CN103757513A - A Al2O3/Ti (C, N) nanocomposite cermet mold material and its prepn - Google Patents

Abstract

The invention discloses an Al2O3/Ti(C,N) nano-composite metal ceramic die material. The Al2O3/Ti(C,N) nano-composite metal ceramic die material is characterized by being formed by performing hot-pressed sintering by taking nano-Al2O3 as a matrix, taking nano-Ti(C,N) as a hard dispersed phase, taking micron metals Mo, Ni and Cr as binding phases, and adding one or two of oxides Y2O3 and TiO2, and two or more of carbides TaC, NbC and VC as sintering aids. Compared with a die taking die steel or hard alloy as a material, the metal ceramic die material disclosed by the invention is more excellent in wear resistance, antioxidation and thermal shock resistance, and good in strength and toughness, as well as also has an application prospect in the aspects of tools and wear-resistant and corrosion-resistant components besides production for dies.

Description

Translated fromChinese

一种Al2O3/Ti(C,N)纳米复合金属陶瓷模具材料及制备方法A kind of Al2O3/Ti(C,N) nanocomposite cermet mold material and its preparation method

 the

    本发明涉及一种陶瓷模具材料及制备方法，特别涉及一种Al₂O₃/Ti(C,N)纳米复合金属陶瓷模具材料及制备方法。The invention relates to a ceramic mold material and a preparation method, in particular to an Al₂ O₃ /Ti(C,N) nanometer composite cermet mold material and a preparation method.

背景技术Background technique

热挤压模具是金属型材热挤压成型的关键零部件和易损件，在铜合金、铝合金的热挤压成型中应用广泛，目前生产中普遍应用的模具材料主要是模具钢、硬质合金等。但不论是模具钢还是硬质合金，由于常处于高温高压的恶劣工作环境中，承受应力大、受热疲劳和热磨损的交互作用，容易发生碎裂、磨损、热震裂纹及与挤压金属及其氧化物粘连，因而模具的使用寿命较低，其硬度、耐磨性能已很难满足实际生产的需要。Hot extrusion dies are key parts and wearing parts for hot extrusion of metal profiles. They are widely used in hot extrusion of copper alloys and aluminum alloys. At present, the mold materials commonly used in production are mainly die steel, hard Alloy etc. However, whether it is die steel or cemented carbide, due to the harsh working environment of high temperature and high pressure, it is subject to high stress, thermal fatigue and thermal wear, and is prone to fragmentation, wear, thermal shock cracks and contact with extruded metal and Its oxide sticks, so the service life of the mold is low, and its hardness and wear resistance can hardly meet the needs of actual production.

 金属陶瓷的热稳定性和耐磨性极佳，且具有高硬度、耐高温、不粘模等特点，其耐磨性比高速钢和硬质合金好，在高温下更具有金属材料不可比拟的优点如高温硬度高、耐腐蚀、抗氧化性能好等，是制造成型模具的理想材料。目前研究和应用陶瓷材料作模具的领域多限于拉丝模和挤压模，所用陶瓷材料主要有Sialon陶瓷、TZP陶瓷、ZTA陶瓷，应用研究报导大多局限于微米级复合陶瓷材料。尽管金属陶瓷有着不可比拟的优点，但其基本特征脆性大、韧性低，因而其作为模具仍需进一步提高强度和韧性，满足实际生产的需要。Cermet has excellent thermal stability and wear resistance, and has the characteristics of high hardness, high temperature resistance, non-stick mold, etc. Its wear resistance is better than high-speed steel and hard alloy, and it has the incomparable performance of metal materials at high temperatures Advantages such as high temperature hardness, corrosion resistance, good oxidation resistance, etc., are ideal materials for manufacturing molding dies. At present, the field of research and application of ceramic materials as molds is mostly limited to wire drawing dies and extrusion dies. The ceramic materials used mainly include Sialon ceramics, TZP ceramics, and ZTA ceramics. Most of the application research reports are limited to micron-scale composite ceramic materials. Although cermets have incomparable advantages, their basic characteristics are high brittleness and low toughness. Therefore, as a mold, the strength and toughness still need to be further improved to meet the needs of actual production.

