技术领域technical field
本发明属于超硬材料制备技术领域，特别涉及一种超硬材料颗粒/钛铝核壳结构复合颗粒及其制备方法。The invention belongs to the technical field of superhard material preparation, in particular to a superhard material particle/titanium aluminum core-shell composite particle and a preparation method thereof.
背景技术Background technique
超硬材料磨具材料，是指用超硬材料如金刚石、立方氮化硼或碳化硼作为磨料，用各种不同结合剂将其粘结具有一定几何形状的材料的总称。金刚石复合材料广泛应用于地质勘探、石材、机械、汽车及国防工业等各个领域，产品已形成系列化，品种规格比较齐全。但是由于超硬材料磨粒具有较大的惰性，不易与结合剂结合，与结合剂界面活性较差，主要为物理结合，因此当超硬材料磨具磨削工件时，超硬材料磨粒容易过早脱落，未充分发挥其磨削作用，从而降低磨料利用率和磨具的使用寿命。磨粒的无序与过早脱落限制了超硬材料磨具材料磨削加工技术的广泛应用。Superhard material abrasive material refers to the general term for materials that use superhard materials such as diamond, cubic boron nitride or boron carbide as abrasives, and bond them with various binders to have a certain geometric shape. Diamond composite materials are widely used in various fields such as geological exploration, stone materials, machinery, automobiles and national defense industries. The products have been serialized with relatively complete varieties and specifications. However, due to the high inertia of the superhard material abrasive grains, it is not easy to combine with the binder, and the interface activity with the binder is poor, mainly physical combination, so when the superhard material abrasive tool grinds the workpiece, the superhard material abrasive grains are easy to Premature shedding does not give full play to its grinding effect, thereby reducing the utilization rate of abrasives and the service life of abrasives. The disorder and premature shedding of abrasive grains limit the wide application of grinding technology for superhard abrasive materials.
为了提高金刚石与陶瓷结合剂的结合强度，目前常采用的方法是金刚石表面通过物理或化学方法镀覆某些强碳化物形成元素，如W、Cr、Ni、Cr 等过渡金属或合金，其主要目的是为了解决过早脱落的问题。其采用的制备技术主要为化学镀或电镀，但化学镀法存在镀层厚度有限、镀覆过程慢、镀液易分解和存在污染等缺点，而电镀法通常则用于化学镀的增厚等。这些镀覆技术均具有能耗高、易污染等缺点。In order to improve the bonding strength between diamond and ceramic bond, the method commonly used at present is to plate some strong carbide-forming elements on the diamond surface by physical or chemical methods, such as W, Cr, Ni, Cr and other transition metals or alloys. The purpose is to solve the problem of premature shedding. The preparation technology used is mainly electroless plating or electroplating, but the electroless plating method has the disadvantages of limited coating thickness, slow plating process, easy decomposition of the plating solution, and pollution, while the electroplating method is usually used for thickening of electroless plating. These plating technologies all have the disadvantages of high energy consumption and easy pollution.
自蔓延高温烧结（SHS）技术作为一种新型合成技术，具有节省时间，设备简单，能源利用充分，生产效率高，可生产大规格的制品等优点。采用高温自蔓延技术制备金刚石超硬材料工具，能够在较短时间内升至高温，提高金刚石与结合剂的把持力。目前已有相关研究采用SHS技术制备了金刚石工具，比如节块、磨块或砂轮。但是到目前为止，还没有通过SHS技术在金刚石表面镀覆涂层的研究报道。Self-propagating high-temperature sintering (SHS) technology, as a new synthesis technology, has the advantages of saving time, simple equipment, sufficient energy utilization, high production efficiency, and the ability to produce large-scale products. The high-temperature self-propagating technology is used to prepare diamond superhard material tools, which can rise to high temperature in a short period of time and improve the holding force of diamond and bonding agent. At present, relevant research has used SHS technology to prepare diamond tools, such as nodes, grinding blocks or grinding wheels. But so far, there is no research report on the coating on diamond surface by SHS technology.
