技术领域technical field
本发明涉及形状记忆合金复合材料领域，特别是涉及一种致密和多孔形状记忆合金复合材料应力诱发马氏体相变临界点的确定方法。The invention relates to the field of shape memory alloy composite materials, in particular to a method for determining the stress-induced martensitic transformation critical point of dense and porous shape memory alloy composite materials.
背景技术Background technique
噪声振动、冲击破坏在很多领域，如航空航天，军事、交通运输、建筑等，普遍存在，且不可避免，这给各行各业带来了众多恶劣影响，甚至造成严重的后果。一方面影响设备的精度、寿命和可靠性，严重的可造成贵重设备丧失功能；另一方面恶化工作环境，危害人的健康和生命。目前噪声振动和冲击破坏防止领域的行业发展迅速，近几十年以来，越来越受到广泛关注，且市场需求都是逐年高速递增。而目前解决的最主要办法就是采用高阻尼材料实现减震吸能。特别是在一些高速列车、高速公路、城市建设、坦克装甲、潜艇等交通运输和国防领域的恶劣使用环境，要求阻尼材料具有高强度、较高的韧性和塑性、宽使用区间(-100～200℃)、耐腐蚀性和长寿命等特性，有机粘弹性材料由于其低熔点、低强度以及不可重复使用等缺点，已经不再适合在这些场合使用。目前主要使用的是高阻尼合金材料，主要有四大类：镁合金轻质高强，但耐腐蚀性较差，不可重复使用；铁磁型的合金价格低廉强度高，但受磁场影响严重，应用场合受到很大局限；复相型的灰铸铁和锌铝合金减震性能差，强度低，不适合高温使用。形状记忆合金(主要包括NiTi基、Cu基等)依靠其丰富的界面(马氏体变体和孪晶界面)运动的粘滞性吸能，高阻尼高强韧，且变形可恢复，并可重复使用。另外，将孔隙和第二相单一或同时引入形状记忆合金，可进一步大幅度提升其阻尼性能，这主要归因于孔壁的弯曲和坍塌也可耗散大量的能量，或者额外增加了第二相与形状记忆合金界面也可吸收能量。因此，这种高强高阻尼的形状记忆合金复合材料在减震抗噪、抗冲击领域有着巨大的应用前景。Noise, vibration, and impact damage are ubiquitous and inevitable in many fields, such as aerospace, military, transportation, construction, etc., which have brought many adverse effects to all walks of life, and even caused serious consequences. On the one hand, it affects the accuracy, life and reliability of the equipment, and in severe cases, it can cause loss of function of valuable equipment; on the other hand, it deteriorates the working environment and endangers people's health and life. At present, the industry in the field of noise vibration and impact damage prevention has developed rapidly. In recent decades, it has attracted more and more attention, and the market demand is increasing rapidly year by year. The most important way to solve at present is to adopt high damping materials to realize shock absorption and energy absorption. Especially in some high-speed trains, highways, urban construction, tank armor, submarines and other harsh environments in the fields of transportation and national defense, damping materials are required to have high strength, high toughness and plasticity, and a wide range of use (-100 to 200 ℃), corrosion resistance and long life, organic viscoelastic materials are no longer suitable for use in these occasions due to their shortcomings such as low melting point, low strength and non-reusable. At present, high-damping alloy materials are mainly used, and there are four main categories: magnesium alloys are light in weight and high in strength, but have poor corrosion resistance and cannot be reused; ferromagnetic alloys are cheap and high in strength, but are seriously affected by magnetic fields. The occasion is greatly limited; the complex-phase gray cast iron and zinc-aluminum alloy have poor shock absorption performance and low strength, and are not suitable for high temperature use. Shape memory alloys (mainly including NiTi-based, Cu-based, etc.) rely on the viscous energy absorption of their rich interface (martensite modification and twin interface) movement, high damping, high strength and toughness, and the deformation can be recovered and repeated use. In addition, the single or simultaneous introduction of pores and second phases into shape memory alloys can further greatly improve its damping performance, which is mainly due to the fact that the bending and collapse of the pore walls can also dissipate a large amount of energy, or additionally increase the second phase. The phase and shape memory alloy interface can also absorb energy. Therefore, this high-strength and high-damping shape memory alloy composite material has great application prospects in the fields of shock absorption, noise resistance and impact resistance.
然而，这种形状记忆合金阻尼材料的高阻尼特性和长寿命受温度影响巨大，这主要因为高温时，诸如NiTi形状记忆合金在高于马氏体逆相变结束温度Af(一般不超过100℃)，形状记忆合金处于母相状态，丧失低温马氏体状态中丰富的界面结构，从而阻尼性能变得非常差，甚至变成一种普通的材料。形状记忆合金在高于马氏体逆相变结束温度Af时，可通过一定应力诱发母相转变为马氏体相，从而恢复其高阻尼特性，卸载应力后可实现重复使用。为了实现形状记忆合金阻尼材料在高温下的使用，需要确定出应力诱发马氏体的临界点。However, the high damping characteristics and long life of this shape memory alloy damping material are greatly affected by temperature, which is mainly because at high temperature, the shape memory alloy such as NiTi is higher than the end temperature Af of the reverse martensitic transformation (generally not more than 100 ℃), the shape memory alloy is in the parent phase state, and loses the rich interface structure in the low-temperature martensitic state, so that the damping performance becomes very poor, and even becomes a common material. When the shape memory alloy is higher than the end temperature Af of the reverse martensitic transformation, the parent phase can be induced by a certain stress to transform into the martensitic phase, thereby restoring its high damping characteristics, and can be reused after unloading the stress. In order to realize the use of shape memory alloy damping materials at high temperature, it is necessary to determine the critical point of stress-induced martensite.
