CN102021504A - Magnesium-based amorphous/porous titanium double-phase three-dimensional communicated composite material and preparation method thereof - Google Patents
Magnesium-based amorphous/porous titanium double-phase three-dimensional communicated composite material and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 79
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- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 77
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000010936 titanium Substances 0.000 title claims abstract description 48
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 46
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Abstract
本发明涉及镁基非晶复合材料，具体为一种镁基非晶/多孔钛双相三维连通复合材料及其制备方法。本发明提供一种镁基非晶/多孔钛双相三维连通复合材料，该复合材料为镁基非晶合金和三维连通多孔钛骨架的复合材料，镁基非晶合金填充于多孔钛骨架中，形成双相三维连通的结构。将选定的镁基非晶合金加热熔化，然后通过渗流法或者挤入法将液态合金填充到三维连通多孔钛的孔隙，最后水淬，得到镁基非晶/多孔钛双相三维连通复合材料。该复合材料非晶相和增强相空间三维连通且分布均匀，两相相互强化，解决了镁基非晶合金易发生脆性断裂的问题。该非晶复合材料在大尺寸样品实验条件下具有优良力学性能，具有比强度高、性能稳定、无缺陷的特点。The invention relates to a magnesium-based amorphous composite material, in particular to a magnesium-based amorphous/porous titanium dual-phase three-dimensional connected composite material and a preparation method thereof. The invention provides a magnesium-based amorphous/porous titanium dual-phase three-dimensional connected composite material. The composite material is a composite material of a magnesium-based amorphous alloy and a three-dimensionally connected porous titanium skeleton. The magnesium-based amorphous alloy is filled in the porous titanium skeleton. A two-phase three-dimensional connected structure is formed. The selected magnesium-based amorphous alloy is heated and melted, and then the liquid alloy is filled into the pores of three-dimensional interconnected porous titanium by infiltration method or extrusion method, and finally quenched in water to obtain a magnesium-based amorphous/porous titanium dual-phase three-dimensional interconnected composite material . The amorphous phase and the reinforced phase space of the composite material are three-dimensionally connected and evenly distributed, and the two phases strengthen each other, which solves the problem that the magnesium-based amorphous alloy is prone to brittle fracture. The amorphous composite material has excellent mechanical properties under the experimental conditions of large-scale samples, and has the characteristics of high specific strength, stable performance and no defects.
Description
技术领域technical field
本发明涉及镁基非晶复合材料，具体为一种镁基非晶/多孔钛双相三维连通复合材料及其制备方法。The invention relates to a magnesium-based amorphous composite material, in particular to a magnesium-based amorphous/porous titanium dual-phase three-dimensional connected composite material and a preparation method thereof.
背景技术Background technique
由于具有独特的长程无序短程有序的原子排列结构，非晶金属材料具有一些优异的使用性能，例如：高强度、高弹性极限以及良好的耐腐蚀性能等等。镁基非晶合金具有比强度高的独特优势而成为具有应用前景的新型工程材料。另外，中国具有丰富的镁资源，更使得开发和研究镁基非晶金属材料具有现实意义。Due to the unique long-range disorder and short-range order atomic arrangement structure, amorphous metal materials have some excellent performances, such as: high strength, high elastic limit, good corrosion resistance and so on. Magnesium-based amorphous alloy has the unique advantage of high specific strength and has become a new type of engineering material with application prospects. In addition, China is rich in magnesium resources, which makes the development and research of magnesium-based amorphous metal materials have practical significance.