发明内容Contents of the invention
本发明的目的是针对现有制备金刚石镀覆层技术的缺陷，提出一种超硬材料磨粒/钛铝核壳结构复合颗粒及其制备方法。The purpose of the present invention is to propose a superhard material abrasive grain/titanium-aluminum core-shell structure composite particle and a preparation method thereof for the defects of the existing diamond coating layer preparation technology.
本发明采用的技术方案如下：The technical scheme that the present invention adopts is as follows:
一种超硬材料颗粒/钛铝核壳结构复合颗粒，所述复合颗粒以超硬材料颗粒为内核，以钛铝相复合材料为包覆层；所述包覆层质量占复合颗粒质量的30-50%。A superhard material particle/titanium-aluminum core-shell structure composite particle, the composite particle uses the superhard material particle as the core, and the titanium-aluminum phase composite material as the cladding layer; the mass of the cladding layer accounts for 30% of the mass of the composite particle -50%.
所述超硬材料颗粒的粒径为20～450μm，包覆层厚度为1-25μm。The particle size of the superhard material particles is 20-450 μm, and the thickness of the coating layer is 1-25 μm.
所述超硬材料颗粒可以为金刚石、碳化硼或立方氮化硼颗粒等。The superhard material particles can be diamond, boron carbide or cubic boron nitride particles, etc.
本发明还提供了一种所述超硬材料颗粒/钛铝核壳结构复合颗粒的制备方法，将钛粉、铝粉和石墨粉充分混合得到混合料A，再将混合料A与超硬材料颗粒充分混合得到混合料B，将混合料B压制后利用高温自蔓延燃烧制得超硬材料颗粒/钛铝核壳结构复合颗粒。The present invention also provides a preparation method of the superhard material particles/titanium-aluminum core-shell structure composite particles, fully mixing titanium powder, aluminum powder and graphite powder to obtain a mixture A, and then mixing the mixture A with the superhard material The particles are fully mixed to obtain a mixture B, and the mixture B is compressed to obtain superhard material particles/titanium-aluminum core-shell structure composite particles by high-temperature self-propagating combustion.
钛粉、铝粉、石墨粉三者的质量百分组成为：钛粉65-75%，铝粉10-20%、石墨粉8-15%。The mass percentage of titanium powder, aluminum powder and graphite powder is composed of: titanium powder 65-75%, aluminum powder 10-20%, graphite powder 8-15%.
原料超硬材料颗粒的粒径优选控制为20-400μm；钛粉、铝粉、石墨粉的粒径优选控制为30-70μm。The particle size of raw superhard material particles is preferably controlled to be 20-400 μm; the particle size of titanium powder, aluminum powder and graphite powder is preferably controlled to be 30-70 μm.
优选采用球磨混合5-10h实现充分混合获得混合料A和混合料B。It is preferred to use ball milling for 5-10 hours to achieve thorough mixing to obtain the mixture A and mixture B.
将混合料B放到钢模具中，压强为100-200MPa，压成直径为20mm的圆片坯体。当然，并不仅限于钢模具以及20mm的圆片坯体，其他可以实现相应功能的模具、坯体的形状和大小都是可行的。Put the mixture B into a steel mold with a pressure of 100-200MPa, and press it into a disc green body with a diameter of 20mm. Of course, it is not limited to the steel mold and the 20mm wafer green body, other molds that can realize corresponding functions, and the shape and size of the green body are all feasible.
利用高温自蔓延燃烧的条件如下：利用等离子体喷枪点燃压制后的混合料B，点燃温度约800-900℃，压力20-50Mpa，反应时间3～5s。制备后可获得较疏松的多孔块体，易于粉碎。The conditions for using high-temperature self-propagating combustion are as follows: use a plasma torch to ignite the pressed mixture B, the ignition temperature is about 800-900°C, the pressure is 20-50Mpa, and the reaction time is 3-5s. After preparation, a loose porous block can be obtained, which is easy to crush.