对于致密形状记忆合金的应力诱发马氏体的临界应力或应变，一般是通过材料测试系统进行拉伸或压缩实验，得到应力-应变曲线上会出现明显的应力诱发马氏体平台区，从弹性变形阶段到平台区，有一个明显的拐点，即为应力诱发马氏体的临界应力，对应的应变值即为应力诱发马氏体的临界应变。然而，对于多孔形状记忆合金或形状记忆复合材料，测试的应力-应变曲线没有明显的应力诱发马氏体平台区，因此很难采用这种方法确定出应力诱发马氏体的临界点。因此，有报道采用高能X射线原位测试应力的加载过程，也可以分析得出应力诱发马氏体的临界点。但是，这种方法测试费用昂贵，需要用到高能X射线源，且设备稀少，操作复杂。能否采用其他普通设备，简易方法确定出多孔形状记忆合金或形状记忆合金复合材料的临界点，这将会具有重要的应用价值。For the critical stress or strain of stress-induced martensite in dense shape memory alloys, tensile or compression experiments are generally carried out through material testing systems, and there will be obvious stress-induced martensite plateaus on the stress-strain curve, from the elastic From the deformation stage to the plateau region, there is an obvious inflection point, which is the critical stress of stress-induced martensite, and the corresponding strain value is the critical strain of stress-induced martensite. However, for porous shape memory alloys or shape memory composites, the tested stress-strain curves have no obvious stress-induced martensite plateau region, so it is difficult to determine the critical point of stress-induced martensite using this method. Therefore, it has been reported that high-energy X-rays are used to test the stress loading process in situ, and the critical point of stress-induced martensite can also be analyzed. However, this method is expensive to test, requires the use of high-energy X-ray sources, and the equipment is scarce and the operation is complicated. Whether other common equipment can be used to determine the critical point of porous shape memory alloy or shape memory alloy composite material in a simple way will have important application value.
发明内容Contents of the invention
为了克服现有方法的缺点与不足，本发明的目的在于提供一种方法可靠、快捷，精确度高，成本低的确定形状记忆合金复合阻尼材料应力诱发马氏体相变临界点的方法。In order to overcome the shortcomings and deficiencies of the existing methods, the object of the present invention is to provide a method for determining the stress-induced martensitic transformation critical point of the shape memory alloy composite damping material with reliable, fast, high precision and low cost.
本发明可以直观地反应出形状记忆合金复合阻尼材料细微的组织结构变化，准确测量出临界相变点；对于致密形状记忆合金，多孔形状记忆合金，形状记忆合金复合材料都适用。The invention can intuitively reflect the subtle structural changes of the shape memory alloy composite damping material and accurately measure the critical phase transition point; it is suitable for compact shape memory alloys, porous shape memory alloys and shape memory alloy composite materials.
本发明的目的通过以下技术方案实现：The object of the present invention is achieved through the following technical solutions:
确定形状记忆合金复合阻尼材料应力诱发马氏体相变临界点的方法，包括以下步骤：The method for determining the stress-induced martensitic transformation critical point of a shape memory alloy composite damping material comprises the following steps:
(1)采用差热式扫描热分析方法(DSC，differential scanning calorimeter)确定样品的马氏体逆相变结束温度Af；(1) Determine the end temperatureAf of the reverse martensitic transformation of the sample by using a differential scanning thermal analysis method (DSC, differential scanning calorimeter);
(2)采用动态机械分析仪(DMA，Dynamic Mechanical Analysis)在高于马氏体逆相变结束温度Af测量出样品的内耗-应变谱；(2) Using a dynamic mechanical analyzer (DMA, Dynamic Mechanical Analysis) to measure the internal friction-strain spectrum of the sample at a temperature higher than the end temperatureAf of the inverse martensitic transformation;
(3)采用切线法分析出步骤(2)获得内耗-应变谱中内耗显著增加的临界点，即为形状记忆合金复合阻尼材料的应力诱发马氏体相变临界点，所对应的应变为应力诱发马氏体相变的临界应变。(3) Use the tangent method to analyze the critical point at which the internal friction increases significantly in the internal friction-strain spectrum obtained in step (2), which is the stress-induced martensitic transformation critical point of the shape memory alloy composite damping material, and the corresponding strain is the stress Critical strain for inducing martensitic transformation.
为进一步实现本发明目的，优选地，步骤(1)所述差热式扫描热分析方法所采用的升温速率为1～20℃/min，确定马氏体逆相变结束温度Af的方法为切线法。In order to further realize the object of the present invention, preferably, the heating rate adopted by the differential thermal scanning thermal analysis method in step (1) is 1 to 20°C/min, and the method for determining the end temperatureAf of the reverse martensitic transformation is as follows: tangent method.
优选地，步骤(2)所述动态机械分析仪采用的测试模式是多重应变扫描模式(Strain-sweep)，采用的夹具为双悬臂梁或单悬臂梁。Preferably, the test mode adopted by the dynamic mechanical analyzer in step (2) is a multiple strain-sweep mode (Strain-sweep), and the used fixture is a double cantilever beam or a single cantilever beam.
优选地，步骤(2)所述动态机械分析仪所设定的最大应变幅度为1.5～2.2％，设定的频率为0.1～200Hz。Preferably, the maximum strain range set by the dynamic mechanical analyzer in step (2) is 1.5-2.2%, and the set frequency is 0.1-200 Hz.
优选地，步骤(2)所述高于马氏体逆相变结束温度Af为马氏体逆相变结束温度Af以上5～50℃。Preferably, the higher than the end temperature Af of the reverse martensitic transformation in step (2) is 5-50° C. above the end temperature Af of the reverse martensitic transformation.