镁基非晶合金的本征脆性严重制约了它的应用，在室温变形时，几乎所有的镁基非晶合金都没有表现出塑性变形行为，往往由于某条剪切带的迅速扩展使材料发生瞬间脆性断裂。为了克服镁基非晶的瞬间脆断，将镁基非晶合金作为基体制备成复合材料，不仅保留了镁基非晶合金比强度高的优点，而且有效地提高材料的抗变形能力。目前，增韧镁基非晶合金的方法主要有添加高强度陶瓷颗粒和韧性金属颗粒或者内生析出韧性相。在这几种不同的增韧方法中，添加高强度陶瓷颗粒所制备的镁基非晶复合材料的室温压缩塑性变形量为1～3％；内生析出韧性相或添加韧性金属颗粒能有效的阻碍剪切带的扩展，吸收剪切带的能量，并且诱发多重剪切带，极大地提高了材料的变形能力，通过这些方法制备的镁基非晶复合材料的室温压缩塑性变形量为12～40％。由于非晶合金力学性能的尺寸效应和缺陷敏感性，利用传统的铜模喷铸法制备的镁基非晶及其复合材料，在小尺寸样品实验条件下具有的良好力学性能，在大尺寸样品实验条件下其力学性能显著下降；到目前为止，还没有报导过测试样品直径大于3mm的实验条件下具有良好力学性能的镁基非晶复合材料。The intrinsic brittleness of magnesium-based amorphous alloys seriously restricts its application. When deformed at room temperature, almost all magnesium-based amorphous alloys do not show plastic deformation behavior, and often due to the rapid expansion of a certain shear band, the material occurs Instantaneous brittle fracture. In order to overcome the instantaneous brittle fracture of magnesium-based amorphous alloys, magnesium-based amorphous alloys are used as the matrix to prepare composite materials, which not only retains the advantages of high specific strength of magnesium-based amorphous alloys, but also effectively improves the deformation resistance of materials. At present, the methods of toughening magnesium-based amorphous alloys mainly include adding high-strength ceramic particles and tough metal particles or endogenous precipitation of tough phases. Among these different toughening methods, the room temperature compression plastic deformation of magnesium-based amorphous composites prepared by adding high-strength ceramic particles is 1-3%; the endogenous precipitation of tough phases or the addition of tough metal particles can effectively It hinders the expansion of the shear band, absorbs the energy of the shear band, and induces multiple shear bands, which greatly improves the deformation ability of the material. The room temperature compression plastic deformation of the magnesium-based amorphous composite material prepared by these methods is 12~ 40%. Due to the size effect and defect sensitivity of the mechanical properties of amorphous alloys, the magnesium-based amorphous and its composites prepared by the traditional copper mold spray casting method have good mechanical properties under the experimental conditions of small-sized samples, and have good mechanical properties under the experimental conditions of large-sized samples. The mechanical properties decreased significantly under the experimental conditions; so far, no magnesium-based amorphous composites with good mechanical properties under the experimental conditions of the test sample diameter greater than 3mm have been reported.
镁基非晶复合材料的实际应用除了受到其材料尺寸的限制，还受到其制备方法的制约。由于内生复合材料中，内生相的析出形貌和析出量受到制备凝固条件显著影响，使其样品的组织结构具有不可预测性，这也严重影响了它的实际应用。对于颗粒增强镁基非晶复合材料，陶瓷颗粒增强复合材料由于其抗变形能力很弱，基本上不具有实际应用价值；为了保证韧性颗粒增强镁基非晶复合材料具有高的比强度，颗粒的体积分数不能太高。而通常只有当加入较高体积分数的韧性相，镁基非晶复合材料的力学性能才能得到显著提高。此外，采用传统的铜模铸造方法，当外加颗粒体积分数过高时，试样中颗粒的分布难以控制，从而导致试样的成分不均匀性；特别是在制备大尺寸的非晶及其复合材料时，铜模铸造方法还会引入较多的缺陷，如气泡，夹杂等，严重影响其力学性能的稳定性。The practical application of magnesium-based amorphous composites is not only limited by the size of the material, but also by its preparation method. In the endogenous composite material, the precipitated morphology and amount of the endogenous phase are significantly affected by the preparation and solidification conditions, making the structure of the sample unpredictable, which also seriously affects its practical application. For particle-reinforced magnesium-based amorphous composites, ceramic particle-reinforced composites basically have no practical application value due to their weak deformation resistance; in order to ensure that tough particle-reinforced magnesium-based amorphous composites have high specific The volume fraction cannot be too high. Usually, only when a higher volume fraction of ductile phase is added, the mechanical properties of magnesium-based amorphous composites can be significantly improved. In addition, using the traditional copper mold casting method, when the volume fraction of the added particles is too high, the distribution of the particles in the sample is difficult to control, resulting in uneven composition of the sample; especially in the preparation of large-sized amorphous and its composites When using materials, the copper mold casting method will also introduce more defects, such as air bubbles, inclusions, etc., which seriously affect the stability of its mechanical properties.
