技术领域Technical Field
本发明涉及金属基复合材料领域，具体涉及一种多层次纳米颗粒增强的高强韧钛基复合材料的制备方法，是一种多层次纳米颗粒增强钛基复合材料强韧化方法。The invention relates to the field of metal-based composite materials, and in particular to a method for preparing a multi-level nanoparticle-reinforced high-strength and tough titanium-based composite material, which is a method for strengthening and toughening a multi-level nanoparticle-reinforced titanium-based composite material.
背景技术Background technique
钛基复合材料具有密度低、比强度高、耐腐蚀性能好、抗氧化等优异性能逐渐成为汽车、航空航天等高科技领域最有潜力的候选结构材料之一。通过在钛合金基体中引入如TiB、TiC、Re2O3等高强高模的陶瓷颗粒并优化其尺度和分布，可显著提高钛基复合材料的模量、耐磨性和高温抗氧化性，是目前是提高钛基复合材料综合力学性能和服役温度的有效途径之一。Titanium-based composites have low density, high specific strength, good corrosion resistance, and oxidation resistance, and have gradually become one of the most promising candidate structural materials in high-tech fields such as automobiles and aerospace. By introducing high-strength and high-modulus ceramic particles such as TiB, TiC, and Re2 O3 into the titanium alloy matrix and optimizing their size and distribution, the modulus, wear resistance, and high-temperature oxidation resistance of titanium-based composites can be significantly improved. This is currently one of the effective ways to improve the comprehensive mechanical properties and service temperature of titanium-based composites.
粉末冶金是制备钛基复合材料的一种净成形方法，与其它基于液相反应的钛基复合材料制备技术相比，该方法具有更强的可控性与可设计性，通过对粉末结构与铺粉工艺的设计，实现对增强体尺寸和分布的调控，构筑“核壳结构”、“层状结构”、“网状结构”等，充分发挥增强体与构型协同强韧化的效果，能够大幅提高复合材料的综合性能，在航空航天、工业、医疗等领域都已有较多的应用。Powder metallurgy is a net forming method for preparing titanium-based composite materials. Compared with other titanium-based composite material preparation technologies based on liquid phase reactions, this method has stronger controllability and designability. By designing the powder structure and powder laying process, the size and distribution of the reinforcement can be regulated, and a "core-shell structure", "layered structure", "network structure" and so on can be constructed. The synergistic strengthening and toughening effect of the reinforcement and the configuration can be fully utilized, which can greatly improve the comprehensive performance of the composite material. It has been widely used in aerospace, industry, medical and other fields.
国内外采用的粉末预处理方式主要包括球磨、静电吸附、流化床气相沉积等。即利用物理方法或化学法在钛合金表面嵌入或吸附增强体反应剂，而后在高温烧结过程中，在钛合金颗粒表面诱发原位反应，从而在颗粒边界自生各类增强体。然而，当增强体引入后，为确保原位反应充分进行并实现材料的致密化，往往需要在材料β相变点以上进行烧结。烧结温度的提高，不可避免地会促进基体晶粒的生长，从而形成包含粗大原始β晶粒的魏氏组织，降低材料的力学性能。为进一步提高复合材料的性能，往往需要在烧结后辅以锻造、轧制等二次热加工途径，大大延长了材料制备的流程，增加了生产成本。因此，如何采用简单有效的方法于高温下抑制基体晶粒长大，实现对基体组织与增强体尺寸分布的调控，从而提高烧结态材料的综合力学性能，已经成为研究者们关注的重点方向之一。The powder pretreatment methods used at home and abroad mainly include ball milling, electrostatic adsorption, fluidized bed vapor deposition, etc. That is, the reinforcement reactant is embedded or adsorbed on the surface of the titanium alloy by physical or chemical methods, and then in the high-temperature sintering process, the in-situ reaction is induced on the surface of the titanium alloy particles, so that various reinforcements are generated at the particle boundaries. However, after the reinforcement is introduced, in order to ensure that the in-situ reaction is fully carried out and the material is densified, it is often necessary to sinter above the β phase transition point of the material. The increase in sintering temperature will inevitably promote the growth of matrix grains, thereby forming a Widmanstätten structure containing coarse original β grains and reducing the mechanical properties of the material. In order to further improve the performance of composite materials, it is often necessary to supplement the sintering with secondary hot processing such as forging and rolling, which greatly prolongs the material preparation process and increases the production cost. Therefore, how to use a simple and effective method to inhibit the growth of matrix grains at high temperature, realize the regulation of matrix structure and reinforcement size distribution, and thus improve the comprehensive mechanical properties of sintered materials has become one of the key directions of researchers.
发明内容Summary of the invention
本发明的目的是针对现有技术中存在的问题，提供一种多层次纳米颗粒增强的高强韧钛基复合材料的制备方法。该方法通过筛选不同粒径具有超细网状结构钛基复合材料材料粉体，控制增强体及网状结构的初始尺度，在低温预压烧结过程中提高纳米增强体的稳定性。随后，在β相区致密化烧结材料成块体，通过工艺优化调控基体组织类型及增强体的尺寸及分布。最终，经随炉时效处理控制合金析出相分布，得到具有均匀细小组织，且纳米增强体呈晶界/晶内多层次分布的高强韧钛基复合材料；该方法解决了烧结温度过高造成钛合金组织粗大的问题，避免了粗大魏氏组织的形成，细化了基体晶粒及增强体尺寸，实现了增强体尺寸分布的精确调控，从而大幅提高了烧结态钛基复合材料的强韧性。该方法和技术有助于指导利用粉末冶金方法直接制备高强韧钛基复合材料及其构件，在航空航天等重大装备领域具有重要的应用价值。The purpose of the present invention is to provide a method for preparing a high-strength and tough titanium-based composite material reinforced with multi-level nanoparticles in view of the problems existing in the prior art. The method screens titanium-based composite material powders with ultrafine mesh structures of different particle sizes, controls the initial size of the reinforcement and the mesh structure, and improves the stability of the nano-reinforcement during low-temperature pre-pressing sintering. Subsequently, the sintered material is densified into a block in the β phase region, and the matrix organization type and the size and distribution of the reinforcement are regulated by process optimization. Finally, the distribution of the alloy precipitation phase is controlled by furnace aging treatment to obtain a high-strength and tough titanium-based composite material with uniform and fine organization and nano-reinforcement distributed in grain boundaries/intragranular layers; the method solves the problem of coarse titanium alloy organization caused by excessively high sintering temperature, avoids the formation of coarse Widmanstatten organization, refines the matrix grains and reinforcement size, and realizes precise regulation of reinforcement size distribution, thereby greatly improving the strength and toughness of the sintered titanium-based composite material. The method and technology are helpful to guide the direct preparation of high-strength and tough titanium-based composite materials and their components using powder metallurgy methods, and have important application value in major equipment fields such as aerospace.