优选地，步骤(2)所述样品采用线切割制得，厚度为1～2mm，依次用800#、1500#、3000#、5000#砂纸把样品各个表面打磨干净，接着采用无水乙醇超声波清洗5～15分钟，吹干后放在干燥箱里烘干24～48h。Preferably, the sample described in step (2) is obtained by wire cutting, with a thickness of 1-2mm, and the surfaces of the sample are polished with 800#, 1500#, 3000#, 5000# sandpaper in sequence, and then ultrasonically cleaned with absolute ethanol 5 to 15 minutes, blow dry and dry in a drying oven for 24 to 48 hours.
本发明的原理是：本发明发现样品稳定在奥氏体状态时，在DMA上对样品逐渐增大应变，可以得到内耗-应变谱，通过分析内耗值显著变化的部分，从而可以确定出诱发马氏体相变的临界应变。其中，动态热机械分析仪(DMA)是测量样品在周期振动应力下，随温度、频率或应变变化的力学性能和粘弹性能的仪器。DMA测试主要针对固体样品，施加力的方式以拉伸和弯曲为主。待测样品置于夹具上，仪器运行后测出动态过程中相应的力和振幅，通过一定的数学关系和参数运算可以得到动态变化过程中实时的应力、应变、模量、相位角和内耗等数据，从而可以分析出样品性能随外界条件的响应。DMA测试方法不损伤样品、无污染、快捷、精确度高、能得到有关样品完整性的大量信息等优点。The principle of the present invention is: the present invention finds that when the sample is stable in the austenitic state, the strain on the sample is gradually increased on the DMA, and the internal friction-strain spectrum can be obtained, and the induced horsepower can be determined by analyzing the part where the internal friction value changes significantly. The critical strain for the transformation. Among them, the Dynamic Thermomechanical Analyzer (DMA) is an instrument for measuring the mechanical properties and viscoelastic properties of samples that vary with temperature, frequency or strain under periodic vibration stress. The DMA test is mainly aimed at solid samples, and the methods of applying force are mainly stretching and bending. The sample to be tested is placed on the fixture, and the corresponding force and amplitude in the dynamic process are measured after the instrument is running. Through certain mathematical relationships and parameter calculations, real-time stress, strain, modulus, phase angle and internal friction during the dynamic change process can be obtained. Data, so that the response of sample performance to external conditions can be analyzed. The DMA test method has the advantages of no damage to the sample, no pollution, fast, high accuracy, and a large amount of information about the integrity of the sample can be obtained.
内耗是指材料在弹性范围内由于其内部各种微观因素的原因致使机械能逐渐转化成为材料内能的现象，是一个对材料的微观组织结构，比如界面、位错等十分敏感的物理参量。形状记忆合金在母相状态只有一些位错和晶界，其内耗值十分小；当应力诱发马氏体形成时，产生大量的孪晶界或马氏体变体之间界面等，从而导致内耗显著增加。可以通过分析应变过程中内耗值的明显变化进而反应出内部结构的细微变化，从而精确标定临界反应点。Internal friction refers to the phenomenon that the mechanical energy of the material is gradually converted into the internal energy of the material due to various internal microscopic factors within the elastic range. It is a physical parameter that is very sensitive to the microstructure of the material, such as interfaces and dislocations. The shape memory alloy has only some dislocations and grain boundaries in the parent phase state, and its internal friction value is very small; when the stress induces the formation of martensite, a large number of twin boundaries or interfaces between martensite variants are generated, resulting in internal friction A significant increase. The critical reaction point can be accurately calibrated by analyzing the obvious changes in the internal friction value during the strain process to reflect the subtle changes in the internal structure.
本发明工艺简单、可靠、成功率高。本发明的有益效果是：The process of the invention is simple, reliable and has a high success rate. The beneficial effects of the present invention are:
(1)本发明方法无损检测，快捷，精确度高，成本低；(1) The non-destructive testing method of the present invention is quick, high in accuracy and low in cost;
(2)本发明方法可以直观的反应出形状记忆合金复合阻尼材料细微的组织结构变化，准确获得临界相变点；对于致密形状记忆合金，多孔形状记忆合金，形状记忆合金复合材料都适用。(2) The method of the present invention can intuitively reflect the subtle structural changes of the shape memory alloy composite damping material, and accurately obtain the critical phase transition point; it is applicable to dense shape memory alloys, porous shape memory alloys, and shape memory alloy composite materials.
附图说明Description of drawings
图1是实施例1致密Ni50Ti50形状记忆合金阻尼材料的扫描电镜照片；Fig. 1 is the scanning electron micrograph of embodiment 1 compact Ni50 Ti50 shape memory alloy damping material;
图2是实施例1致密Ni50Ti50样品的DSC曲线；Fig. 2 is the DSC curve of embodiment 1 compact Ni50 Ti50 sample;
图3是实施例1致密Ni50Ti50样品在150℃，奥氏体状态下的内耗-应变谱；Fig. 3 is the internal friction-strain spectrum of the dense Ni50 Ti50 sample in Example 1 at 150°C in the austenitic state;
图4是实施例2致密Ni46Ti54形状记忆合金复合阻尼材料的扫描电镜照片；Fig. 4 is the scanning electron micrograph of embodiment 2 compact Ni46 Ti54 shape memory alloy composite damping material;
图5是实施例2致密Ni46Ti54样品的DSC曲线；Fig. 5 is the DSC curve of embodiment 2 compact Ni46 Ti54 sample;
图6是实施例2致密Ni46Ti54样品在奥氏体(130℃)状态下的内耗-应变谱；Fig. 6 is the internal friction-strain spectrum of the dense Ni46 Ti54 sample in the austenite (130°C) state of Example 2;
图7a是实施例3多孔Ni46Ti54形状记忆合金复合阻尼材料的金相照片；Fig. 7a is the metallographic photo of embodiment 3 porous Ni46 Ti54 shape memory alloy composite damping material;
图7b是实施例3多孔Ni46Ti54形状记忆合金复合阻尼材料的扫描电镜照片；Figure 7b is a scanning electron micrograph of the porous Ni46 Ti54 shape memory alloy composite damping material of Example 3;
图8是实施例3多孔Ni46Ti54样品的DSC曲线；Fig. 8 is the DSC curve of embodiment 3 porous Ni46 Ti54 samples;
图9是实施例3多孔Ni46Ti54样品在奥氏体(120℃)状态下的内耗-应变谱。Fig. 9 is the internal friction-strain spectrum of the porous Ni46 Ti54 sample in the austenite (120°C) state of Example 3.