综上所述，为了能够使镁基非晶及其复合材料成为工程应用材料，我们必须优化合金成分，开发新型制备工艺，制备出成分均匀、结构稳定、大尺寸的具有优良力学性能的镁基非晶复合材料。In summary, in order to make magnesium-based amorphous and its composite materials into engineering application materials, we must optimize the alloy composition, develop new preparation processes, and prepare magnesium-based materials with uniform composition, stable structure, and large size with excellent mechanical properties. Amorphous composite materials.
发明内容Contents of the invention
本发明的目的在于提供一种镁基非晶/多孔钛双相三维连通复合材料及其制备方法，该复合材料非晶相和增强相空间三维连通且分布均匀，两相相互强化，解决了镁基非晶合金易发生脆性断裂的问题。该非晶复合材料在大尺寸样品实验条件下具有优良力学性能，具有比强度高、性能稳定、无缺陷的特点。The object of the present invention is to provide a magnesium-based amorphous/porous titanium two-phase three-dimensional connected composite material and its preparation method. The amorphous phase and the reinforced phase space of the composite material are three-dimensionally connected and evenly distributed, and the two phases strengthen each other, solving the problem of magnesium The base amorphous alloy is prone to brittle fracture. The amorphous composite material has excellent mechanical properties under the experimental conditions of large-scale samples, and has the characteristics of high specific strength, stable performance and no defects.
本发明的技术方案是：Technical scheme of the present invention is:
本发明提供一种镁基非晶/多孔钛双相三维连通复合材料，该复合材料为镁基非晶合金和三维连通多孔钛骨架的复合材料，镁基非晶合金填充于多孔钛骨架中，形成双相三维连通的结构。其中，镁基非晶合金为各种具有较大玻璃形成能力的镁基非晶合金。The invention provides a magnesium-based amorphous/porous titanium dual-phase three-dimensional connected composite material. The composite material is a composite material of a magnesium-based amorphous alloy and a three-dimensionally connected porous titanium skeleton. The magnesium-based amorphous alloy is filled in the porous titanium skeleton. A two-phase three-dimensional connected structure is formed. Among them, the magnesium-based amorphous alloys are various magnesium-based amorphous alloys with relatively large glass-forming ability.
该镁基非晶/多孔钛双相三维连通复合材料的制备方法，将选定的镁基非晶合金加热熔化，然后通过渗流法或者挤入法将液态合金填充到三维连通多孔钛的孔隙，最后水淬，得到镁基非晶/多孔钛双相三维连通复合材料。该方法制备的复合材料力学性能指标如下：压缩塑性应变εp＝8％～50％；压缩断裂强度σf＝1000～1700MPa。The preparation method of the magnesium-based amorphous/porous titanium dual-phase three-dimensional connected composite material is to heat and melt the selected magnesium-based amorphous alloy, and then fill the liquid alloy into the pores of the three-dimensional connected porous titanium by a percolation method or an extrusion method, Finally, it is quenched in water to obtain a magnesium-based amorphous/porous titanium dual-phase three-dimensional interconnected composite material. The mechanical property indexes of the composite material prepared by the method are as follows: compressive plastic strain ε p =8%-50%; compressive fracture strength σ f =1000-1700MPa.
本发明提供的镁基非晶/多孔钛双相三维连通复合材料，该复合材料可以为：具有一定塑性变形能力和极高断裂强度的含Er(稀土元素-铒)镁基非晶合金Mg63Cu16.8Ag11.2Er9(at.％)和三维连通多孔钛骨架的复合材料，镁基非晶合金填充于多孔钛骨架中，形成双相三维连通的结构。The magnesium-based amorphous/porous titanium dual-phase three-dimensional connected composite material provided by the present invention can be: an Er (rare earth element-erbium) magnesium-based amorphous alloy Mg 63 containing Er (rare earth element-erbium) with certain plastic deformation capacity and extremely high fracture strength A composite material of Cu 16.8 Ag 11.2 Er 9 (at.%) and a three-dimensionally connected porous titanium framework, and a magnesium-based amorphous alloy is filled in the porous titanium framework to form a two-phase three-dimensionally connected structure.
