技术领域technical field
本发明涉及一种微纳尺度孪晶马氏体的形成方法，属于合金钢热处理领域。The invention relates to a method for forming micro-nano-scale twinned martensite, which belongs to the field of alloy steel heat treatment.
背景技术Background technique
近年来，有关纳米孪晶金属材料方面的大量研究及实践证明，孪晶界是一种特殊的低能态共格晶界，孪晶界两侧的晶格呈镜面对称，同普通大角晶界相似，孪晶界可有效地阻碍位错运动，从而使材料强化。但是微米尺度的孪晶片层其强化效果并不显著，当孪晶片层厚度细化至纳米量级时，其强化效果开始显现。纳米孪晶金属材料具有非常独特的力学性能和物理性能，利用纳米尺度孪晶界面强化材料已成为一种提高材料综合性能的新途经。含高密度微纳尺度孪晶亚结构的金属材料具有很多常规金属材料所不具有的性能，如超高的强度硬度、可观的塑性、超高的导电性、高的应变速率敏感性和抗疲劳裂纹萌生性能等。可见，含有高密度纳米孪晶的金属材料具有很多优良的性能，因而，这样的材料也具有广阔的应用空间。In recent years, a large number of studies and practices on nano-twinned metal materials have proved that the twin boundary is a special low-energy coherent grain boundary, and the crystal lattices on both sides of the twin boundary are mirror-symmetrical, similar to ordinary high-angle grain boundaries. , the twin boundaries can effectively hinder the movement of dislocations, thereby strengthening the material. However, the strengthening effect of the micron-scale twinned wafer layer is not significant, and the strengthening effect begins to appear when the thickness of the twinned wafer layer is refined to the nanometer level. Nano-twinned metal materials have very unique mechanical and physical properties, and strengthening materials with nano-scale twinning interfaces has become a new way to improve the comprehensive performance of materials. Metal materials containing high-density micro-nano-scale twin substructures have many properties that conventional metal materials do not have, such as ultra-high strength and hardness, considerable plasticity, ultra-high electrical conductivity, high strain rate sensitivity and fatigue resistance. Crack initiation performance, etc. It can be seen that metal materials containing high-density nano-twins have many excellent properties, and therefore, such materials also have broad application space.
孪晶并不罕见，在一些金属间化合物，很多金属材料，特别是低层错能的金属材料中，都能观察到孪晶。但这些材料中所含的孪晶，要么含量太少，孪晶结构的存在，不足以影响块体材料的力学性能；要么就是材料中含的是尺寸粗大的孪晶片层，粗大的孪晶对强度硬度的贡献不大，反而降低材料的韧塑性能。目前，对微纳尺度孪晶方面的研究及实践工作方面，主要是运用磁控溅射法制得的含高密度纳米孪晶的纯铜材料，在实验条件下，显示出了诸多优异的力学性能和物理性能。但这项技术制得的纳米孪晶纯铜材料尚未得到广泛的应用，原因在于通过这种方法制备的含高密度孪晶的纯铜材料尺寸有限，据文献报到其板状拉伸样的厚度仅为40um。而大块的纳米孪晶纯铜其自身的层错能较低，在受力的条件下，极易因原子面的滑移失去纳米孪晶的孪生关系，转变成常规的粗晶纯铜的结构，失去了纳米孪晶结构的强化作用。从而导致用磁控溅射法制得的含高密度纳米孪晶的纯铜材料无法得到广泛的应用。Twins are not uncommon. Twins can be observed in some intermetallic compounds and many metallic materials, especially those with low stacking fault energy. However, the twins contained in these materials are either too small, and the existence of the twin structure is not enough to affect the mechanical properties of the bulk material; or the material contains a coarse twin layer, and the coarse twin pairs The contribution of strength and hardness is not large, but reduces the ductility and plasticity of the material. At present, the research and practical work on micro-nano-scale twins are mainly pure copper materials containing high-density nano-twins prepared by magnetron sputtering. Under experimental conditions, they have shown many excellent mechanical properties. and physical properties. However, the nano-twinned pure copper material prepared by this technology has not been widely used. The reason is that the size of the pure copper material containing high-density twins prepared by this method is limited. According to the literature, the thickness of the plate-shaped tensile sample Only 40um. However, the stacking fault energy of bulk nano-twinned pure copper is low. Under the condition of stress, it is very easy to lose the twinning relationship of nano-twinned crystals due to the slip of atomic planes, and transform into conventional coarse-grained pure copper. The structure loses the strengthening effect of the nano-twin structure. As a result, pure copper materials containing high-density nano-twins prepared by magnetron sputtering cannot be widely used.