具体实施方式detailed description
为更好地理解本发明，下面结合实施例及附图对本发明作进一步的描述，但本发明的实施方式不限于此。In order to better understand the present invention, the present invention will be further described below in conjunction with the examples and accompanying drawings, but the embodiments of the present invention are not limited thereto.
实施例1Example 1
以成分为Ni50Ti50的致密形状记忆合金阻尼材料为例，即该合金含有原子比为50％的Ni元素，50％的Ti元素，样品扫描电镜照片如图1所示，表面平整，由单一NiTi相组成。Take the dense shape memory alloy damping material with the composition of Ni50 Ti50 as an example, that is, the alloy contains 50% Ni element and 50% Ti element in atomic ratio. The scanning electron microscope photo of the sample is shown in Figure 1. Single NiTi phase composition.
确定形状记忆合金复合阻尼材料应力诱发马氏体相变临界点的方法，包括以下步骤：The method for determining the stress-induced martensitic transformation critical point of a shape memory alloy composite damping material comprises the following steps:
(1)采用差热式扫描热分析方法测出该致密Ni50Ti50形状记忆合金样品的DSC曲线，如图2所示，所采用的升温或降温速率为5℃/min，测试温度范围为-60～200℃，先将样品加热到200℃停留2分钟，然后以5℃/min速度冷却到-60℃，获得冷却曲线，即图2中上部的曲线，接着停留2分钟，然后以5℃/min速度升温到200℃，获得加热曲线，即图2中下部的曲线。冷却曲线出现一个明显的放热峰，加热曲线出现一个明显的吸热峰，表明样品随温度变化展现出明显的马氏体相变，冷却曲线表明样品由母相(B2相)完全转变成马氏体相(B19'相)，加热曲线表明样品由马氏体相完全转变母相，因此采用切线法可以确定马氏体逆相变结束温度Af为100℃；(1) The DSC curve of the dense Ni50 Ti50 shape memory alloy sample was measured by the differential thermal scanning thermal analysis method, as shown in Figure 2. The heating or cooling rate used was 5°C/min, and the test temperature range was -60～200°C, first heat the sample to 200°C for 2 minutes, then cool it to -60°C at a rate of 5°C/min to obtain the cooling curve, which is the upper curve in Figure 2, then stay for 2 minutes, and then cool at 5°C The temperature is raised to 200°C at a rate of °C/min, and the heating curve is obtained, which is the curve in the lower part of Figure 2. There is an obvious exothermic peak in the cooling curve, and an obvious endothermic peak in the heating curve, indicating that the sample exhibits obvious martensitic phase transformation with temperature changes, and the cooling curve shows that the sample is completely transformed from the parent phase (B2 phase) to martensitic phase. In the B19' phase, the heating curve shows that the sample is completely transformed from the martensite phase to the parent phase, so the tangent method can be used to determine the end temperature Af of the martensite reverse phase transformation to be 100 °C;
(2)将样品采用线切割制得，厚度为1mm，宽度为4mm，长度为30mm的薄片，依次用800#、1500#、3000#、5000#砂纸把样品各个表面打磨干净，厚度变为0.6mm，接着采用无水乙醇超声波清洗10分钟，吹干后放在干燥箱里烘干24h。采用动态机械分析仪在150℃(Af温度以上50℃)测量出该样品的内耗-应变谱，如图3所示，采用的测试模式是多重应变扫描模式(Strain-sweep)，采用的夹具为双悬臂梁，所设定的最大应变幅度为2.1％，测试频率为1Hz；图3体现样品内耗值随应变发生突变过程，这个突变是由于其微观结构发生变化所致。(2) The sample is made by wire cutting, with a thickness of 1mm, a width of 4mm, and a length of 30mm. The surface of the sample is polished with 800#, 1500#, 3000#, and 5000# sandpaper in sequence, and the thickness becomes 0.6 mm, followed by ultrasonic cleaning with anhydrous ethanol for 10 minutes, drying in a drying oven for 24 hours after drying. The internal friction-strain spectrum of the sample was measured at 150°C (50°C above theAf temperature) by a dynamic mechanical analyzer, as shown in Figure 3. The test mode used was the multiple strain sweep mode (Strain-sweep), and the fixture used It is a double cantilever beam, the set maximum strain range is 2.1%, and the test frequency is 1Hz; Figure 3 shows the mutation process of the internal friction value of the sample with the strain, which is caused by the change of its microstructure.