本发明中，多孔钛骨架的孔隙度为10％～90％(优选为20％～80％)，孔径大小为30～500μm(优选为100～200μm)，钛的纯度为99.9wt％以上。In the present invention, the porosity of the porous titanium skeleton is 10% to 90% (preferably 20% to 80%), the pore size is 30 to 500 μm (preferably 100 to 200 μm), and the purity of titanium is above 99.9 wt%.
上述镁基非晶合金Mg63Cu16.8Ag11.2Er9(at.％)和三维连通多孔钛骨架复合材料的制备方法，具体步骤如下：The specific steps of the preparation method of the magnesium-based amorphous alloy Mg 63 Cu 16.8 Ag 11.2 Er 9 (at.%) and the three-dimensional interconnected porous titanium skeleton composite material are as follows:
(1)将Cu、Ag和Er(纯度为99.9wt％以上)三种纯金属按成分比例配比称重混合后，在惰性气体气氛中电弧熔炼成中间合金；(1) After three kinds of pure metals, Cu, Ag and Er (purity is more than 99.9wt%) are weighed and mixed according to the composition ratio, arc melting in an inert gas atmosphere to form a master alloy;
(2)按成分比例，将Mg(纯度为99.9wt％以上)纯金属块与中间合金混合后，在惰性气体气氛中感应熔炼成Mg63Cu16.8Ag11.2Er9(at.％)合金；(2) According to the composition ratio, Mg (purity is more than 99.9wt%) pure metal block is mixed with the master alloy, and then induction smelted into Mg 63 Cu 16.8 Ag 11.2 Er 9 (at.%) alloy in an inert gas atmosphere;
(3)在高真空(真空度低于2×10-3Pa)条件下，将三维连通多孔钛骨架和Mg63Cu16.8Ag11.2Er9(at.％)合金加热到600～650℃，采用渗流法或者挤入法将合金熔液填充到三维连通多孔钛骨架的孔隙；(3) Under the condition of high vacuum (vacuum degree lower than 2×10 -3 Pa), heat the three-dimensional interconnected porous titanium framework and Mg 63 Cu 16.8 Ag 11.2 Er 9 (at.%) alloy to 600-650°C, using The infiltration method or the extrusion method fills the alloy melt into the pores of the three-dimensional connected porous titanium skeleton;
(4)待合金熔液充分填充满多孔钛骨架的孔隙后，快速冷却(淬火)，获得镁基非晶/多孔钛双相三维连通复合材料。(4) After the alloy melt fully fills the pores of the porous titanium skeleton, it is rapidly cooled (quenched) to obtain a magnesium-based amorphous/porous titanium dual-phase three-dimensional interconnected composite material.
本发明中所制备的镁基非晶合金复合材料经X射线衍射(XRD)和差热分析(DSC)证实，所获得的非晶合金复合材料具有典型的非晶合金的特征。与多孔钛骨架复核后，镁基非晶合金的非晶形成能力和热力学性质都没有发生改变。The magnesium-based amorphous alloy composite material prepared in the present invention is confirmed by X-ray diffraction (XRD) and differential thermal analysis (DSC), and the obtained amorphous alloy composite material has the characteristics of a typical amorphous alloy. After rechecking with the porous titanium framework, neither the amorphous-forming ability nor the thermodynamic properties of the Mg-based amorphous alloy changed.
室温压缩试验样品尺寸是直径为4mm、高径比2∶1，测试应变速率为5×10-4s-1，并且利用扫描电镜(SEM)对压缩断裂后样品的表面和剪切面都进行了观察。性能指标为：The size of the sample in the compression test at room temperature is 4mm in diameter, the ratio of height to diameter is 2:1, and the test strain rate is 5×10 -4 s -1 . observed. The performance indicators are:
断裂强度：σf＝1400±15MPa(多孔钛骨架孔隙度30％，孔径大小为100～200μm)；Fracture strength: σ f ＝1400±15MPa (porosity of porous titanium skeleton is 30%, pore size is 100～200μm);
塑性变形量：εplastic＝28±2％(多孔钛骨架孔隙度30％，孔径大小为100～200μm)。Plastic deformation: ε plastic = 28±2% (the porosity of the porous titanium skeleton is 30%, and the pore size is 100-200 μm).