本发明采用高温自蔓延技术，在常压条件下，利用等离子体喷枪或激光焊接机在10秒内点燃试样，发生自蔓延反应，高温烧结合成钛铝核壳结构材料，使其在金刚石等超硬材料表面形成Ti-Al-C结构。高温自蔓延反应使用的设备、工艺简单，反应迅速、时间短，生产效率高，能耗低，可以减少金刚石的热损伤，提高制品的耐用度和使用寿命。The present invention adopts high-temperature self-propagation technology, under normal pressure conditions, uses a plasma spray gun or a laser welding machine to ignite the sample within 10 seconds, a self-propagation reaction occurs, and high-temperature sintering is combined into a titanium-aluminum core-shell structure material, so that it can be used in diamond, etc. A Ti-Al-C structure is formed on the surface of the superhard material. The equipment and process used in the high-temperature self-propagating reaction are simple, the reaction is rapid, the time is short, the production efficiency is high, and the energy consumption is low, which can reduce the thermal damage of diamond and improve the durability and service life of the product.
制备的超硬材料颗粒/钛铝核壳结构复合颗粒可以在金属或树脂基结合剂磨具材料中得到应用。采用相同的树脂粘结剂，本发明获得的砂轮要比表面没有处理的普通金刚石磨粒制备的砂轮工作效率得到很大的提高。其磨削效率提高了25%。使用过程中，复合颗粒不易脱落，使用寿命提高了33%以上。The prepared superhard material particles/titanium-aluminum core-shell structure composite particles can be applied in metal or resin-based bond abrasive materials. Using the same resin binder, the working efficiency of the grinding wheel obtained by the invention is greatly improved compared with the grinding wheel prepared by ordinary diamond abrasive grains without surface treatment. Its grinding efficiency has increased by 25%. During use, the composite particles are not easy to fall off, and the service life is increased by more than 33%.
本发明与现有技术相比具有以下优点：Compared with the prior art, the present invention has the following advantages:
本发明利用SHS技术合成一种新的超硬材料颗粒/钛铝核壳结构复合颗粒，具有节省时间，设备简单，能源利用充分，生产效率高，可生产大规格的制品，成本低等优势，具有巨大的经济效益和社会效益。The invention uses SHS technology to synthesize a new superhard material particle/titanium-aluminum core-shell structure composite particle, which has the advantages of saving time, simple equipment, sufficient energy utilization, high production efficiency, large-scale products can be produced, and low cost. It has huge economic and social benefits.
附图说明Description of drawings
图1为实施例1获得的金刚石/钛铝核壳结构复合颗粒的SEM图；Fig. 1 is the SEM picture of the diamond/titanium aluminum core-shell structure composite particle that embodiment 1 obtains;
图2为实施例1获得的金刚石/钛铝核壳结构复合颗粒的EDS图。FIG. 2 is an EDS diagram of the diamond/titanium aluminum core-shell composite particles obtained in Example 1. FIG.
图3为使用实施例1获得的复合颗粒作为磨粒制备的磨具产品。Fig. 3 is an abrasive tool product prepared by using the composite particles obtained in Example 1 as abrasive grains.