(3)采用切线法分析图3中内耗-应变谱中内耗显著增加的临界点，箭头所指应变为1.26％，即为致密NiTi形状记忆合金的应力诱发马氏体相变临界点，所对应的应变为应力诱发马氏体相变的临界应变。150℃(完全奥氏体状态)时测得该样品的阻尼系数随应变逐渐增大的响应曲体状态(测试温度维持在150℃时)，随着应变的逐渐增大，阻尼系数先是达到一个稳定的值(大约0.008左右)维持一段时间。而后达到一个临界点后，阻尼系数会突然增大，且随应变的逐渐增大而增大。根据形状记忆合金的相变特性，在奥氏体状态增大应力，会发生应力诱发马氏体相变，而马氏体孪晶界面及不同变体之间界面的移动等等，会显著增大阻尼系数。所以，从应变-内耗谱上可以准确确定应力诱发马氏体相变的临界应力(1.26％)。(3) Using the tangent method to analyze the critical point where the internal friction increases significantly in the internal friction-strain spectrum in Figure 3, the strain indicated by the arrow is 1.26%, which is the stress-induced martensitic transformation critical point of the dense NiTi shape memory alloy, corresponding to The strain is the critical strain for stress-induced martensitic transformation. At 150°C (full austenitic state), the damping coefficient of the sample is measured in response to the curved body state (when the test temperature is maintained at 150°C), and the damping coefficient first reaches a A stable value (around 0.008) is maintained for a period of time. After reaching a critical point, the damping coefficient will suddenly increase and increase with the gradual increase of strain. According to the phase transformation characteristics of shape memory alloys, when the stress is increased in the austenite state, the stress-induced martensite transformation will occur, and the movement of the martensitic twin interface and the interface between different variants will increase significantly. Large damping coefficient. Therefore, the critical stress (1.26%) of stress-induced martensitic transformation can be accurately determined from the strain-internal friction spectrum.
本实施例相对于高能X射线原位测试应力确定法，具有可靠、精确度高，成功率高的特点，主要是因为DMA测试方法，其测量的应变和内耗精度高，测量应变的精度可达到10-9，内耗值的精度可达到0.00001，且应变变化由计算机程序控制，稳定可靠，只要样品能够发生应变诱发马氏体，就能DMA方法测出。然而，高能X射线原位测试应力确定法，需要将高能X射线引入材料测试系统中，X射线对中样品需要由人操作，稳定性不好，且材料测试系统中，应变的精度只有0.0005，需要分析相结构，才能获得应力诱发马氏体的临界点，人为因素较多。Compared with the high-energy X-ray in-situ test stress determination method, this embodiment has the characteristics of reliability, high accuracy, and high success rate, mainly because the DMA test method has high precision in measuring strain and internal friction, and the accuracy of measuring strain can reach 10-9 , the accuracy of the internal friction value can reach 0.00001, and the strain change is controlled by a computer program, which is stable and reliable. As long as the sample can produce strain-induced martensite, it can be measured by the DMA method. However, the high-energy X-ray in-situ test stress determination method needs to introduce high-energy X-rays into the material testing system. The X-ray centering sample needs to be operated by a human, and the stability is not good. In the material testing system, the strain accuracy is only 0.0005. It is necessary to analyze the phase structure to obtain the critical point of stress-induced martensite, and there are many artificial factors.
实施例2Example 2
以成分为Ni46Ti54的致密形状记忆合金复合阻尼材料为例，即该合金含有原子比为46％的Ni元素，54％的Ti元素，该样品的微观结构为两相组成，半网状和颗粒状的Ti2Ni相，分布在NiTi基体相中，如图4所示，深色相为Ti2Ni相，浅色为NiTi相。Take the dense shape memory alloy composite damping material with the composition of Ni46 Ti54 as an example, that is, the alloy contains 46% Ni element and 54% Ti element in atomic ratio. The microstructure of this sample is composed of two phases, semi-network And the granular Ti2 Ni phase is distributed in the NiTi matrix phase, as shown in Figure 4, the dark phase is the Ti2 Ni phase, and the light color is the NiTi phase.
确定形状记忆合金复合阻尼材料应力诱发马氏体相变临界点的方法，包括以下步骤：The method for determining the stress-induced martensitic transformation critical point of a shape memory alloy composite damping material comprises the following steps:
(1)采用差热式扫描热分析方法测出该致密NiTi形状记忆合金样品的DSC曲线，如图5所示，所采用的升温或降温速率为10℃/min，测试温度范围为-60～200℃，先将样品加热到200℃停留2分钟，然后以10℃/min速度冷却到-60℃，获得冷却曲线，即图5中上部的曲线，接着停留2分钟，然后以10℃/min速度升温到200℃，获得加热曲线，即图5中下部的曲线。冷却曲线出现一个明显的放热峰，加热曲线出现一个明显的吸热峰，表明样品随温度变化展现出明显的马氏体相变，冷却曲线表明样品由母相(B2相)完全转变成马氏体相(B19'相)，加热曲线表明样品由马氏体相完全转变母相，因此采用切线法确定马氏体逆相变结束温度Af为103℃。(1) The DSC curve of the dense NiTi shape memory alloy sample was measured by the differential thermal scanning thermal analysis method, as shown in Figure 5, the heating or cooling rate used was 10°C/min, and the test temperature range was -60～ 200°C, first heat the sample to 200°C and stay for 2 minutes, then cool to -60°C at a rate of 10°C/min to obtain the cooling curve, which is the upper curve in Figure 5, then stay for 2 minutes, and then cool at 10°C/min Raise the temperature to 200°C to obtain a heating curve, that is, the lower curve in Fig. 5 . There is an obvious exothermic peak in the cooling curve, and an obvious endothermic peak in the heating curve, indicating that the sample exhibits obvious martensitic phase transformation with temperature changes, and the cooling curve shows that the sample is completely transformed from the parent phase (B2 phase) to martensitic phase. In the tensite phase (B19' phase), the heating curve shows that the sample completely transforms from the martensite phase to the parent phase, so the tangent method is used to determine the end temperatureAf of the reverse martensite transformation to be 103°C.