本发明具有以下优点：The present invention has the following advantages:
1.本发明采用的镁基非晶合金为Mg63Cu16.8Ag11.2Er9(at.％)，多孔钛骨架的孔隙度为10％～90％，钛的纯度为99.9wt％，该复合材料为镁基非晶合金与三维连通多孔钛骨架复合，具有抗变形能力强、强度高、密度低的特征。与多孔钛骨架复合后，非晶基体的非晶形成能力并没有发生变化。由于钛的密度和镁基非晶合金的密度非常接近，可以在很大范围内调整多孔钛骨架的孔隙度，使得复合材料的密度与复合基体的密度也非常接近，从而保留了镁基非晶合金高比强度的优点。1. The magnesium-based amorphous alloy used in the present invention is Mg 63 Cu 16.8 Ag 11.2 Er 9 (at.%), the porosity of the porous titanium skeleton is 10% to 90%, and the purity of titanium is 99.9wt%. The composite material It is a composite of magnesium-based amorphous alloy and three-dimensional connected porous titanium framework, which has the characteristics of strong deformation resistance, high strength and low density. After compounding with the porous Ti framework, the amorphous matrix's amorphous-forming ability did not change. Since the density of titanium is very close to that of the magnesium-based amorphous alloy, the porosity of the porous titanium skeleton can be adjusted in a wide range, so that the density of the composite material is also very close to that of the composite matrix, thereby retaining the magnesium-based amorphous alloy. The advantages of alloy high specific strength.
2.本发明不同孔隙度的多孔钛骨架和镁基非晶合金复合后，非晶相和增强相分布均匀，而且双相三维连通的结构，使得镁基非晶的剪切变形均匀分布，通过镁基非晶合金与韧性钛骨架的协同变形，极大地提高了材料的塑性变形能力。2. After the porous titanium skeleton with different porosities of the present invention is combined with the magnesium-based amorphous alloy, the amorphous phase and the reinforcing phase are evenly distributed, and the two-phase three-dimensional connected structure makes the shear deformation of the magnesium-based amorphous evenly distributed. The synergistic deformation of Mg-based amorphous alloys and ductile titanium framework greatly improves the plastic deformation ability of the material.
3.本发明所采用的复合方法为熔渗水淬法，与传统的非晶复合材料制备方法(喷铸法)相比较，熔渗水淬法能制备出较大尺寸且性能优异稳定的样品，制备得到的样品具有较少的缺陷，如气孔、夹杂等，而且工艺条件简单易于控制。3. The composite method adopted in the present invention is the infiltration water quenching method. Compared with the traditional amorphous composite material preparation method (spray casting method), the infiltration water quenching method can prepare samples with larger size and excellent and stable performance. The obtained samples have fewer defects, such as pores, inclusions, etc., and the process conditions are simple and easy to control.
4.本发明可制备大尺寸或者形状不规则的复合材料，且该复合材料在大尺寸实验条件下具有良好的力学性能。4. The present invention can prepare large-sized or irregular-shaped composite materials, and the composite materials have good mechanical properties under large-scale experimental conditions.
总之，上述优点表明，本发明具有一定的工程应用前景，各种具有较大玻璃形成能力的镁基非晶合金均适用于此制备方法。In conclusion, the above advantages indicate that the present invention has certain engineering application prospects, and various magnesium-based amorphous alloys with greater glass-forming ability are applicable to this preparation method.
附图说明Description of drawings
图1为复合材料截面的SEM照片。Figure 1 is the SEM photograph of the cross-section of the composite material.
图2为镁基非晶合金与多孔钛骨架增强镁基非晶合金复合材料的X射线衍射曲线。Fig. 2 is the X-ray diffraction curve of magnesium-based amorphous alloy and porous titanium framework reinforced magnesium-based amorphous alloy composite material.