具体实施方式Detailed ways
以下以具体实施例来说明本发明的技术方案，但本发明的保护范围不限于此：The technical scheme of the present invention is described below with specific examples, but protection scope of the present invention is not limited thereto:
实施例1Example 1
采用钛粉、铝粉和石墨粉为原料，其原料配比按质量百分比计分别为71.1%、20%和8.9%，通过球磨5h充分混合均匀获得混合料A，再选用粒度为200μm的金刚石磨料与混合料A进行球磨5h，使这些粉料充分混合均匀获得混合料B，其中金刚石磨料按原料总的质量百分比50%的比例称取；将所得混合料B填充入钢模具中，在压片机上加压100MPa，得到相对密度约70%的直径为20mm的圆形坯体（下同），最后通过等离子体喷枪点燃坯体，使其发生自蔓延高温合成反应，点燃温度800℃，反应时间5秒钟，最后得到疏松多孔块体，简单粉碎后筛选得到复合颗粒。Titanium powder, aluminum powder and graphite powder are used as raw materials, and the proportions of raw materials are 71.1%, 20% and 8.9% in terms of mass percentage, and the mixture A is obtained by ball milling for 5 hours, and then the diamond abrasive with a particle size of 200 μm is selected. Carry out ball milling with mixture A for 5 hours, make these powders fully mix uniformly to obtain mixture B, wherein the diamond abrasive is weighed according to the ratio of 50% of the total mass percentage of raw materials; fill the obtained mixture B into a steel mold, and press Pressurize 100MPa on the machine to obtain a circular body with a diameter of 20mm (the same below) with a relative density of about 70%. Finally, the green body is ignited by a plasma spray gun to cause a self-propagating high-temperature synthesis reaction. The ignition temperature is 800°C and the reaction time is After 5 seconds, a loose porous block is finally obtained, which is simply crushed and screened to obtain composite particles.
获得的复合颗粒内核粒径约220μm，包覆层厚度约10μm。The particle diameter of the inner core of the obtained composite particle is about 220 μm, and the thickness of the coating layer is about 10 μm.
图3为使用本实施例复合颗粒作磨粒制备的金刚石树脂砂轮的外观。实验表明，采用相同的树脂粘结剂，本砂轮要比表面没有处理的普通金刚石磨粒制备的砂轮工作效率得到了很大的提高。制备砂轮规格:300*15*20,浓度为100%的树脂结合剂砂轮。磨削聚晶金刚石复合片材料，采用普通金刚石磨粒制备的砂轮，使用寿命为295件/每片砂轮，采用本文复合颗粒制备的砂轮使用寿命为390件/每片砂轮；因此，本砂轮比未自蔓延工艺处理的金刚石树脂砂轮,在使用过程中，复合颗粒不易脱落，使用寿命提高了33%以上。Fig. 3 is the appearance of the diamond resin grinding wheel prepared by using the composite particles of this embodiment as abrasive grains. Experiments show that, using the same resin binder, the grinding wheel has a greatly improved work efficiency than the grinding wheel prepared by ordinary diamond abrasive grains without surface treatment. Preparation of grinding wheel specifications: 300*15*20, resin bonded grinding wheel with a concentration of 100%. Grinding polycrystalline diamond composite sheet materials, the grinding wheel prepared by ordinary diamond abrasive grains has a service life of 295 pieces/each grinding wheel, and the grinding wheel prepared by using the composite particles in this paper has a service life of 390 pieces/each grinding wheel; therefore, the grinding wheel ratio The diamond resin grinding wheel that has not been treated by self-propagating process, during use, the composite particles are not easy to fall off, and the service life is increased by more than 33%.
实施例2Example 2
采用钛粉、铝粉和石墨粉为原料，其原料配比按质量百分比计分别为73.8%、13.8%和12.4%，通过球磨6h使这些粉料充分混合均匀得混合料A，再选用粒度为400μm的立方氮化硼磨料与混合料A球磨5h，使这些粉料充分混合均匀得混合料B，其中立方氮化硼磨料按质量百分比50%的比例称取；将所得混合料B填充入钢模具中，在压片机上加压100MPa，得到相对密度约65%的坯体，最后通过等离子体喷枪点燃坯体，使其发生自蔓延高温合成反应，点燃温度850℃，反应时间4秒钟，最后得到疏松多孔块体，简单粉碎后筛选得到复合颗粒。Titanium powder, aluminum powder and graphite powder are used as raw materials, and the raw material proportions are 73.8%, 13.8% and 12.4% respectively by mass percentage. These powders are fully mixed and evenly obtained by ball milling for 6 hours to obtain a mixture A, and then the particle size is selected. The 400μm cubic boron nitride abrasive is ball milled with the mixture A for 5 hours, and these powders are fully mixed to obtain a mixture B, wherein the cubic boron nitride abrasive is weighed in a proportion of 50% by mass; the obtained mixture B is filled into steel In the mold, press 100 MPa on the tablet press to obtain a green body with a relative density of about 65%. Finally, the green body is ignited by a plasma spray gun to cause a self-propagating high-temperature synthesis reaction. The ignition temperature is 850 ° C, and the reaction time is 4 seconds. Finally, a loose porous block is obtained, which is simply crushed and screened to obtain composite particles.