本发明的目的可以通过以下方案来实现：The purpose of the present invention can be achieved by the following scheme:
本发明提供了一种多层次纳米颗粒增强的高强韧钛基复合材料的制备方法，所述制备方法包括以下步骤：The present invention provides a method for preparing a multi-level nanoparticle-reinforced high-strength and tough titanium-based composite material, the preparation method comprising the following steps:
A、筛选不同粒径的内嵌超细网状结构的钛基复合材料粉体；A. Screening titanium-based composite powders with embedded ultrafine mesh structures of different particle sizes;
B、将筛选后的钛基复合材料粉末加热至材料β相变温度(Tβ)以下20～200℃，进行预压烧结；B. heating the screened titanium-based composite material powder to 20 to 200° C. below the material β phase transition temperature (Tβ ) for pre-pressing and sintering;
C、将炉温上升至Tβ以上20～300℃进行致密化烧结；C. Raise the furnace temperature to 20-300°C above Tβ for densification sintering;
D、烧结后冷至材料设定的时效温度，进行时效处理，即得所述纳米增强体在基体中呈现晶界/晶内多层次分布的高强韧钛基复合材料。D. After sintering, the material is cooled to a set aging temperature and subjected to aging treatment, thereby obtaining a high-strength and tough titanium-based composite material in which the nano-reinforcement presents a multi-level distribution of grain boundaries/intra-grains in the matrix.
优选的，步骤A中所述的内嵌超细网状结构的钛基复合材料粉体包括钛基和增强体，且增强体在钛基中呈超细网状结构分布；基体包括纯钛及钛合金，增强体包括TiB、TiC、La2O3、Ti5Si3、(Ti，Zr)xSi3(x＝5～6)增强体中的一种或多种，优选TiB与其它增强体的组合。该粉体的制备技术为专利CN110340371A，该专利详细描述了粉体的制备方法。Preferably, the titanium-based composite material powder embedded with ultrafine mesh structure described in step A comprises a titanium matrix and a reinforcement, and the reinforcement is distributed in the titanium matrix in an ultrafine mesh structure; the matrix comprises pure titanium and titanium alloy, and the reinforcement comprises oneor more of TiB, TiC,La2O3 ,Ti5Si3 , (Ti, Zr)xSi3 (x =5-6) reinforcements, preferably a combination of TiB and other reinforcements. The preparation technology of the powder is patentCN110340371A , which describes the preparation method of the powder in detail.
优选的，步骤A中所述钛基复合材料粉体的粒径范围为15～53μm、53～100μm、100～150μm、150～225μm中的一种。粉体内增强体体积分数为1～5％，增强体均为纳米尺寸(直径或宽度＜100nm)，且呈超细网状结构分布。不同粒径的粉体内部网状结构的尺寸不同，一般网状结构尺寸会随增强体体积分数的提高以及粉体粒径的降低而减小，网状结构尺寸会明显减小，单个网格尺寸在2～10μm之间，对应烧结态材料中增强体的长径比和弥散程度越高。Preferably, the particle size range of the titanium-based composite material powder in step A is one of 15 to 53 μm, 53 to 100 μm, 100 to 150 μm, and 150 to 225 μm. The volume fraction of the reinforcement in the powder is 1 to 5%, and the reinforcements are all nanometer-sized (diameter or width <100 nm) and distributed in an ultrafine mesh structure. The size of the internal mesh structure of powders of different particle sizes is different. Generally, the size of the mesh structure will decrease with the increase of the volume fraction of the reinforcement and the decrease of the particle size of the powder. The size of the mesh structure will be significantly reduced. The size of a single grid is between 2 and 10 μm, and the higher the aspect ratio and dispersion of the reinforcement in the corresponding sintered material.
优选的，步骤B中所述预压烧结的方式包括热压烧结(HP)、热等静压烧结(HIP)、放电等离子烧结(SPS)中的一种。预压烧结温度范围为：β相变温度(Tβ)以下20～200℃，预压温度不超过900℃，压强范围为：50～300MPa，升温速率为：10℃～200℃/min，保温时间为：5～60min。Preferably, the pre-pressing sintering method in step B includes one of hot pressing sintering (HP), hot isostatic pressing sintering (HIP), and spark plasma sintering (SPS). The pre-pressing sintering temperature range is: 20 to 200°C below the β phase transition temperature (Tβ ), the pre-pressing temperature does not exceed 900°C, the pressure range is: 50 to 300MPa, the heating rate is: 10°C to 200°C/min, and the holding time is: 5 to 60min.
优选的，步骤C中所述致密化烧结的烧结温度范围为：β相变温度(Tβ)以上20～300℃，压强范围为：50～300MPa，升温速率为：10～200℃/min，保温时间为：5～240min。其中烧结方式包括：热压烧结(HP)，热等静压烧结(HIP)和放电等离子烧结(SPS)。一般烧结温度越低、升温速率越快、保温时间越短，材料中基体晶粒尺寸及增强体的尺寸约小，材料的强度越高。但烧结温度过低会导致材料致密性差，材料中存在明显的孔洞等缺陷。Preferably, the sintering temperature range of the densification sintering in step C is: 20-300°C above the β phase transition temperature (Tβ ), the pressure range is: 50-300MPa, the heating rate is: 10-200°C/min, and the holding time is: 5-240min. The sintering methods include: hot pressing sintering (HP), hot isostatic pressing sintering (HIP) and spark plasma sintering (SPS). Generally, the lower the sintering temperature, the faster the heating rate, and the shorter the holding time, the smaller the matrix grain size and the size of the reinforcement in the material, and the higher the strength of the material. However, if the sintering temperature is too low, the material will have poor density and obvious defects such as holes in the material.
优选的，步骤D中所述时效处理方式为随炉冷却至时效温度；时效温度为400～800℃之间，时效时间为0.5～8h。时效温度根据材料的不同控制Preferably, the aging treatment method in step D is to cool to the aging temperature with the furnace; the aging temperature is between 400 and 800°C, and the aging time is 0.5 to 8 hours. The aging temperature is controlled according to different materials.