图3为镁基非晶合金与多孔钛骨架增强镁基非晶合金复合材料的室温压缩断裂曲线。Fig. 3 is the room temperature compression fracture curve of magnesium-based amorphous alloy and porous titanium framework reinforced magnesium-based amorphous alloy composite material.
图4a-图4d为复合材料断裂后试样外表面以及断口SEM照片。其中，图4a为复合材试样外表面宏观形貌；图4b为外表面的局部放大图；图4c为非晶合金中剪切带的相互交割；图4d为复合材料的断口局部形貌。Figures 4a-4d are SEM photos of the outer surface of the sample and the fracture after the composite material is fractured. Among them, Figure 4a is the macroscopic appearance of the outer surface of the composite material sample; Figure 4b is a partial enlarged view of the outer surface; Figure 4c is the mutual delivery of shear bands in the amorphous alloy; Figure 4d is the local fracture morphology of the composite material.
具体实施方式Detailed ways
以下通过实施例详述本发明。The present invention is described in detail below by way of examples.
本发明按照如下方法制备镁基非晶/多孔钛双相三维连通复合材料：The present invention prepares the magnesium-based amorphous/porous titanium dual-phase three-dimensional connected composite material according to the following method:
将Cu、Ag和Er(纯度为99.9wt％以上)三种纯金属按成分比例配比称重混合后，在惰性气体气氛中电弧熔炼成中间合金；按成分比例，将Mg(纯度为99.9wt％以上)纯金属块与中间合金混合后，在惰性气体气氛中感应熔炼成Mg63Cu16.8Ag11.2Er9(at.％)合金。将不同孔隙度的三维连通多孔钛骨架和非晶合金在高真空(真空度1.5×10-3Pa)下加热到640℃，合金充分熔化后，采用气压浸渗或者高压挤入方法，将合金熔液填充到三维连通多孔钛骨架的孔隙，待合金熔液充分填充满多孔钛骨架的孔隙后，快速冷却(淬火)，获得镁基非晶/多孔钛双相三维连通复合材料。复合材料的SEM照片如图1所示，镁基非晶合金很好的填充在多孔钛骨架的孔隙中。观察压缩断裂后复合材料表面形貌，如图4所示，多孔钛骨架有效地阻止了剪切带的运动和扩展，大量密集的剪切带均匀地分布在复合材料的表面，通过自身的变形，多孔钛骨架能有效地吸收剪切带扩展所带来的不均匀变形，将剪切带的扩展限制在很小的区域，有效地促进了剪切带的相互交割和二次剪切带的萌生，使变形均匀的分布在整个试样上，从而赋予了材料优良的塑性变形能力。After Cu, Ag and Er (purity is more than 99.9wt%) three kinds of pure metals are weighed and mixed according to the composition ratio, arc melting is formed into an intermediate alloy in an inert gas atmosphere; according to the composition ratio, Mg (purity is 99.9wt%) %) pure metal block mixed with the master alloy, induction melting in an inert gas atmosphere into a Mg 63 Cu 16.8 Ag 11.2 Er 9 (at.%) alloy. The three-dimensional interconnected porous titanium framework and amorphous alloy with different porosities were heated to 640°C under high vacuum (vacuum degree 1.5×10 -3 Pa). After the alloy was fully melted, the alloy was infiltrated by air pressure or high pressure The melt is filled into the pores of the three-dimensionally connected porous titanium framework, and after the alloy melt fully fills the pores of the porous titanium framework, it is rapidly cooled (quenched) to obtain a magnesium-based amorphous/porous titanium dual-phase three-dimensionally connected composite material. The SEM photo of the composite material is shown in Figure 1. The magnesium-based amorphous alloy is well filled in the pores of the porous titanium framework. Observing the surface morphology of the composite material after compression fracture, as shown in Figure 4, the porous titanium skeleton effectively prevents the movement and expansion of the shear bands, and a large number of dense shear bands are evenly distributed on the surface of the composite material. , the porous titanium framework can effectively absorb the uneven deformation caused by the expansion of the shear band, restrict the expansion of the shear band to a small area, and effectively promote the mutual delivery of the shear band and the formation of the secondary shear band Initiation, so that the deformation is evenly distributed on the entire sample, thus endowing the material with excellent plastic deformation ability.