通过相变的方法在钢中制备微纳尺度孪晶有较大难度。一方面由于碳钢的层错能较高不易形成形变孪晶，其变形机制主要以位错的滑移为主，因此只能以相变方式来获得孪晶。而通过马氏体相变获得的孪晶比较粗大，对强度贡献不大反而显著降低韧塑性，为此必须首先要解决晶粒超细化达到1-2μm才能保证后续形成的孪晶块尺寸在300nm以内。另一方面还必须通过其它方式提高奥氏体相的强度，才能获得一定数量的微纳尺度孪晶马氏体。目前还未见在一般大块体低合金碳钢中获得微纳尺度孪晶来实现强化和塑化的文献报道。It is difficult to prepare micro-nano-scale twins in steel by phase transformation. On the one hand, due to the high stacking fault energy of carbon steel, it is difficult to form deformation twins, and its deformation mechanism is mainly dislocation slip, so twins can only be obtained by phase transformation. However, the twins obtained through the martensitic transformation are relatively coarse, and do not contribute much to the strength but significantly reduce the ductility and plasticity. Therefore, it is necessary to first solve the problem of ultra-fine grains reaching 1-2 μm in order to ensure that the size of the twins formed subsequently is within Within 300nm. On the other hand, the strength of the austenite phase must be increased by other means in order to obtain a certain amount of micro-nano-scale twinned martensite. At present, there is no literature report on obtaining micro-nano-scale twins in general bulk low-alloy carbon steels to achieve strengthening and plasticization.
发明内容Contents of the invention
本发明的目的在于：提供一种中高碳铬钒钢中形成微纳尺度孪晶马氏体的工艺方法，以解决通过马氏体相变获得的孪晶比较粗大，对强度贡献不大反而显著降低韧塑性的问题。The purpose of the present invention is to provide a process for forming micro-nano-scale twinned martensite in medium-high carbon chromium-vanadium steel, so as to solve the problem that the twins obtained through martensitic transformation are relatively coarse and do not contribute much to strength but significantly The problem of reducing toughness and plasticity.
为解决上述问题，拟采用这样一种中高碳铬钒钢中形成微纳尺度孪晶马氏体的工艺方法，包括：In order to solve the above problems, it is proposed to adopt such a process method for forming micro-nano-scale twinned martensite in medium-high carbon chromium vanadium steel, including:
步骤一.选取中高碳铬钒钢，通过大功率感应加热方法对其加热，加热到790～830℃，保温时间为t，t为1～10秒，室温～500℃时的加热速率为200～300℃/s，500～830℃时的加热速率为800～1000℃/s；Step 1. Select medium-high carbon chromium-vanadium steel, heat it by high-power induction heating method, heat it to 790-830°C, hold time t, t is 1-10 seconds, and the heating rate is 200-200°C at room temperature-500°C 300℃/s, the heating rate at 500～830℃ is 800～1000℃/s;
步骤二.保温时间t后，对合金钢进行快速冷却，在830℃～400℃范围冷却速率＞300℃/s；400℃～室温范围冷却速率＞150℃/s；Step 2. After the holding time t, the alloy steel is rapidly cooled, and the cooling rate in the range of 830°C to 400°C is >300°C/s; the cooling rate in the range of 400°C to room temperature is >150°C/s;
步骤三.重复上述步骤一和步骤二的淬火工艺，获得微纳尺度孪晶马氏体。Step 3. Repeat the quenching process of the above step 1 and step 2 to obtain micro-nano scale twinned martensite.
前述工艺方法中，所选取的合金钢的成分和尺寸范围如下：元素含量(wt％)，C：0.45～0.55、Cr：0.8～1.4、V：0.08～0.14，其余为杂质含量，料径小于Φ16mm。In the aforementioned process method, the composition and size range of the selected alloy steel are as follows: element content (wt%), C: 0.45-0.55, Cr: 0.8-1.4, V: 0.08-0.14, the rest is impurity content, and the material diameter is less than Φ16mm.
