好。 In order to solve the above-mentioned technical problems, the present invention provides a Zr-Cu-Ni-Al amorphous alloy with a trace amount of boron and a preparation method thereof. The amorphous alloy has low cooling rate, large size, high hardness, good thermal stability, and Wide supercooled liquid phase region, good amorphous formation ability.

本发明的技术方案是:一种添加微量硼的Zr-Cu-Ni-Al非晶合金,其成分表达式为ZraCubAlcNidBe,所述a,b,c,d,e为合金中各元素原子所占百分比,其中a=50%,b=24~30%,c=10%,d=10%,e=0~6%,a+b+c+d+e=100%。 The technical scheme of the present invention is: a kind of Zr-Cu-Ni-Al amorphous alloy that adds trace amount of boron, and its compositional expression is ZraCubAlcNidBe, and described a, b, c, d, e are the atoms of each element in the alloy. Percentage, where a=50%, b=24~30%, c=10%, d=10%, e=0~6%, a+b+c+d+e=100%.

上述添加微量硼的Zr-Cu-Ni-Al非晶合金的优选方案为: a= 50%, b= 28%, c= 10%, d= 10%,e=2%。 The preferred scheme of the above-mentioned Zr-Cu-Ni-Al amorphous alloy with a trace amount of boron added is: a=50%, b=28%, c=10%, d=10%, e=2%.

上述添加微量硼的Zr-Cu-Ni-Al非晶合金的优选方案为: a= 50%, b= 26%, c= 10%, d= 10%,e=4%。 The preferred scheme of the above-mentioned Zr-Cu-Ni-Al amorphous alloy with a trace amount of boron added is: a=50%, b=26%, c=10%, d=10%, e=4%.

上述添加微量硼的Zr-Cu-Ni-Al非晶合金的优选方案为: a= 50%, b= 24%, c= 10%, d= 10%,e=6%。 The preferred scheme of the above-mentioned Zr-Cu-Ni-Al amorphous alloy with a trace amount of boron added is: a=50%, b=24%, c=10%, d=10%, e=6%.

一种上述添加微量硼的Zr-Cu-Ni-Al非晶合金的制备方法,其步骤如下:将Zr、Cu、Ni、Al元素的高纯度金属材料在经过钛纯化的氩气气氛下电弧熔炼成母合金,然后用电火花线把母合金切割成铜模所需的体积重量,切割好后放入盛97%酒精的烧杯并放入超声波清洗仪器中清洗,将清洗后的母合金样品放在吸铸的坩埚内,重复前面的步骤,至母合金样品熔融后将其吸入铜模内,充入空气,打开炉门清洗坩埚,最后将铜模卸下,即得铜模中添加微量硼的Zr-Cu-Ni-Al非晶合金。 A method for preparing the above-mentioned Zr-Cu-Ni-Al amorphous alloy with a trace amount of boron added, the steps are as follows: high-purity metal materials of Zr, Cu, Ni, Al elements are arc smelted under an argon atmosphere purified by titanium Then use the EDM wire to cut the master alloy into the required volume and weight of the copper mold. After cutting, put it into a beaker containing 97% alcohol and put it into an ultrasonic cleaning instrument for cleaning. Put the cleaned master alloy sample in In the suction-casting crucible, repeat the previous steps until the master alloy sample is melted, suck it into the copper mold, fill it with air, open the furnace door to clean the crucible, and finally remove the copper mold, that is, add a trace amount of boron to the copper mold Zr-Cu-Ni-Al amorphous alloy.

本发明的有益效果在于:本发明提供的添加微量硼的Zr-Cu-Ni-Al非晶合金具有其非晶合金冷却速率低,尺寸大,硬度高,热稳定性好,具有较宽的过冷液相区,其制备方法将电弧熔炼合金技术与铜模铸造技术融为一体,既利用电弧熔炼合金的无污染、均匀性好的优点,又利用了吸铸技术熔体充型号,铜模冷却快的长处,特别是这种技术使合金的熔炼、充型、凝固过程在真空腔内通过一次抽真空来完成,属于一种短流程制备方法。 The beneficial effect of the present invention is that: the Zr-Cu-Ni-Al amorphous alloy added with a trace amount of boron provided by the present invention has the advantages of low cooling rate, large size, high hardness, good thermal stability, and wide The cold liquid phase area, its preparation method integrates the arc melting alloy technology and the copper mold casting technology, which not only utilizes the advantages of no pollution and good uniformity of the arc melting alloy, but also uses the suction casting technology The advantages of fast cooling, especially this technology enables the alloy melting, filling and solidification process to be completed in a vacuum chamber through one vacuum pumping, which belongs to a short-process preparation method.