获得的复合颗粒内核粒径450μm，包覆层厚度为25μm。The core particle diameter of the obtained composite particle is 450 μm, and the thickness of the coating layer is 25 μm.
实施例3Example 3
采用钛粉、铝粉和石墨粉为原料，其原料配比按质量百分比计分别为65%、20%和15%，通过球磨5h使这些粉料充分混合均匀得混合料A，再选用粒度为100μm的碳化硼磨料与混合料A通过球磨5h，使这些粉料充分混合均匀得混合料B，其中碳化硼磨料按质量百分比50%的比例称取；将所得混合料B填充入钢模具中，在压片机上加压100MPa，得到相对密度约75%的坯体，最后通过等离子体喷枪点燃坯体，使其发生自蔓延高温合成反应，点燃温度800℃，反应时间3.5秒钟，最后得到疏松多孔块体，简单粉碎后筛选得到复合颗粒。Titanium powder, aluminum powder and graphite powder are used as raw materials, and the raw material proportions are 65%, 20% and 15% respectively by mass percentage. These powders are fully mixed and uniformly obtained by ball milling for 5 hours to obtain a mixture A, and then the particle size is selected. The 100 μm boron carbide abrasive and the mixture A are ball milled for 5 hours, and these powders are fully mixed to obtain the mixture B, wherein the boron carbide abrasive is weighed in a proportion of 50% by mass; the obtained mixture B is filled into a steel mold, Press 100MPa on the tablet press to obtain a green body with a relative density of about 75%. Finally, the green body is ignited by a plasma spray gun to cause a self-propagating high-temperature synthesis reaction. The ignition temperature is 800°C, and the reaction time is 3.5 seconds. Porous block, simple crushing and screening to obtain composite particles.
获得的复合颗粒内核粒径130μm，包覆层厚度为15μm。The core diameter of the obtained composite particle is 130 μm, and the thickness of the coating layer is 15 μm.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410816419.4ACN104531069A (en) | 2014-12-25 | 2014-12-25 | Superhard material particle/titanium-aluminum composite particle having core-shell structure and preparation method thereof |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410816419.4ACN104531069A (en) | 2014-12-25 | 2014-12-25 | Superhard material particle/titanium-aluminum composite particle having core-shell structure and preparation method thereof |
| Publication Number | Publication Date |
|---|---|
| CN104531069Atrue CN104531069A (en) | 2015-04-22 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410816419.4APendingCN104531069A (en) | 2014-12-25 | 2014-12-25 | Superhard material particle/titanium-aluminum composite particle having core-shell structure and preparation method thereof |
| Country | Link |
|---|---|
| CN (1) | CN104531069A (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104842286A (en)* | 2015-05-20 | 2015-08-19 | 广东工业大学 | Superhard grinding tool and manufacturing method thereof |
| CN109136605A (en)* | 2017-06-27 | 2019-01-04 | 中国科学院上海硅酸盐研究所 | A kind of self-propagating synthesis of copper-based composite granule and its application |
| CN109913684A (en)* | 2019-03-19 | 2019-06-21 | 丽水学院 | A kind of method for rapidly preparing titanium-aluminum porous material |
| CN110078511A (en)* | 2019-03-11 | 2019-08-02 | 昆明理工大学 | A kind of Ti3AlC2The preparation method of base ceramic bond diamond boring means cutter head |
| Title |
|---|
| 梁宝岩等: "自蔓延高温烧结制备陶瓷结合剂金刚石复合材料", 《金刚石与磨料磨具工程》* |
| 穆云超等: "自蔓延高温法在金刚石表面涂覆钛铝涂层的研究", 《金刚石与磨料磨具工程》* |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104842286A (en)* | 2015-05-20 | 2015-08-19 | 广东工业大学 | Superhard grinding tool and manufacturing method thereof |
| CN109136605A (en)* | 2017-06-27 | 2019-01-04 | 中国科学院上海硅酸盐研究所 | A kind of self-propagating synthesis of copper-based composite granule and its application |