优选的，步骤D中所述的高强韧钛基复合材料具有均匀细小的等轴或近片层组织、增强体为纳米尺度，且在基体中呈晶界/晶内多层次分布。且钛基复合材料的力学性能优异，其强塑性与同类钛基复合材料锻件相当。同时，晶粒及增强体尺寸和分布可以通过烧结温度、保温时间、粉体粒度进行调控，在不同工艺下，其等轴组织尺度范围为5～20μm，增强体尺度范围为100nm～2μm。Preferably, the high-strength and tough titanium-based composite material described in step D has a uniform and fine equiaxed or near-lamellar structure, a reinforcement of nanometer scale, and a multi-level distribution at grain boundaries/intragranular in the matrix. The titanium-based composite material has excellent mechanical properties, and its strength and plasticity are comparable to similar titanium-based composite forgings. At the same time, the size and distribution of grains and reinforcements can be regulated by sintering temperature, holding time, and powder particle size. Under different processes, the equiaxed structure scale ranges from 5 to 20 μm, and the reinforcement scale ranges from 100 nm to 2 μm.
优选的，高强韧钛基复合材料还可利用常规热加工技术(如锻造、挤压、轧制等)进行后处理。Preferably, the high-strength and toughness titanium-based composite material can also be post-processed using conventional hot processing techniques (such as forging, extrusion, rolling, etc.).
综上所述，与现有技术相比，本发明具有如下有益效果：In summary, compared with the prior art, the present invention has the following beneficial effects:
(1)本发明通过筛选不同粒径的钛基复合材料粉体，可以获得不同尺寸的超细网状结构，通过对粉体粒径的筛分获得不用尺寸的网状结构，达到调控超细网状结构的尺寸的目的。首先，粉体内的网状结构突破了传统混粉工艺仅能在粉体颗粒边界引入增强体的局限，同时细化了网状结构的尺寸与增强体的尺寸，保证了复合材料粉末内嵌纳米增强体的分布均匀性；其次，网状结构及增强体的尺寸随粉体粒径的增加而增大，通过粉体筛选可以直接控制增强体尺寸及网状结构尺寸。(1) The present invention can obtain ultrafine mesh structures of different sizes by screening titanium-based composite material powders of different particle sizes, and obtain mesh structures of different sizes by screening the powder particle size, thereby achieving the purpose of regulating the size of the ultrafine mesh structure. First, the mesh structure in the powder breaks through the limitation that the traditional powder mixing process can only introduce reinforcements at the boundaries of powder particles, and at the same time refines the size of the mesh structure and the size of the reinforcement, ensuring the uniformity of the distribution of nano-reinforcements embedded in the composite material powder; secondly, the size of the mesh structure and the reinforcement increases with the increase of the powder particle size, and the size of the reinforcement and the mesh structure can be directly controlled by powder screening.
(2)在烧结过程中，由于粉体内部已经预先植入超细网状增强体，因此，增强体仅在高温下经历热扩散和长大过程，与传统机械混粉后通过原位反应引入增强体的方法具有本质区别，避免了机械混粉后增强体分布不均匀且容易引入杂质的问题。(2) During the sintering process, since the ultrafine mesh reinforcement has been pre-implanted inside the powder, the reinforcement only undergoes thermal diffusion and growth at high temperature. This is fundamentally different from the traditional method of introducing reinforcement through in-situ reaction after mechanical mixing of powders, and avoids the problem of uneven distribution of reinforcement and easy introduction of impurities after mechanical mixing of powders.
(3)纳米增强体的热稳定性较差，对于粉体中的纳米增强体而言，其热稳定性温度控制在900℃以下，通过预压烧结可以促进纳米增强体的稳定化，减少高温烧结过程中增强体的粗化。(3) The thermal stability of nano-reinforcements is poor. For nano-reinforcements in powder, their thermal stability temperature is controlled below 900°C. Pre-pressing and sintering can promote the stabilization of nano-reinforcements and reduce the coarsening of reinforcements during high-temperature sintering.
(4)本发明主要适用于温度在Tβ以上的烧结过程，只有当烧结温度高于材料β相变点时，粉体中预制的超细网状结构才能发挥明显的组织调控效果，在保证所得的材料具有较高的致密度的同时，显著细化晶粒，抑制了粗大魏氏组织的形成。同时，通过烧结工艺的优化，能够精准调控增强体在基体组织中的分布形式，使纳米增强体在基体中呈晶界/晶内多层次分布。(4) The present invention is mainly applicable to sintering processes at temperatures above Tβ. Only when the sintering temperature is higher than the β phase transition point of the material, the prefabricated ultrafine mesh structure in the powder can play a significant organizational control effect, while ensuring that the obtained material has a high density, the grains are significantly refined, and the formation of coarse Widmanstatten structure is inhibited. At the same time, through the optimization of the sintering process, the distribution form of the reinforcement in the matrix organization can be accurately controlled, so that the nano reinforcement is distributed in the matrix at multiple levels of grain boundaries/intragranularity.