前述工艺方法中，步骤一中选取合金钢后，先将其进行均匀化退火，然后去除表层杂质，避免杂质影响其加热速率和冷却速率；In the aforementioned process method, after the alloy steel is selected in step 1, it is first subjected to homogenization annealing, and then the impurities on the surface are removed, so as to prevent the impurities from affecting its heating rate and cooling rate;
前述工艺方法中，步骤三中，重复进行步骤一和步骤二的淬火工艺6次，获得最大密度的微纳尺度孪晶马氏体，经实验证实，重复进行步骤一和步骤二的淬火工艺6次时，合金中微纳尺度孪晶马氏体的含量最高。In the foregoing process method, in step three, the quenching process of step one and step two is repeated 6 times to obtain the maximum density of micro-nano scale twinned martensite. It is confirmed by experiments that the quenching process of step one and step two is repeated for 6 times At the second time, the content of micro-nano scale twinned martensite in the alloy is the highest.
与现有技术相比，本发明采用在接近临界点的低温区，通过快速加热过程具有一定回火效应，由于时间很短、温度低，回火不充分部分碳化物以及细化的尺寸在基体析出同时有部分溶解导致每个细化晶粒中都有局部的高碳区(碳含量大于0.7％以上)，然后快速冷却，这种过程重复几次后未溶解的碳化物量显著降低，晶粒显著细化，但同时又在每个晶粒局部保持不均匀的高碳浓度区。这种状态以超快速率冷却将能够获得一定数量的微纳尺度孪晶马氏体。由于这种类型钢的变形机制主要以位错的滑移为主，不会破坏孪晶的孪生关系，从而保证了其中所含的微纳尺度孪晶对材料宏观强度的贡献。另一方面塑性变形过程中位错与微纳尺度孪晶的反应和交互作用能有效释放形变应力导致材料塑性提高。因此这种方法可通过在大块体材料中获得微纳尺度孪晶马氏体来显著提高这类材料的强塑性，具有重要的实际应用价值。目前微纳尺度孪晶的密度只能在10％体积分数以内不算很高，已经可使这类材料的强度达到2000MPa以上，同时塑性指标(断面收缩率)可以获得45％左右，一旦本发明含高密度(大于15％体积分数)的纳米孪晶马氏体的钢铁材料推广应用，那将直接导致钢铁材料应用领域的革命性变化。Compared with the prior art, the present invention adopts the low-temperature region close to the critical point, and has a certain tempering effect through the rapid heating process. Due to the short time and low temperature, insufficient tempering and partial carbides and refined sizes are in the matrix Precipitation and partial dissolution lead to local high-carbon areas (carbon content greater than 0.7%) in each refined grain, and then rapid cooling. After this process is repeated several times, the amount of undissolved carbides is significantly reduced, and the grains Significantly refined, but at the same time maintain regions of high carbon concentration inhomogeneously locally within each grain. This state will be able to obtain a certain amount of micro-nano scale twinned martensite by cooling at an ultra-fast rate. Since the deformation mechanism of this type of steel is mainly based on the slip of dislocations, the twinning relationship of the twins will not be destroyed, thus ensuring the contribution of the micro-nano-scale twins contained in it to the macroscopic strength of the material. On the other hand, the reaction and interaction between dislocations and micro-nano-scale twins during plastic deformation can effectively release the deformation stress and lead to the improvement of material plasticity. Therefore, this method can significantly improve the strong plasticity of such materials by obtaining micro-nano scale twinned martensite in bulk materials, and has important practical application value. At present, the density of micro-nano-scale twins can only be considered very high within 10% volume fraction, which can make the strength of this type of material reach more than 2000MPa, and the plasticity index (reduction of area) can obtain about 45% at the same time, once the present invention The popularization and application of iron and steel materials containing high-density (greater than 15% volume fraction) nano-twinned martensite will directly lead to revolutionary changes in the application field of iron and steel materials.