本发明采用的铜模铸造法是在加热装置的下方设置一水冷铜模,非晶合金组分熔化后靠吸铸或其他方法进入水冷铜模冷却形成非晶。此法虽然要求有专门的设备,但由于冷速较高能制备较大尺寸的非晶样品,而且可用不同的模具制备出不同形状的非晶样品,也可制备形状复杂的非晶样品。铜模铸造法,尤其是带有吸铸装置的,由于有这些优点而被广泛应用。 The copper mold casting method adopted in the present invention is to set a water-cooled copper mold under the heating device, and after the amorphous alloy component is melted, it enters the water-cooled copper mold to be cooled by suction casting or other methods to form an amorphous. Although this method requires special equipment, it can prepare larger-sized amorphous samples due to its high cooling rate, and can prepare amorphous samples of different shapes with different molds, and can also prepare amorphous samples with complex shapes. Copper mold casting, especially with suction casting devices, is widely used because of these advantages.

  the

附图说明 Description of drawings

图1为各实施例中非晶合金的X-射线衍射谱。 Fig. 1 is the X-ray diffraction spectrum of the amorphous alloy in each embodiment.

图2为实施例1所述合金的剪切带形貌。 Figure 2 is the shear band morphology of the alloy described in Example 1.

图3为实施例2所述合金的剪切带形貌。 Figure 3 is the shear band morphology of the alloy described in Example 2.

图4为实施例3所述合金的剪切带形貌。 Figure 4 is the shear band morphology of the alloy described in Example 3.

图5为各实施例的非晶合金压缩时的应力—应变曲线图。 FIG. 5 is a stress-strain curve diagram of the amorphous alloys of various embodiments during compression.

具体实施方式 Detailed ways

实施例1 Example 1

一种添加微量硼的Zr-Cu-Ni-Al非晶合金,其成分表达式为:ZraCubAlcNidBe,其中a,b,c,d,e为原子百分比, a= 50%, b= 28%, c= 10%, d= 10%,e=2%,a+b+c+d+e=100%,其X-射线衍射谱如图1中最上的波形所示,其剪切带形貌如图2所示,压缩时的应力—应变曲线如图5中标记3线型所示。其制备方法如下:以上述原子百分比取纯金属Zr、Cu、Ni、Al元素的棒材、块体或粉料材料,首先在经过钛纯化的氩气气氛下电弧熔炼,合金需要反复熔炼数次以保证成分的均匀性。再用电火花线把母合金满足不同的模所需的体积重量的需求切割,把切割好的材料放入盛97%酒精的烧杯中,一起放入超声波清洗仪器中清洗1分钟。将清洗后的母合金样品放在吸铸的坩埚内,重复前面的步骤,在母合金样品熔融后按吸铸按钮,将其吸入模内。然后充入空气,打开炉门清洗坩埚,将铜模(模具规格为Φ5*75mm)卸下,取出铜模中的添加微量硼的Zr-Cu-Ni-Al非晶合金。母合金样品熔融后以大于100℃/秒的冷却速率冷却,可形成非晶态材料,非晶相的体积百分数不少于50%。 A Zr-Cu-Ni-Al amorphous alloy with a trace amount of boron added, its composition expression is: Zr a Cu b Al c Ni d B e , where a, b, c, d, e are atomic percentages, a= 50%, b= 28%, c= 10%, d= 10%, e=2%, a+b+c+d+e=100%, its X-ray diffraction spectrum is shown in the top waveform in Fig. 1 The shape of the shear band is shown in Figure 2, and the stress-strain curve during compression is shown in Figure 5 as the marked 3 line. Its preparation method is as follows: take the rod, block or powder material of pure metal Zr, Cu, Ni and Al at the above atomic percentage, and first arc melt it in an argon atmosphere purified by titanium, and the alloy needs to be smelted several times To ensure the uniformity of the composition. Then use electric discharge wire to cut the master alloy to meet the volume and weight requirements of different molds, put the cut materials into a beaker filled with 97% alcohol, and put them together in an ultrasonic cleaning instrument for cleaning for 1 minute. Put the cleaned master alloy sample in the suction casting crucible, repeat the previous steps, press the suction casting button after the master alloy sample is melted, and suck it into the mold. Then fill in the air, open the furnace door to clean the crucible, remove the copper mold (the mold size is Φ5*75mm), and take out the Zr-Cu-Ni-Al amorphous alloy with trace boron added in the copper mold. After the master alloy sample is melted and cooled at a cooling rate greater than 100°C/s, an amorphous material can be formed, and the volume percentage of the amorphous phase is not less than 50%.