(5)本发明利用粉末冶金法制备出的烧结态纳米颗粒增强钛基复合材料具有优异的力学性能，在不经过二次热变形加工的情况下，其强塑性可以与同类锻态钛基复合材料相当；(5) The sintered nanoparticle-reinforced titanium-based composite material prepared by the powder metallurgy method of the present invention has excellent mechanical properties. Without secondary thermal deformation processing, its strength and plasticity are comparable to those of similar forged titanium-based composite materials;
(6)本发明适用于含有TiB的各类单元增强钛基复合材料，以及含有TiB增强体与其它增强体混杂增强的钛基复合材料，如TiB+TiC、TiB+Ti5Si3、TiB+La2O3及其他TiB+RexOy及TiB+TiC+RexOy等混杂增强系列；(6) The present invention is applicable to various unit-reinforced titanium-based composite materials containing TiB, and titanium-based composite materials containing TiB reinforcement and other reinforcements, such as TiB+TiC, TiB+Ti5 Si3 , TiB+La2 O3 and other TiB+Rex Oy and TiB+TiC+Rex Oy mixed reinforcement series;
(7)本发明适用于纯钛或钛合金基体，包括Ti-6Al-4V和IMI834等，适用范围广；(7) The present invention is applicable to pure titanium or titanium alloy substrates, including Ti-6Al-4V and IMI834, and has a wide range of applications;
(8)本发明适用于热压烧结，热等静压烧结，等离子放电烧结等多种在高温高压下，实现粉末成型的制备工艺体系；(8) The present invention is applicable to a variety of preparation process systems for achieving powder molding under high temperature and high pressure, such as hot pressing sintering, hot isostatic pressing sintering, and plasma discharge sintering;
(9)本发明在粉末中预制的超细网状结构在烧结时可有效阻碍晶粒长大，具有显著的细晶化效果，消除了由烧结温度过高导致材料组织粗大的问题。通过粉体改性制备的钛基复合材料微观组织，展现出均匀细小的等轴或近片层组织形貌，且增强体为纳米尺度，且在基体中呈晶界/晶内多层次分布，能够充分发挥增强体的协同强化效果。相较于同工艺下制备的合金及其它复合材料，组织得到了明显的优化，所制备的复合材料无各向异性，组织均匀且力学性能优异。(9) The ultrafine mesh structure prefabricated in the powder of the present invention can effectively hinder the growth of grains during sintering, has a significant refinement effect, and eliminates the problem of coarse material structure caused by excessive sintering temperature. The microstructure of the titanium-based composite material prepared by powder modification shows a uniform and fine equiaxed or near-lamellar structure morphology, and the reinforcement is nanoscale and distributed in the matrix at multiple levels of grain boundaries/intragranularity, which can give full play to the synergistic strengthening effect of the reinforcement. Compared with alloys and other composite materials prepared under the same process, the organization has been significantly optimized, and the prepared composite material has no anisotropy, uniform organization and excellent mechanical properties.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
通过阅读参照以下附图对非限制性实施例所作的详细描述，本发明的其它特征、目的和优点将会变得更明显：Other features, objects and advantages of the present invention will become more apparent from the detailed description of non-limiting embodiments made with reference to the following drawings:
图1为实施例1采用气雾化法制备的1.2vol.％TiB+La2O3/IMI834耐热钛基复合材料粉末剖面组织图；其中a为粉体表面形貌，b为粉体截面组织特征；FIG1 is a cross-sectional microstructure diagram of a 1.2 vol.% TiB+La2 O3 /IMI834 heat-resistant titanium-based composite material powder prepared by gas atomization in Example 1; a is the surface morphology of the powder, and b is the microstructure feature of the powder cross section;
图2为实施例1制备的1.2vol.％TiB+La2O3/IMI834钛基复合材料微观组织形貌图(a)和实施例2制备的2.4vol.％TiB+La2O3增/IMI834钛基复合材料微观组织形貌图(b)；FIG2 is a microstructure morphology of a 1.2 vol.% TiB+La2 O3 /IMI834 titanium-based composite material prepared in Example 1 (a) and a microstructure morphology of a 2.4 vol.% TiB+La2 O3 /IMI834 titanium-based composite material prepared in Example 2 (b);
图3为实施例1烧结态1.2vol.％TiB+La2O3/IMI834复合材料中，位于晶界/晶内的纳米增强体示意图；FIG3 is a schematic diagram of nano-reinforcements located at grain boundaries/inside grains in the sintered 1.2 vol.% TiB+La2 O3 /IMI834 composite material of Example 1;
图4为实施例2所得的钛基复合材料(b)与同工艺下基体合金(a)的EBSD组织对比图；FIG4 is an EBSD microstructure comparison diagram of the titanium-based composite material (b) obtained in Example 2 and the matrix alloy (a) obtained under the same process;
图5为实施例1和2制备的纳米TiB+La2O3/IMI834钛基复合材料的室温拉伸性能。FIG. 5 shows the room temperature tensile properties of the nano-TiB+La2 O3 /IMI834 titanium-based composite materials prepared in Examples 1 and 2. FIG.
具体实施方式Detailed ways
以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变化和改进，这些都属于本发明的保护范围。下面结合具体实施例对本发明进行详细说明：The following examples will help those skilled in the art to further understand the present invention, but are not intended to limit the present invention in any form. For those skilled in the art, several changes and improvements can be made without departing from the concept of the present invention, which all belong to the protection scope of the present invention. The present invention is described in detail below in conjunction with specific embodiments:
一种多层次纳米颗粒增强钛基复合材料强韧化方法，包括以下步骤：A method for strengthening and toughening a multi-level nanoparticle-reinforced titanium-based composite material, comprising the following steps:
A、筛选不同粒径内嵌超细网状结构的钛基复合材料粉体；A. Screening titanium-based composite powders with different particle sizes and embedded ultrafine mesh structures;
B、将筛选后不同粒径的钛基复合材料粉末装填入模具中，并在烧结炉中随炉加热至材料β相变温度以下20～200℃，进行预压烧结；B. Filling the screened titanium-based composite powders of different particle sizes into a mold, and heating them in a sintering furnace to 20 to 200° C. below the β phase transition temperature of the material, and performing pre-pressing and sintering;
C、将炉温上升至Tβ以上20～300℃，进行致密化烧结；C. Raise the furnace temperature to 20-300°C above Tβ for densification sintering;
D、烧结后炉冷至材料设定的时效温度，进行时效处理。即得所述纳米增强体在基体中呈现晶界/晶内多层次分布的高强韧钛基复合材料。D. After sintering, the furnace is cooled to the aging temperature set for the material, and aging treatment is performed, so that the high-strength and tough titanium-based composite material with the nano-reinforcement presenting a multi-level distribution of grain boundaries/intra-grains in the matrix is obtained.