(2)将样品采用线切割制得，厚度为1mm，宽度为4mm，长度为30mm的薄片，依次用800#、1500#、3000#、5000#砂纸把样品各个表面打磨干净，厚度变为0.6mm，接着采用无水乙醇超声波清洗15分钟，吹干后放在干燥箱里烘干30h。采用动态机械分析仪在130℃(马氏体逆相变结束温度Af温度以上27℃)测量出该样品的内耗-应变谱，如图6所示，采用的测试模式是多重应变扫描模式(Strain-sweep)，采用的夹具为双悬臂梁，所设定的最大应变幅度为2.1％，测试频率为10Hz；(2) The sample is made by wire cutting, with a thickness of 1mm, a width of 4mm, and a length of 30mm. The surface of the sample is polished with 800#, 1500#, 3000#, and 5000# sandpaper in sequence, and the thickness becomes 0.6 mm, followed by ultrasonic cleaning with anhydrous ethanol for 15 minutes, drying in a drying oven for 30 hours after drying. The internal friction-strain spectrum of the sample was measured by a dynamic mechanical analyzer at 130°C (27°C above the martensitic inverse transformation end temperature Af temperature), as shown in Figure 6, and the test mode used was the multiple strain scanning mode ( Strain-sweep), the fixture used is a double cantilever beam, the set maximum strain range is 2.1%, and the test frequency is 10Hz;
(3)采用切线法分析图6中内耗-应变谱中内耗显著增加的临界点，箭头所指应变为1.12％，即为致密NiTi形状记忆合金复合阻尼材料的应力诱发马氏体相变临界点，所对应的应变为应力诱发马氏体相变的临界应变。图6体现样品内耗值随应变发生突变过程，这个突变是由于其微观结构(应力诱发马氏体相变，导致马氏体变体间界面和孪晶界面增加)发生变化所致。这个样品采用一般材料测试系统没有明显的应力平台区，也无法确定出应力诱发马氏体临界点。(3) Using the tangent method to analyze the critical point where the internal friction increases significantly in the internal friction-strain spectrum in Figure 6, the strain indicated by the arrow is 1.12%, which is the stress-induced martensitic transformation critical point of the dense NiTi shape memory alloy composite damping material , the corresponding strain is the critical strain of stress-induced martensitic transformation. Figure 6 shows the mutation process of the internal friction value of the sample with strain. This mutation is due to the change of its microstructure (stress-induced martensitic transformation, which leads to the increase of the interface between martensite variants and the twin interface). This sample has no obvious stress plateau area using the general material testing system, and the stress-induced martensitic critical point cannot be determined.
在奥氏体状态(测试温度维持在130℃时)，随着应变的逐渐增大，阻尼系数先是达到一个稳定的值(大约0.01左右)维持一段时间。而后达到一个临界点后，阻尼系数会突然增大，且随应变的逐渐增大而增大。根据形状记忆合金的相变特性，在奥氏体状态增大应力，会发生应力诱发马氏体相变。而且由于Ti2Ni相和NiTi相之间弹性模量的差异，导致复合材料在承受应力时，会在Ti2Ni相周围产生一个附加的应力场，导致周围的NiTi相提前发生应力诱发马氏体相变，即临界应力点变小，该样品的临界应变为1.12％，比图3致密单相NiTi形状记忆合金减少0.14％，这种微小的改变都能被本发明方法所测量出。In the austenite state (when the test temperature is maintained at 130°C), as the strain increases gradually, the damping coefficient first reaches a stable value (about 0.01) for a period of time. After reaching a critical point, the damping coefficient will suddenly increase and increase with the gradual increase of strain. According to the phase transformation characteristics of shape memory alloys, stress-induced martensitic transformation will occur when the stress is increased in the austenite state. Moreover, due to the difference in elastic modulus between the Ti2 Ni phase and the NiTi phase, when the composite material is subjected to stress, an additional stress field will be generated around the Ti2 Ni phase, resulting in the stress-induced Martensite in the surrounding NiTi phase in advance. Bulk phase transformation, that is, the critical stress point becomes smaller. The critical strain of this sample is 1.12%, which is 0.14% lower than that of the dense single-phase NiTi shape memory alloy in Figure 3. This small change can be measured by the method of the present invention.
实施例3Example 3
以成分为Ni46Ti54的多孔形状记忆合金复合阻尼材料为例，即该合金含有原子比为46％的Ni元素，54％的Ti元素，该样品为多孔材料，孔隙率为37％，孔隙大小为200μm左右，图7a是本实施例多孔Ni46Ti54形状记忆合金复合阻尼材料的金相照片；图7b是本实施例多孔Ni46Ti54形状记忆合金复合阻尼材料的扫描电镜照片；如图7a所示，其微观结构为两相组成，颗粒状的Ti2Ni相，分布在NiTi基体相中，如图7b所示，深色相为Ti2Ni相，浅色为NiTi相，表明该样品中既有许多孔隙表面，也增加了第二相与基体的界面，这都有助于增加记忆合金复合材料的阻尼性能。Take the porous shape memory alloy composite damping material with the composition of Ni46 Ti54 as an example, that is, the alloy contains 46% Ni element and 54% Ti element in atomic ratio. The sample is a porous material with a porosity of 37%. The size is about 200 μm. Figure 7a is a metallographic photo of the porous Ni46 Ti54 shape memory alloy composite damping material of this embodiment; Figure 7b is a scanning electron microscope photo of the porous Ni46 Ti54 shape memory alloy composite damping material of this embodiment; As shown in Figure 7a, its microstructure is composed of two phases, the granular Ti2 Ni phase is distributed in the NiTi matrix phase, as shown in Figure 7b, the dark phase is the Ti2 Ni phase, and the light color is the NiTi phase, indicating that There are not only many pore surfaces in this sample, but also the interface between the second phase and the matrix is increased, which all help to increase the damping performance of the memory alloy composite.