实施例2 Example 2

本实施例与实施例1的不同之处仅在于, a= 50%, b= 26%, c= 10%, d= 10%,e=4%。其X-射线衍射谱如图1中间的波形所示,其剪切带形貌如图3所示,压缩时的应力—应变曲线如图5中标记4线型所示。其制备方法与实施例1相同。 The only difference between this embodiment and embodiment 1 is that a=50%, b=26%, c=10%, d=10%, e=4%. Its X-ray diffraction spectrum is shown in the waveform in the middle of Fig. 1, its shear band morphology is shown in Fig. 3, and the stress-strain curve during compression is shown in Fig. 5 as marked 4 lines. Its preparation method is identical with embodiment 1.

实施例3 Example 3

本实施例与实施例1的不同之处仅在于, a= 50%, b= 24%, c= 10%, d= 10%,e=6%,a+b+c+d+e=100%。其X-射线衍射谱如图1最下部的波形所示,其剪切带形貌如图4所示,压缩时的应力—应变曲线如图5中标记2线型所示。其制备方法与实施例1相同。 The only difference between this embodiment and embodiment 1 is that a= 50%, b= 24%, c= 10%, d= 10%, e=6%, a+b+c+d+e=100 %. Its X-ray diffraction spectrum is shown in the waveform at the bottom of Fig. 1, its shear band morphology is shown in Fig. 4, and the stress-strain curve during compression is shown in Fig. 5 as marked 2 lines. Its preparation method is identical with embodiment 1.

 本发明提供的添加微量硼的Zr-Cu-Ni-Al非晶合金中允许存在有少量杂质,如氧、氮、磷等,杂质元素主要来自于起始原料、合金冶炼过程中的气氛、外部杂质等。某些占有较小比例的元素可能会对非晶态合金性能产生影响,如氧含量对合金玻璃形成能力有较大影响,本发明提供合金的主要元素Zr是非常活泼的元素,与氧等气体杂质元素具有很强的亲和力,因此,少量的氧化物的存在仍可保证合金具有较好的玻璃形成能力,但合金中氧含量不应超过0.1%(重量比)。 A small amount of impurities such as oxygen, nitrogen, phosphorus, etc. are allowed to exist in the Zr-Cu-Ni-Al amorphous alloy with a trace amount of boron added by the present invention. The impurity elements mainly come from the starting materials, the atmosphere in the alloy smelting process, and Impurities, etc. Some elements occupying a small proportion may have an impact on the performance of the amorphous alloy, such as the oxygen content has a greater impact on the glass-forming ability of the alloy. The main element Zr of the alloy provided by the present invention is a very active element, and it can be mixed with gases such as oxygen. Impurity elements have a strong affinity, therefore, the existence of a small amount of oxides can still ensure that the alloy has a good glass-forming ability, but the oxygen content in the alloy should not exceed 0.1% (weight ratio).

Claims (6)

1.1 a Zr-Cu-Ni-Al non-crystaline amorphous metal that adds trace B is characterized in that: its composition expression formula is Zr aCu bAl cNi dB e, said a, b, c, d, e are the shared per-cent of each element atom in the alloy, a=50% wherein, b=24 ~ 30%, c=10%, d=10%, e=0 ~ 6%, a+b+c+d+e=100%.
2. the Zr-Cu-Ni-Al non-crystaline amorphous metal of interpolation trace B according to claim 1 is characterized in that: a=50%, and b=28%, and c=10%, and d=10%, e=2%.
3. the Zr-Cu-Ni-Al non-crystaline amorphous metal of interpolation trace B according to claim 1 is characterized in that: a=50%, and b=26%, and c=10%, and d=10%, e=4%.
4. the Zr-Cu-Ni-Al non-crystaline amorphous metal of interpolation trace B according to claim 1 is characterized in that: a=50%, and b=24%, and c=10%, and d=10%, e=6%.
5. the preparation method of the Zr-Cu-Ni-Al non-crystaline amorphous metal of the said interpolation trace B of claim 1; Its step is following: the high purity metal material of Zr, Cu, Ni, Al element arc melting under through the argon gas atmosphere of titanium purifying is become mother alloy, cut into the required volume weight of copper mold to mother alloy with wire electric discharge, put into the beaker of Sheng 97% alcohol behind the well cutting and clean at the ultrasonic cleaning instrument; Mother alloy sample after cleaning is placed in the crucible of inhaling casting; To the mother alloy sample melted, it is sucked in the copper mold, charge into air, open the fire door cleaning crucible; At last copper mold is unloaded, promptly get the Zr-Cu-Ni-Al non-crystaline amorphous metal that adds trace B in the copper mold.
6. the preparation method of the Zr-Cu-Ni-Al non-crystaline amorphous metal of interpolation trace B according to claim 5 is characterized in that: cool off with the rate of cooling greater than 100 ℃/second after the said mother alloy sample melted.
CN2011104070029A 2011-12-09 2011-12-09 Zr-Cu-Ni-Al amorphous alloy added with trace boron and preparation method thereof Pending CN102418053A (en)

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