钛基复合材料粉体通过以下方法制备：Titanium-based composite powders are prepared by the following method:
以TiB+La2O3/IMI834复合材料粉末为例Take TiB+La2 O3 /IMI834 composite powder as an example
步骤一、以海绵钛、海绵锆、铝丝以及铝钼(Al-Mo)、钛锡(Ti-Sn)、铝铌(Al-Nb)等中间合金为合金原料、六硼化镧(LaB6)粉末为增强体原料，以2.5kg每份称取，其中控制增强体体积分数分别为1.2vol.％和2.4vol.％，倒入模具中，用机械压制为自耗电极；Step 1: Use titanium sponge, zirconium sponge, aluminum wire, and master alloys such as aluminum-molybdenum (Al-Mo), titanium-tin (Ti-Sn), and aluminum-niobium (Al-Nb) as alloy raw materials, and lanthanum hexaboride (LaB6 ) powder as reinforcement raw material, weigh 2.5 kg each, wherein the volume fraction of the reinforcement is controlled to be 1.2 vol.% and 2.4 vol.%, respectively, pour them into a mold, and use a machine to press them into a consumable electrode;
步骤二、将电极放入真空自耗电弧炉中进行第一次真空熔炼，控制熔炼电流为1kA，真空度为5×10-3Pa，该熔炼过程重复进行三次，保证铸锭成分均匀，原位反应进行完全，得到三次锭；Step 2: Place the electrode in a vacuum consumable arc furnace for the first vacuum melting, control the melting current to 1kA, and the vacuum degree to 5×10-3 Pa. Repeat the melting process three times to ensure that the composition of the ingot is uniform and the in-situ reaction is complete, and obtain three ingots;
步骤三、将所得的三次锭1100℃下进行锻造拔长，得到粗坯棒料，外径55mm，长度450mm，机加工车光为规整圆棒，外径50mm，长度500mm；Step 3: Forge and stretch the obtained tertiary ingot at 1100° C. to obtain a rough bar with an outer diameter of 55 mm and a length of 450 mm, and machine and polish it into a regular round bar with an outer diameter of 50 mm and a length of 500 mm;
步骤四、采用电极感应熔炼气雾化制粉设备，用感应线圈将棒料电极加热至2000℃，熔体经漏孔自由向下流入气体雾化炉，雾化压力为2.5MPa，采用的气体为氩气，合金熔体破碎为细小液滴，经过快速冷却得到钛基复合材料粉末，并被收集起来；Step 4: Using electrode induction melting gas atomization powder making equipment, the rod electrode is heated to 2000°C with an induction coil, and the melt flows freely downward into the gas atomization furnace through the leak hole. The atomization pressure is 2.5MPa. The gas used is argon. The alloy melt is broken into fine droplets, and the titanium-based composite material powder is obtained after rapid cooling and collected;
步骤五、制得的钛基复合材料粉末经过筛分，按照0～53μm、53～150μm和150μm以上三种粒径分布进行，得到15～53μm粉末占比32％，53～100μm粉末占比41％，100～150μm粉末占比22％，150μm以上粉末占比5％。Step 5: The obtained titanium-based composite material powder is sieved according to three particle size distributions of 0-53 μm, 53-150 μm and above 150 μm, and the powder of 15-53 μm accounts for 32%, the powder of 53-100 μm accounts for 41%, the powder of 100-150 μm accounts for 22%, and the powder of above 150 μm accounts for 5%.
评价标准及方法：Evaluation criteria and methods:
1、粉末组织形貌--内部TiB、TiC、La2O3等增强体呈网络结构分布，实现了增强体的内嵌；烧结态复合材料组织-经粉体改性后材料组织得到了明显细化，呈现均匀的等轴组织，同时增强体以微纳双尺度均匀分布在基体中；1. Powder structure morphology - the internal reinforcements such as TiB,TiC ,La2O3 are distributed in a network structure, realizing the embedding of the reinforcements; Sintered composite material structure - after powder modification, the material structure has been significantly refined, showing a uniform equiaxed structure, and the reinforcements are evenly distributed in the matrix at micro-nano dual scales;
测试方法为：在TASCAN RISE-MAGNA上设置5kV电压观察微观组织。The test method is: set 5kV voltage on TASCAN RISE-MAGNA to observe the microstructure.
2、拉伸性能测试--抗拉强度、延伸率；2. Tensile performance test-tensile strength and elongation;
测试方法为：在Zwick Z100万能试验机上进行力学性能测试，试样为片状拉伸试样，采用引伸计来测定延伸率。The test method is: the mechanical properties test is carried out on a Zwick Z100 universal testing machine, the sample is a sheet tensile sample, and the elongation is measured using an extensometer.
实施例1Example 1
本实施例提供了一种多层次纳米颗粒增强钛基复合材料强韧化方法，包括以下步骤：This embodiment provides a method for strengthening and toughening a multi-level nanoparticle-reinforced titanium-based composite material, comprising the following steps:
A、选用气雾化方法制备得到的0.91vol.％TiB+0.29vol.％La2O3增强IMI834复合材料粉末(1.2vol.％TiB+La2O3/IMI834)，通过振动筛分，筛选出粒径为53～100μm的粉末；A. 0.91 vol.% TiB+0.29 vol.% La2 O3 reinforced IMI834 composite powder (1.2 vol.% TiB+La2 O3 /IMI834) prepared by gas atomization method was selected, and powder with a particle size of 53-100 μm was screened out by vibration screening;
B、将筛选后不同粒径的钛基复合材料粉末装填如模具中，并在热压烧结炉中进行预压烧结。预压烧结温度范围为：900℃，压强范围为：50MPa，升温速率为：10℃/min，保温时间为：60min，真空度大于5×10-2Pa。B. Fill the screened titanium-based composite powders of different particle sizes into a mold and pre-press and sinter them in a hot pressing sintering furnace. The pre-pressing sintering temperature range is 900°C, the pressure range is 50MPa, the heating rate is 10°C/min, the holding time is 60min, and the vacuum degree is greater than 5×10-2 Pa.
C、预压烧结完成后随炉升温至1200℃进行致密化烧结，其烧结压强为：50MPa，升温速率为：10℃/min，保温时间为：60min，真空度大于5×10-2Pa。C. After pre-pressing and sintering, the furnace temperature is raised to 1200°C for densification sintering. The sintering pressure is 50MPa, the heating rate is 10°C/min, the holding time is 60min, and the vacuum degree is greater than 5×10-2 Pa.
D、烧结后炉冷至700℃进行时效处理，保温2h后炉冷至室温。即得所述具备均匀细小组织且纳米增强体在基体中呈现晶界/晶内多层次分布的高强韧钛基复合材料。D. After sintering, the furnace is cooled to 700°C for aging treatment, and then cooled to room temperature after keeping the temperature for 2 hours. Thus, the high-strength and tough titanium-based composite material with uniform fine structure and nano-reinforcement in the matrix showing multi-level distribution of grain boundaries/intra-grains is obtained.