本发明中，渗流法采用气压浸渗，气压浸渗的工艺参数如下：In the present invention, the infiltration method adopts air pressure infiltration, and the process parameters of air pressure infiltration are as follows:
合金熔化时间：1～3分钟；Alloy melting time: 1 to 3 minutes;
合金熔液温度：6000～650℃；Alloy melt temperature: 6000～650℃;
骨架温度：600～650℃；Skeleton temperature: 600～650℃;
外加气压压力：2～4大气压；Applied air pressure: 2 to 4 atmospheres;
气压保持时间：2～4分钟。Air pressure maintenance time: 2 to 4 minutes.
本发明中，挤入法采用高压挤入，高压挤入的工艺参数如下：Among the present invention, extrusion method adopts high-pressure extrusion, and the processing parameters of high-pressure extrusion are as follows:
合金熔化时间：1～3分钟；Alloy melting time: 1 to 3 minutes;
合金熔液温度：600～650℃；Alloy melt temperature: 600～650℃;
骨架温度：600～650℃；Skeleton temperature: 600～650℃;
挤压压力：50～80MPa；Extrusion pressure: 50~80MPa;
挤入和保压时间：1～2分钟。Squeeze in and hold pressure time: 1 to 2 minutes.
实施例1Example 1
Mg63Cu16.8Ag11.2Er9(at.％)非晶合金，其室温压缩断裂曲线见图3曲线1。For Mg 63 Cu 16.8 Ag 11.2 Er 9 (at.%) amorphous alloy, its room temperature compression fracture curve is shown in
室温压缩试验样品尺寸是直径为4mm、高径比2∶1，测试应变速率为5×10-4s-1，并且利用扫描电镜(SEM)对压缩断裂后样品的表面和剪切面都进行了观察。性能指标为：The size of the sample in the compression test at room temperature is 4mm in diameter, the ratio of height to diameter is 2:1, and the test strain rate is 5×10 -4 s -1 . observed. The performance indicators are:
断裂强度：σf＝1098±20MPa；Fracture strength: σ f =1098±20MPa;
塑性变形量：εplastic＝0％。Plastic deformation amount: ε plastic =0%.
实施例2Example 2
当Mg63Cu16.8Ag11.2Er9(at.％)合金与50％孔隙度多孔钛骨架(孔径大小为100～200μm)复合后，其室温压缩断裂曲线见图3曲线2。When the Mg 63 Cu 16.8 Ag 11.2 Er 9 (at.%) alloy is composited with a 50% porosity porous titanium framework (pore size 100-200 μm), its room temperature compression fracture curve is shown in Figure 3,
室温压缩试验样品尺寸是直径为4mm、高径比2∶1，测试应变速率为5×10-4s-1，并且利用扫描电镜(SEM)对压缩断裂后样品的表面和剪切面都进行了观察。性能指标为：The size of the sample in the compression test at room temperature is 4mm in diameter, the ratio of height to diameter is 2:1, and the test strain rate is 5×10 -4 s -1 . observed. The performance indicators are:
断裂强度：σf＝1190±20MPa；Fracture strength: σ f =1190±20MPa;
塑性变形量：εplastic＝19±2％。Plastic deformation: ε plastic = 19±2%.
实施例3Example 3
当Mg63Cu16.8Ag11.2Er9(at.％)合金与30％孔隙度多孔钛骨架(孔径大小为100～200μn)复合后，其室温压缩断裂曲线见图3曲线3。When the Mg 63 Cu 16.8 Ag 11.2 Er 9 (at.%) alloy is compounded with a 30% porosity porous titanium framework (pore size 100-200μn), its room temperature compression fracture curve is shown in Figure 3,
室温压缩试验样品尺寸是直径为4mm、高径比2∶1，测试应变速率为5×10-4s-1，并且利用扫描电镜(SEM)对压缩断裂后样品的表面和剪切面都进行了观察。性能指标为：The size of the sample in the compression test at room temperature is 4mm in diameter, the ratio of height to diameter is 2:1, and the test strain rate is 5×10 -4 s -1 . observed. The performance indicators are:
断裂强度：σf＝1400±15MPa；Fracture strength: σ f =1400±15MPa;
塑性变形量：εplastic＝28±2％。Plastic deformation: ε plastic = 28±2%.