| CN109136605B (en)* | 2017-06-27 | 2021-02-12 | 中国科学院上海硅酸盐研究所 | Self-propagating synthesis of copper-based composite powder and application thereof |
| CN110078511A (en)* | 2019-03-11 | 2019-08-02 | 昆明理工大学 | A kind of Ti3AlC2The preparation method of base ceramic bond diamond boring means cutter head |
| CN109913684A (en)* | 2019-03-19 | 2019-06-21 | 丽水学院 | A kind of method for rapidly preparing titanium-aluminum porous material |
| CN109913684B (en)* | 2019-03-19 | 2021-03-23 | 丽水学院 | Method for rapidly preparing titanium-aluminum porous material |
| Publication | Publication Date | Title |
|---|---|---|
| CN103722174B (en) | A self-sharpening polycrystalline diamond composite sheet and its preparation method | |
| CN101560624B (en) | Method for preparing polycrystalline cubic boron nitride | |
| CN103273433B (en) | Diamond cutting abrasive disc | |
| CN107098704A (en) | A kind of preparation method of polycrystalline cubic boron nitride sintered material | |
| CN106378717A (en) | Production method and application of multicrystal diamond tablet | |
| WO2012024884A1 (en) | A diamond grinding wheel with self-propagating and pressureless sintered metal bonding agents and the method for making the same | |
| CN103009270A (en) | Online self-sharpening metallic bond and super-hard abrasive precision grinding pellet and preparation method thereof | |
| CN106985085A (en) | A kind of metal anchoring agent diamond wheel | |
| CN103464764B (en) | Metal matrix wear-resistant corrosion-resistant surface coating composite and preparation method thereof | |
| CN101524779A (en) | Brazing technology for diamond | |
| CN104531069A (en) | Superhard material particle/titanium-aluminum composite particle having core-shell structure and preparation method thereof | |
| CN103521774A (en) | Method for preparing diamond segment tool through self-propagating reaction | |
| CN101869985B (en) | Method for preparing metal ceramic coating material with plasma/combustion synthesis/quasistatic pressing process | |
| CN105437091A (en) | Large-pore resin binder superhard material grinding wheel for stainless steel end face grinding and manufacturing method thereof | |
| CN108789187A (en) | A kind of bronze base diamond grinding wheel and preparation method thereof | |
| CN104607110A (en) | Manufacturing method for cubic boron nitride crystal | |
| CN111673087B (en) | A kind of preparation method of aluminum magnesium boron abrasive tool and abrasive tool | |
| CN101829587B (en) | Powdered catalyst for synthesizing octahedral diamond | |
| CN105154706A (en) | Preparation method for high-performance ultrafine hard alloy | |
| CN102601746A (en) | Abrasive disc for flexible abrasive tool and method for manufacturing abrasive disc | |
| CN113462358A (en) | Production process of super-hard wear-resistant polymerized abrasive | |
| CN103243252B (en) | Binder-phase wolfram-carbide (WC) hard alloy and preparation method thereof | |
| CN108818329B (en) | Diamond grinding wheel and preparation method thereof | |
| CN109227411B (en) | An environmentally friendly resin cymbal grinding wheel | |
| CN104175237B (en) | Rare earth modified tungstenio binder diamond emery wheel and manufacture method thereof |
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | Application publication date:20150422 | |
| RJ01 | Rejection of invention patent application after publication |