确定形状记忆合金复合阻尼材料应力诱发马氏体相变临界点的方法，包括以下步骤：The method for determining the stress-induced martensitic transformation critical point of a shape memory alloy composite damping material comprises the following steps:
(1)采用差热式扫描热分析方法测出该致密NiTi形状记忆合金样品的DSC曲线，如图8所示，所采用的升温速率为5℃/min，测试温度范围为-60～200℃，先将样品加热到200℃停留2分钟，然后以5℃/min速度冷却到-60℃，获得冷却曲线，即图8中上部的曲线，接着停留2分钟，然后以10℃/min速度升温到200℃，获得加热曲线，即图8中下部的曲线。冷却曲线出现一个明显的放热峰，加热曲线出现一个明显的吸热峰，表明样品随温度变化展现出明显的马氏体相变，冷却曲线表明样品由母相(B2相)完全转变成马氏体相(B19'相)，加热曲线表明样品由马氏体相完全转变母相，因此采用切线法确定马氏体逆相变结束温度Af为103℃。(1) The DSC curve of the dense NiTi shape memory alloy sample was measured by the differential thermal scanning thermal analysis method, as shown in Figure 8, the heating rate used was 5°C/min, and the test temperature range was -60 to 200°C , first heat the sample to 200°C and stay for 2 minutes, then cool to -60°C at a rate of 5°C/min to obtain the cooling curve, which is the upper curve in Figure 8, then stay for 2 minutes, and then heat up at a rate of 10°C/min Up to 200° C., a heating curve is obtained, namely the lower curve in FIG. 8 . There is an obvious exothermic peak in the cooling curve, and an obvious endothermic peak in the heating curve, indicating that the sample exhibits obvious martensitic phase transformation with temperature changes, and the cooling curve shows that the sample is completely transformed from the parent phase (B2 phase) to martensitic phase. In the tensite phase (B19' phase), the heating curve shows that the sample completely transforms from the martensite phase to the parent phase, so the tangent method is used to determine the end temperatureAf of the reverse martensite transformation to be 103°C.
(2)将待测试样品采用线切割制得，厚度为2mm，宽度为4mm，长度为20mm的薄片，依次用800#、1500#、3000#、5000#砂纸把样品各个表面打磨干净，厚度变为1.5mm，接着采用无水乙醇超声波清洗5分钟，吹干后放在干燥箱里烘干48h。采用动态机械分析仪在120℃(马氏体逆相变结束温度Af以上17℃)测量出该样品的内耗-应变谱，如图9所示，采用的测试模式是多重应变扫描模式(Strain-sweep)，采用的夹具为单悬臂梁，所设定的最大应变幅度为1.9％，测试频率为5Hz。(2) The sample to be tested is obtained by wire cutting, with a thickness of 2mm, a width of 4mm, and a length of 20mm. Use 800#, 1500#, 3000#, 5000# sandpaper to polish each surface of the sample, and the thickness becomes 1.5mm, followed by ultrasonic cleaning with anhydrous ethanol for 5 minutes, drying in a drying oven for 48 hours after drying. The internal friction-strain spectrum of the sample was measured by a dynamic mechanical analyzer at 120°C (17°C above the end temperatureAf of the inverse martensitic transformation), as shown in Figure 9, and the test mode used was the multiple strain scanning mode (Strain -sweep), the fixture used is a single cantilever beam, the set maximum strain range is 1.9%, and the test frequency is 5Hz.
(3)采用切线法分析图9中内耗-应变谱中内耗显著增加的临界点，箭头所指应变为0.6％，即为多孔NiTi形状记忆合金复合阻尼材料的应力诱发马氏体相变临界点，所对应的应变为应力诱发马氏体相变的临界应变。图9体现样品内耗值随应变发生突变过程，这个突变是由于其微观结构(应力诱发马氏体相变，导致马氏体变体间界面和孪晶界面增加)发生变化所致。这个样品采用一般材料测试系统没有明显的应力平台区，也无法确定出应力诱发马氏体临界点。(3) Using the tangent method to analyze the critical point where the internal friction increases significantly in the internal friction-strain spectrum in Figure 9, the strain indicated by the arrow is 0.6%, which is the stress-induced martensitic phase transformation critical point of the porous NiTi shape memory alloy composite damping material , the corresponding strain is the critical strain of stress-induced martensitic transformation. Figure 9 shows the mutation process of the internal friction value of the sample with strain, which is caused by the change of its microstructure (stress-induced martensitic transformation, resulting in the increase of the interface between martensite variants and the twin interface). This sample has no obvious stress plateau area using the general material testing system, and the stress-induced martensitic critical point cannot be determined.