具体实施方式Detailed ways
图1是本发明实施例的循环淬火工艺图；Fig. 1 is the circulation quenching process figure of the embodiment of the present invention;
图2是本发明实施例采用循环淬火工艺获得的超细化晶粒扫描电镜(SEM)图，图中1至6表示淬火1次至6次的试样；Fig. 2 is the scanning electron microscope (SEM) picture of the ultra-fine grain obtained by the cyclic quenching process in the embodiment of the present invention, 1 to 6 in the figure represent the samples quenched 1 to 6 times;
图3是本发明实施例制得的微纳尺度孪晶马氏体组织的透射电子显微镜(TEM)图和孪晶片层厚度示意图。Fig. 3 is a transmission electron microscope (TEM) image and a schematic diagram of the thickness of the twinned lamellar layer of the micro-nano scale twinned martensite structure prepared in the embodiment of the present invention.
具体实施方式Detailed ways
为使本发明的目的、技术方案和优点更加清楚，下面将对本发明作进一步地详细描述。In order to make the purpose, technical solution and advantages of the present invention clearer, the present invention will be further described in detail below.
实施例：Example:
中高碳铬、钒钢中形成微纳尺度孪晶马氏体的新工艺，其工艺如图1所示。A new process for forming micro-nano-scale twinned martensite in medium-high carbon chromium and vanadium steel, the process is shown in Figure 1.
第1步：将试样加工至合适尺寸，先将试样进行均匀化退火。然后人工去除试样表层的氧化膜等会影响其加热速率和冷却速率的杂质。Step 1: Process the sample to a suitable size, and first perform homogenization annealing on the sample. Then manually remove the oxide film on the surface of the sample and other impurities that will affect its heating rate and cooling rate.
第2步：按图1所示的工艺对钢进行循环淬火热处理。Step 2: Perform cyclic quenching heat treatment on the steel according to the process shown in Figure 1.
具体工艺规范如下：The specific process specifications are as follows:
参照图2和图3，通过上述循环淬火工艺，从细化晶粒、固溶强化和弥散强化三种强化方式强化钢奥氏体相，促进钢形成微纳尺度孪晶马氏体。循环淬火6次后，晶粒尺寸最细，晶粒度达到了16级，对钢的奥氏体相强化效果最佳，此时形成的孪晶马氏体密度也最大，孪晶所占面积与样品总面积的比值为6.78％，孪晶片层厚度在11.71nm左右。循环淬火+400℃×40min回火后，经6次淬火的试验钢的综合力学性能最佳，最高屈服强度、抗拉强度和断面收缩率分别达1792.93MPa、2036.2MPa和44％。Referring to Figure 2 and Figure 3, through the above-mentioned cyclic quenching process, the austenite phase of steel is strengthened from three strengthening methods of grain refinement, solid solution strengthening and dispersion strengthening, and the formation of micro-nano scale twin martensite in steel is promoted. After cyclic quenching for 6 times, the grain size is the smallest, and the grain size reaches 16 grades, which has the best effect on the austenite phase strengthening of steel. At this time, the density of twin martensite formed is also the largest, and the area occupied by twins The ratio to the total area of the sample is 6.78%, and the thickness of the twinned lamellar layer is about 11.71nm. After cyclic quenching + tempering at 400℃×40min, the comprehensive mechanical properties of the test steel quenched six times are the best, with the highest yield strength, tensile strength and reduction of area reaching 1792.93MPa, 2036.2MPa and 44%, respectively.
所述钢循环淬火1～6次的力学性能数据如表1所示：The mechanical property data of the cyclic quenching of the steel for 1 to 6 times are shown in Table 1:
表1 循环淬火1～6次的试验钢的力学性能Table 1 Mechanical properties of test steels subjected to cyclic quenching for 1 to 6 times
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| CN201610956866.9ACN106282495B (en) | 2016-10-27 | 2016-10-27 | The process of micro/nano-scale twin crystal martensite is formed in medium high carbon chrome-vanadium steel |
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| CN201610956866.9ACN106282495B (en) | 2016-10-27 | 2016-10-27 | The process of micro/nano-scale twin crystal martensite is formed in medium high carbon chrome-vanadium steel |
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| CN201610956866.9AActiveCN106282495B (en) | 2016-10-27 | 2016-10-27 | The process of micro/nano-scale twin crystal martensite is formed in medium high carbon chrome-vanadium steel |
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