图1为粉末组织形貌，可见内部TiB与La2O3增强体呈网络结构分布，实现了增强体的内嵌。图2(a)为烧结组织示意图，从材料组织中并未观测到粗大的原始β晶及魏氏组织，材料呈现均匀细小的近片层组织。图3为制得的1.2vol.％TiB+La2O3/IMI834耐热钛基复合材料增强体形貌及分布示意图，可以看出TiB与La2O3均保持为纳米尺寸，且在晶界/晶内程多层次分布。图5为拉伸性能测试结果，对于1.2vol.％的复合材料其抗拉强度达到了1100MPa，且保持10％以上的延伸率，与同工艺下制备的基体合金相比，在不损失强度的前提下，延伸率提高了5倍。Figure 1 is the powder structure morphology, which shows that the internal TiB and La2 O3 reinforcements are distributed in a network structure, achieving the embedding of the reinforcements. Figure 2 (a) is a schematic diagram of the sintered structure. No coarse original β crystals and Widmanstätten structure were observed in the material structure, and the material showed a uniform and fine near-lamellar structure. Figure 3 is a schematic diagram of the reinforcement morphology and distribution of the 1.2 vol.% TiB + La2 O3 /IMI834 heat-resistant titanium-based composite material obtained. It can be seen that both TiB and La2 O3 remain in nanometer size and are distributed in multiple levels at the grain boundary/intragranular. Figure 5 is the tensile performance test results. For the 1.2 vol.% composite material, its tensile strength reaches 1100 MPa, and the elongation is maintained at more than 10%. Compared with the matrix alloy prepared under the same process, the elongation is increased by 5 times without losing strength.
实施例2Example 2
本实施例提供了一种多层次纳米颗粒增强钛基复合材料强韧化方法，包括以下步骤：This embodiment provides a method for strengthening and toughening a multi-level nanoparticle-reinforced titanium-based composite material, comprising the following steps:
A、选用气雾化方法制备得到的2.4vol TiB+La2O3/IMI834，通过振动筛分，筛选出粒径为53～100μm的粉末；A. 2.4 vol TiB+La2 O3 /IMI834 prepared by gas atomization method was selected and vibrated to screen out powder with a particle size of 53-100 μm;
B、将筛选后不同粒径的钛基复合材料粉末装填如模具中，并在热压烧结炉中进行预压烧结。预压烧结温度范围为：900℃，压强范围为：50MPa，升温速率为：10℃/min，保温时间为：60min，真空度大于5×10-2Pa。B. Fill the screened titanium-based composite powders of different particle sizes into a mold and pre-press and sinter them in a hot pressing sintering furnace. The pre-pressing sintering temperature range is 900°C, the pressure range is 50MPa, the heating rate is 10°C/min, the holding time is 60min, and the vacuum degree is greater than 5×10-2 Pa.
C、预压烧结完成后随炉升温至1100℃进行致密化烧结，其烧结压强为：50MPa，升温速率为：10℃/min，保温时间为：60min，真空度大于5×10-2Pa。C. After the pre-pressing sintering is completed, the furnace temperature is raised to 1100°C for densification sintering. The sintering pressure is 50MPa, the heating rate is 10°C/min, the holding time is 60min, and the vacuum degree is greater than 5×10-2 Pa.
D、烧结后炉冷至700℃进行时效处理，保温2h后炉冷至室温。即得所述具备均匀细小组织且纳米增强体在基体中呈现晶界/晶内多层次分布的高强韧钛基复合材料。D. After sintering, the furnace is cooled to 700°C for aging treatment, and then cooled to room temperature after keeping the temperature for 2 hours. Thus, the high-strength and tough titanium-based composite material with uniform fine structure and nano-reinforcement in the matrix showing multi-level distribution of grain boundaries/intra-grains is obtained.
本实施例制得的材料中，微观组织形貌与实施例1相似，粉体中均形成了网状结构，此外从图2(b)的组织照片中可以看出，增强体体积分数的提高促进了对基体的细化作用，将基体进一步细化为细小的等轴组织，达到了组织调控的目的。图4为所得2.4vol.％TiB+La2O3/IMI834耐热钛基复合材料与同工艺下IMI834基体合金的EBSD组织对比图，发现复合材料粉体中的超细网状结构在细化晶粒，调控基体组织中发挥的作用。图5为拉伸性能测试，2.4vol.％TiB+La2O3增强复合材料，其抗拉强度达到了1181MPa以上，且延伸率高于3.5％，与同工艺下制备的基体合金相比，强度和塑性同时得到了提高。In the material prepared in this embodiment, the microstructure morphology is similar to that in Example 1, and a network structure is formed in the powder. In addition, it can be seen from the organizational photograph of Figure 2 (b) that the increase in the volume fraction of the reinforcement promotes the refinement of the matrix, further refining the matrix into a fine equiaxed structure, thereby achieving the purpose of organizational regulation. Figure 4 is an EBSD organizational comparison diagram of the obtained 2.4vol.%TiB+La2 O3 /IMI834 heat-resistant titanium-based composite material and the IMI834 matrix alloy under the same process. It is found that the ultrafine network structure in the composite powder plays a role in refining grains and regulating the matrix structure. Figure 5 is a tensile performance test. The tensile strength of the 2.4vol.%TiB+La2 O3 reinforced composite material reaches more than 1181MPa, and the elongation is higher than 3.5%. Compared with the matrix alloy prepared under the same process, the strength and plasticity are improved at the same time.
实施例3Example 3
本实施例提供了一种多层次纳米颗粒增强钛基复合材料强韧化方法，包括以下步骤：This embodiment provides a method for strengthening and toughening a multi-level nanoparticle-reinforced titanium-based composite material, comprising the following steps:
A、选用气雾化方法制备得到的2.5vol.％TiB/IMI834，通过振动筛分，筛选出粒径为15～53μm的粉末；A. 2.5 vol.% TiB/IMI834 prepared by aerosolization method was selected, and a powder with a particle size of 15 to 53 μm was screened out by vibration screening;
B、将筛选后不同粒径的钛基复合材料粉末装填入模具中，并在热压烧结炉中进行预压烧结。预压烧结温度范围为：900℃，压强范围为：50MPa，升温速率为：10℃/min，保温时间为：60min，真空度大于5×10-2Pa。B. Fill the screened titanium-based composite powders of different particle sizes into a mold and perform pre-pressing and sintering in a hot pressing sintering furnace. The pre-pressing and sintering temperature range is: 900°C, the pressure range is: 50MPa, the heating rate is: 10°C/min, the holding time is: 60min, and the vacuum degree is greater than 5×10-2 Pa.