如图2所示，比较镁基非晶合金和本实施例的X射线衍射曲线可知，镁基非晶合金基体和多孔钛骨架复合后没有发生任何化学反应，也没有影响非晶合金的非晶形成能力。As shown in Figure 2, comparing the X-ray diffraction curves of the magnesium-based amorphous alloy and the present embodiment, it can be seen that no chemical reaction occurs after the composite of the magnesium-based amorphous alloy matrix and the porous titanium skeleton, and the amorphous state of the amorphous alloy is not affected. ability to form.
图4a-图4d为复合材料断裂后外表面和断口的SEM照片。如图4(a)所示，通过自身的变形，多孔钛骨架有效地阻止了剪切带的运动和扩展，大量丰富的剪切带均匀地分布在试样的表面，暴露在表面的钛骨架由于变形而明显地凸起，其中插入图为试样表面产生褶皱的钛颗粒；剪切带的运动和扩展被多孔钛骨架限制在很小的区域，有效地避免了主剪切带的快速扩展。图4(b)示出一条剪切带穿过了钛颗粒后，在剪切带的末端萌生出大量的二次剪切带，并且促使不同方向的剪切带发生交割。图4(c)为放大后的与试样变形方向呈45°相互交割的多重剪切带。图4(d)示出复合材料试样断口上，既有多孔钛骨架断裂后钛颗粒经过强烈的剪切变形后产生撕裂面的断口特征，又存在有非晶合金典型的脉纹断口特征，断口上的金属熔滴表面非晶合金发生了非常明显的熔化现象。Figures 4a-4d are SEM pictures of the outer surface and fracture of the composite material after fracture. As shown in Figure 4(a), through its own deformation, the porous titanium skeleton effectively prevents the movement and expansion of the shear bands, and a large number of abundant shear bands are evenly distributed on the surface of the sample, and the titanium skeleton exposed on the surface It is obviously raised due to deformation, and the insert picture shows the wrinkled titanium particles on the surface of the sample; the movement and expansion of the shear band are restricted to a small area by the porous titanium framework, effectively avoiding the rapid expansion of the main shear band . Figure 4(b) shows that after a shear band passes through the titanium particles, a large number of secondary shear bands are initiated at the end of the shear band, and the shear bands in different directions are promoted to be delivered. Figure 4(c) shows the enlarged multiple shear bands that cross each other at 45° to the deformation direction of the sample. Figure 4(d) shows that on the fracture of the composite sample, there are not only the fracture characteristics of the tear surface produced by the titanium particles after the fracture of the porous titanium skeleton, but also the typical veined fracture characteristics of the amorphous alloy , the amorphous alloy on the surface of the metal droplet on the fracture surface has a very obvious melting phenomenon.
相关比较例1Related comparative example 1
铜模喷铸法制备的韧性钼颗粒增强镁基非晶复合材料[参考文献：J.S.C.Jang，X.H.Du.Appl.Phys.Lett.92(2008)011930]。该复合材料
相关比较例2Related comparative example 2
铜模喷铸法制备的含内生片状析出相的镁基非晶合金复合材料[参考文献：X.Hui，K.F.Yao，Acta.Mater.55(2007)907]。该复合材料
相关比较例3Related comparative example 3
铜模喷铸法制备的Ti颗粒增强镁基非晶复合材料[参考文献：M.Kinaka，A.Inoue.Mat.Sci.Eng.A.494(2008)299]。该复合材料
结果表明，本发明双相三维连通复合材料具有优异的力学性能，克服了非晶合金易发生脆性断裂和力学性能对缺陷的敏感性的缺点。与传统镁基非晶合金及复合材料比较，本发明简便易行，具有重要的工程应用前景。The results show that the two-phase three-dimensional interconnected composite material of the invention has excellent mechanical properties, and overcomes the disadvantages of the amorphous alloys being prone to brittle fracture and the mechanical properties being sensitive to defects. Compared with traditional magnesium-based amorphous alloys and composite materials, the invention is simple and easy to implement, and has important engineering application prospects.
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