在奥氏体状态(测试温度维持在150℃时)，随着应变的逐渐增大，阻尼系数先是达到一个稳定的值(大约0.015左右)维持一段时间。而后达到一个临界点后，阻尼系数会突然增大，且随应变的逐渐增大而增大。根据记忆合金的相变特性，在奥氏体状态增大应力，会发生应力诱发马氏体相变。而且由于Ti2Ni相和NiTi相之间弹性模量，以及孔隙与NiTi相之间弹性模量的显著的差异，导致多孔复合材料在承受应力时，会在Ti2Ni相和孔隙周围产生一个附加的巨大应力场，导致周围的NiTi相提前发生应力诱发马氏体相变，即临界应力点显著变小，该样品的临界应变为0.6％，比图3致密单相NiTi形状记忆合金和图6致密双相NiTi形状记忆合金复合材料都要小很多，且这种改变都能被本发明的方法所测量出。In the austenite state (when the test temperature is maintained at 150°C), as the strain increases gradually, the damping coefficient first reaches a stable value (about 0.015) for a period of time. After reaching a critical point, the damping coefficient will suddenly increase and increase with the gradual increase of strain. According to the phase transformation characteristics of the memory alloy, stress-induced martensitic transformation will occur when the stress is increased in the austenite state. Moreover, due to the significant difference in the elastic modulus between the Ti2 Ni phase and the NiTi phase, as well as between the pores and the NiTi phase, when the porous composite is subjected to stress, a gap will be formed around the Ti2 Ni phase and the pores. The additional huge stress field causes the surrounding NiTi phase to undergo stress-induced martensitic transformation in advance, that is, the critical stress point becomes significantly smaller. The critical strain of this sample is 0.6%, which is denser than that of the single-phase NiTi shape memory alloy in Fig. 3 and Fig. 6. The dense dual-phase NiTi shape memory alloy composite materials are much smaller, and this change can be measured by the method of the present invention.
本发明的实施方式并不受所述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。The embodiments of the present invention are not limited by the examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods. Included within the protection scope of the present invention.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610831405.9ACN106404656A (en) | 2016-09-18 | 2016-09-18 | Method for determining stress-induced martensitic transformation critical point of shape memory alloy composite damping material |
| Application Number | Priority Date | Filing Date | Title |
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| CN201610831405.9ACN106404656A (en) | 2016-09-18 | 2016-09-18 | Method for determining stress-induced martensitic transformation critical point of shape memory alloy composite damping material |
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| CN106404656Atrue CN106404656A (en) | 2017-02-15 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610831405.9APendingCN106404656A (en) | 2016-09-18 | 2016-09-18 | Method for determining stress-induced martensitic transformation critical point of shape memory alloy composite damping material |
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| CN (1) | CN106404656A (en) |
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| CN107991179A (en)* | 2017-11-03 | 2018-05-04 | 合肥通用机械研究院 | A kind of method for measuring strain inducing martensitic traoformation kinetic curve |
| CN113484469A (en)* | 2021-06-30 | 2021-10-08 | 中国科学院青海盐湖研究所 | In-situ characterization method for nano-scale phase separation of phase change energy storage material of hydrated salt system |
| CN114352239A (en)* | 2021-12-17 | 2022-04-15 | 华南理工大学 | Ultra-high strain recovery shape memory alloy screen material and preparation method and application |
| CN114734207A (en)* | 2022-04-14 | 2022-07-12 | 山东大学 | NiTi alloy surface cutting process and roughness adjusting method |
| CN119851827A (en)* | 2024-12-27 | 2025-04-18 | 西安交通大学 | Phase-change refrigeration material performance prediction method and related device |
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| JP2002356747A (en)* | 2001-03-28 | 2002-12-13 | Kobe Steel Ltd | Steel product with excellent toughness |
| CN1766593A (en)* | 2005-10-14 | 2006-05-03 | 沈阳理工大学 | Determination method of thermal shock temperature of titanium nickel base shape memory alloy |
| US20060257773A1 (en)* | 2005-05-11 | 2006-11-16 | Xerox Corporation | Polyalkylene materials |
| CN103163172A (en)* | 2011-12-19 | 2013-06-19 | 中国科学院金属研究所 | Testing method of shape memory alloy transient damping |
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| JP2002356747A (en)* | 2001-03-28 | 2002-12-13 | Kobe Steel Ltd | Steel product with excellent toughness |
| US20060257773A1 (en)* | 2005-05-11 | 2006-11-16 | Xerox Corporation | Polyalkylene materials |
| CN1766593A (en)* | 2005-10-14 | 2006-05-03 | 沈阳理工大学 | Determination method of thermal shock temperature of titanium nickel base shape memory alloy |
| CN103163172A (en)* | 2011-12-19 | 2013-06-19 | 中国科学院金属研究所 | Testing method of shape memory alloy transient damping |
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| CHEN CHIEN ET AL.: "Damping Capacities of Ti50Ni50-xCux Shape Memory Alloys Measured under Temperature, Strain, and Frequency Sweeps", 《MATERIALS TRANSACTIONS》* |
| SHIH-HANG CHANGE ET AL.: "Damping Characteristics of the Inherent and Intrinsic Internal Friction of Ti50Ni50-xFex (x=2, 3, and 4) Shape Memory Alloys", 《MATERIALS TRANSACTIONS》* |
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| CN107991179A (en)* | 2017-11-03 | 2018-05-04 | 合肥通用机械研究院 | A kind of method for measuring strain inducing martensitic traoformation kinetic curve |
| CN113484469A (en)* | 2021-06-30 | 2021-10-08 | 中国科学院青海盐湖研究所 | In-situ characterization method for nano-scale phase separation of phase change energy storage material of hydrated salt system |
| CN114352239A (en)* | 2021-12-17 | 2022-04-15 | 华南理工大学 | Ultra-high strain recovery shape memory alloy screen material and preparation method and application |
| CN114734207A (en)* | 2022-04-14 | 2022-07-12 | 山东大学 | NiTi alloy surface cutting process and roughness adjusting method |
| US11964337B2 (en) | 2022-04-14 | 2024-04-23 | Shandong University | NiTi alloy surface cutting process and roughness adjustment method |
| CN119851827A (en)* | 2024-12-27 | 2025-04-18 | 西安交通大学 | Phase-change refrigeration material performance prediction method and related device |
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| CN106404656A (en) | Method for determining stress-induced martensitic transformation critical point of shape memory alloy composite damping material | |
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| RJ01 | Rejection of invention patent application after publication | Application publication date:20170215 |