C、预压烧结完成后随炉升温至1200℃进行致密化烧结，其烧结压强为：50MPa，升温速率为：10℃/min，保温时间为：60min，真空度大于5×10-2Pa。C. After pre-pressing and sintering, the furnace temperature is raised to 1200°C for densification sintering. The sintering pressure is 50MPa, the heating rate is 10°C/min, the holding time is 60min, and the vacuum degree is greater than 5×10-2 Pa.
D、烧结后炉冷至700℃进行时效处理，保温2h后炉冷至室温。即得所述具备均匀细小组织且纳米增强体在基体中呈现晶界/晶内多层次分布的高强韧钛基复合材料。D. After sintering, the furnace is cooled to 700°C for aging treatment, and then cooled to room temperature after keeping the temperature for 2 hours. Thus, the high-strength and tough titanium-based composite material with uniform fine structure and nano-reinforcement in the matrix showing multi-level distribution of grain boundaries/intra-grains is obtained.
本实施例制得的材料中，微观组织形貌与实施例2相似，粉体中均形成了网状结构，且烧结钛合金呈现均匀细小的等轴组织。In the material prepared in this embodiment, the microstructure morphology is similar to that of Embodiment 2, a network structure is formed in the powder, and the sintered titanium alloy presents a uniform and fine equiaxed structure.
实施例4Example 4
本实施例提供了一种多层次纳米颗粒增强钛基复合材料强韧化方法，包括以下步骤：This embodiment provides a method for strengthening and toughening a multi-level nanoparticle-reinforced titanium-based composite material, comprising the following steps:
A、选用气雾化方法制备得到的4vol.％TiB+1vol.％TiC增强的TC4复合材料粉体，通过振动筛分，筛选出粒径为53～100μm的粉末；A. Select 4 vol.% TiB+1 vol.% TiC reinforced TC4 composite material powder prepared by gas atomization method, and screen out powder with a particle size of 53-100 μm by vibration screening;
B、将筛选后不同粒径的钛基复合材料粉末装填如模具中，并在热压烧结炉中进行预压烧结。预压烧结温度范围为：800℃，压强范围为：50MPa，升温速率为：10℃/min，保温时间为：60min，真空度大于5×10-2Pa。B. Fill the screened titanium-based composite powders of different particle sizes into a mold and pre-press and sinter them in a hot pressing sintering furnace. The pre-pressing sintering temperature range is 800°C, the pressure range is 50MPa, the heating rate is 10°C/min, the holding time is 60min, and the vacuum degree is greater than 5×10-2 Pa.
C、预压烧结完成后随炉升温至1200℃进行致密化烧结，其烧结压强为：50MPa，升温速率为：10℃/min，保温时间为：60min，真空度大于5×10-2Pa。C. After pre-pressing and sintering, the furnace temperature is raised to 1200°C for densification sintering. The sintering pressure is 50MPa, the heating rate is 10°C/min, the holding time is 60min, and the vacuum degree is greater than 5×10-2 Pa.
D、烧结后炉冷至600℃进行时效处理，保温2h后炉冷至室温。即得所述具备均匀细小组织且TiB和TiC两种纳米增强体在基体中呈现晶界/晶内多层次分布的高强韧钛基复合材料。D. After sintering, the furnace is cooled to 600°C for aging treatment, and then cooled to room temperature after being kept at this temperature for 2 hours. Thus, the high-strength and tough titanium-based composite material with uniform fine structure and TiB and TiC nano-reinforcements in the matrix presenting multi-level distribution of grain boundaries/intra-grains is obtained.
本实施例制得的材料中，基体的微观组织形貌与实施例2相同，均为细小的等轴组织。但随着TiC的加入，烧结态组织得到进一步的细化，TiB与TiC纳米增强体在晶界/晶内呈现多层次分布。In the material prepared in this embodiment, the microstructure of the matrix is the same as that in embodiment 2, both of which are fine equiaxed structures. However, with the addition of TiC, the sintered structure is further refined, and the TiB and TiC nano-reinforcements are distributed in multiple levels at the grain boundaries/intra-grains.
实施例5Example 5
本实施例提供了一种多层次纳米颗粒增强钛基复合材料强韧化方法，包括以下步骤：This embodiment provides a method for strengthening and toughening a multi-level nanoparticle-reinforced titanium-based composite material, comprising the following steps:
A、选用气雾化方法制备得到的2.5vol.％TiB+2.5vol.％TiC增强的TC4复合材料粉体，通过振动筛分，筛选出粒径为15～53μm的粉末；A. Select TC4 composite material powder reinforced with 2.5 vol.% TiB+2.5 vol.% TiC prepared by gas atomization method, and select powder with a particle size of 15 to 53 μm by vibration screening;
B、将筛选后不同粒径的钛基复合材料粉末装填如模具中，并在热压烧结炉中进行预压烧结。预压烧结温度范围为：800℃，压强范围为：50MPa，升温速率为：10℃/min，保温时间为：60min，真空度大于5×10-2Pa。B. Fill the screened titanium-based composite powders of different particle sizes into a mold and pre-press and sinter them in a hot pressing sintering furnace. The pre-pressing sintering temperature range is 800°C, the pressure range is 50MPa, the heating rate is 10°C/min, the holding time is 60min, and the vacuum degree is greater than 5×10-2 Pa.
C、预压烧结完成后随炉升温至1200℃进行致密化烧结，其烧结压强为：50MPa，升温速率为：10℃/min，保温时间为：60min，真空度大于5×10-2Pa。C. After pre-pressing and sintering, the furnace temperature is raised to 1200°C for densification sintering. The sintering pressure is 50MPa, the heating rate is 10°C/min, the holding time is 60min, and the vacuum degree is greater than 5×10-2 Pa.
D、烧结后炉冷至600℃进行时效处理，保温2h后炉冷至室温。即得所述具备均匀细小组织且TiB和TiC两种纳米增强体在基体中呈现晶界/晶内多层次分布的高强韧钛基复合材料。D. After sintering, the furnace is cooled to 600°C for aging treatment, and then cooled to room temperature after being kept at this temperature for 2 hours. Thus, the high-strength and tough titanium-based composite material with uniform fine structure and TiB and TiC nano-reinforcements in the matrix presenting multi-level distribution of grain boundaries/intra-grains is obtained.
本实施例制得的材料中，烧结态材料的微观组织形貌与实施例2类似，证实了该方法可以适用于不同的钛合金体系，且可以适用于高体积分数的复合材料。In the material prepared in this example, the microstructure morphology of the sintered material is similar to that of Example 2, which proves that the method can be applied to different titanium alloy systems and can be applied to composite materials with high volume fraction.
对比例1Comparative Example 1
本对比例提供了一种多层次纳米颗粒增强钛基复合材料强韧化方法，其步骤与实施例1基本相同，不同之处仅在于：未进行预压烧结，在1100～1200℃进行致密化烧结，烧结压强为：50MPa，升温速率为：10℃/min，保温时间为：120min，真空度大于5×10-2Pa。This comparative example provides a method for strengthening and toughening a multi-level nanoparticle-reinforced titanium-based composite material. The steps are basically the same as those in Example 1, except that no pre-pressing sintering is performed, densification sintering is performed at 1100-1200°C, the sintering pressure is 50MPa, the heating rate is 10°C/min, the holding time is 120min, and the vacuum degree is greater than 5×10-2 Pa.
相较于两步烧结工艺，一步烧结工艺虽然得到致密化的块体材料，但是由于纳米增强体在高温下热稳定性较差，未经过低温稳定化处理的材料增强体尺寸粗化明显，大多生长为微米尺寸的增强体，导致材料强度和塑性同时下降，利用一步致密化烧结的材料较两步烧结的材料强度降低30～50MPa，延伸率降低1～3％。Compared with the two-step sintering process, although the one-step sintering process can obtain a densified bulk material, due to the poor thermal stability of the nano-reinforcement at high temperature, the material reinforcement size that has not undergone low-temperature stabilization treatment is significantly coarsened, and most of them grow into micron-sized reinforcements, resulting in a simultaneous decrease in material strength and plasticity. The material sintered by one-step densification has a strength reduction of 30 to 50 MPa and an elongation reduction of 1 to 3% compared with the material sintered by two-step sintering.
对比例2Comparative Example 2
本对比例提供了一种多层次纳米颗粒增强钛基复合材料强韧化方法，其步骤与实施例1基本相同，不同之处仅在于：步骤A中采用常规等量的TiB2、La2O3增强体反应剂与球形钛合金粉体混合，并在步骤C中利用高温原位反应得到钛基复合材料。This comparative example provides a method for strengthening and toughening a multi-level nanoparticle-reinforced titanium-based composite material, and its steps are basically the same as those of Example 1, except that: in step A, conventional equal amounts of TiB2 and La2 O3 reinforcement reactants are mixed with spherical titanium alloy powders, and in step C, a high-temperature in-situ reaction is used to obtain the titanium-based composite material.
该工艺与专利CN101333607中公开的方法类似，其本质区别在于：(1)本方法采用的钛基复合材料粉体在烧结前已经实现了增强体的均匀化复合，无需经过球磨等均匀化或表面包覆工艺，缩短了制备流程，并避免了杂质引入；(2)对比工艺需要利用高温下的反应剂与基体的原位反应引入增强体，一般烧结致密化所需温度较高，使增强体与基体明显粗化，一般增强体尺寸为＞5μm，且基体呈粗大的片层组织，本发明制备得到的材料具有细小的等轴组织，且增强体均为纳米尺度，具有更好的室温强塑性；(3)对比工艺增强体反应剂一般会附着在球形钛合金粉表面，在烧结后在颗粒边界形成直径约50～150μm的网状结构，而本发明得到的材料纳米增强体在晶界/晶内呈多层次分布，弥散程度更高，在组织特征上具有明显的差别。This process is similar to the method disclosed in patent CN101333607, and the essential difference between them is that: (1) the titanium-based composite material powder used in this method has achieved homogenized composite reinforcement before sintering, and does not need to undergo homogenization or surface coating processes such as ball milling, which shortens the preparation process and avoids the introduction of impurities; (2) the comparative process requires the introduction of reinforcement by in-situ reaction between the reactant and the matrix at high temperature. Generally, the temperature required for sintering densification is relatively high, which makes the reinforcement and the matrix significantly coarsened. Generally, the size of the reinforcement is greater than 5μm, and the matrix has a coarse lamellar structure. The material prepared by the present invention has a fine equiaxed structure, and the reinforcement is nanoscale, which has better room temperature strength and plasticity; (3) the reinforcement reactant of the comparative process generally adheres to the surface of the spherical titanium alloy powder, and forms a mesh structure with a diameter of about 50 to 150μm at the particle boundary after sintering, while the nano-reinforcement of the material obtained by the present invention is multi-layered distributed at the grain boundary/intragranular, with a higher degree of dispersion, and has obvious differences in organizational characteristics.
对比例3Comparative Example 3
本对比例提供了一种多层次纳米颗粒增强钛基复合材料强韧化方法，其步骤与实施例1基本相同，不同之处仅在于：步骤C中的致密化烧结温度分别为950℃和1000℃，低于β相变温度。低的烧结温度虽然可以显著细化晶粒尺寸，但是材料致密度分别仅为91.6％和96.3％远低于实施例1的99.3％，材料的微观组织中存在大量的微孔，使得材料表现出明显的室温脆性，延伸率分别为1.1％和4.3％远低于实施例1，因此本发明优选的制备参数是材料组织调控及综合性能提升重要的依据。This comparative example provides a method for strengthening and toughening a multi-level nanoparticle-reinforced titanium-based composite material, and its steps are basically the same as those in Example 1, except that the densification sintering temperatures in step C are 950°C and 1000°C, respectively, which are lower than the β phase transition temperature. Although the low sintering temperature can significantly refine the grain size, the material density is only 91.6% and 96.3%, respectively, which is far lower than 99.3% in Example 1. There are a large number of micropores in the microstructure of the material, which makes the material show obvious room temperature brittleness, and the elongation is 1.1% and 4.3%, respectively, which is far lower than Example 1. Therefore, the preferred preparation parameters of the present invention are an important basis for material organization regulation and comprehensive performance improvement.
以上对本发明的具体实施例进行了描述。需要理解的是，本发明并不局限于上述特定实施方式，本领域技术人员可以在权利要求的范围内做出各种变形或修改，这并不影响本发明的实质内容。The above describes the specific embodiments of the present invention. It should be understood that the present invention is not limited to the above specific embodiments, and those skilled in the art may make various modifications or variations within the scope of the claims, which do not affect the essence of the present invention.
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