发明内容Contents of the invention

本发明的目的是为了克服金属陶瓷模具韧性低、整体性能差的缺点，提供了一种Al₂O₃/Ti(C,N)纳米复合金属陶瓷模具材料及制备方法。The object of the present invention is to provide an Al₂ O₃ /Ti(C,N) nanocomposite cermet mold material and a preparation method thereof in order to overcome the disadvantages of low toughness and poor overall performance of the cermet mold.

一种Al₂O₃/Ti(C,N)纳米复合金属陶瓷模具材料，其特征在于，是以纳米Al₂O₃为基体，纳米Ti(C,N)作为硬质弥散相，微米金属Mo、Ni、Cr为粘结相，添加氧化物Y₂O₃和TiO₂中的一种或两种和碳化物TaC、NbC和VC中的两种或两种以上作为烧结助剂，经热压烧结制成。An Al₂ O₃ /Ti(C,N) nanocomposite cermet mold material, characterized in that it uses nanometer Al₂ O₃ as a matrix, nanometer Ti(C,N) as a hard dispersed phase, and micron metal Mo , Ni, Cr as the binder phase, add one or two of oxides Y₂ O₃ and TiO₂ and two or more of carbides TaC, NbC and VC as sintering aids, after hot pressing Made by sintering.

上述Al₂O₃/Ti(C,N)纳米复合金属陶瓷模具材料各组分体积比例为：纳米Ti(C,N)为20％～60％，微米Mo为0.5％～5％，微米Ni为0.5％～5％，微米Cr为1％～5％，Y₂O₃为0.2％～2％，TiO₂为0.2％～2％，T_aC为0.5%～5%、N_bC为 0.5%～5%、VC为0.5%～5%，余量为纳米Al₂O₃，所述的弥散相Ti(C,N)的体积百分比为30％～40％，所述各金属粘结相的体积百分比Mo为0.5％～2％，Ni为0.5％～2％，Cr为1％～3％，所述氧化物Y₂O₃和TiO₂中的一种或两种占材料总体积的百分比为0.2％～1％，所述碳化物TaC、NbC和VC中的两种或两种以上占材料总体积的百分比为1.5％～3％。 The volume ratio of each component of the above Al₂ O₃ /Ti(C,N) nanocomposite cermet mold material is: nano Ti(C,N) is 20%~60%, micron Mo is 0.5%~5%, micron Ni 0.5% to 5%, micron Cr is 1% to 5%, Y₂ O₃ is 0.2% to 2%, TiO₂ is 0.2% to 2%, T_a C is 0.5% to 5%, N_b C is 0.5% to 5%, VC is 0.5% to 5%, the balance is nano Al₂ O₃ , the volume percentage of the dispersed phase Ti(C,N) is 30% to 40%, and the metal bonding The volume percentage of the phase Mo is 0.5% to 2%, Ni is 0.5% to 2%, and Cr is 1% to 3%, and one or both of the oxides Y₂ O₃ and TiO₂ account for the total volume of the material The percentage of two or more of the carbides TaC, NbC and VC in the total volume of the material is 1.5% to 3%.

上述Al₂O₃粉为：市售的α- Al₂O₃粉，其纯度均大于99％，粒度为60nm；Ti(C,N)粉采用市售的Ti(C,N)粉，其纯度均大于99％，粒度为50nm。The above-mentioned Al₂ O₃ powder is: commercially available α-Al₂ O₃ powder, the purity of which is greater than 99%, and the particle size is 60nm; the Ti(C,N) powder is commercially available Ti(C,N) powder, whose The purity is greater than 99%, and the particle size is 50nm.

纳米复合金属陶瓷模具材料及制备方法，包括下述工艺步骤：Nanocomposite cermet mold material and preparation method, comprising the following process steps:

 1、将Ti(C,N)为20-60%、Mo0.5-5%、Ni0.5-5%、Cr1-5%、Y₂O₃0.2-2%_、TiO₂0.2-2%、TaC0.5-5%、Nb0.5-5%、VC0.5-5%，Al₂O₃为余量的原料，混合放入球磨罐中，以无水乙醇为介质，以氧化锆球为研磨体，球磨20～48h；与氧化锆球的料球重量比为1：2～10。1. Make Ti(C,N) 20-60%, Mo0.5-5%, Ni0.5-5%, Cr1-5%, Y₂ O₃ 0.2-2%_, TiO₂ 0.2-2%, TaC0.5-5%, Nb0.5-5%, VC0.5-5%, Al₂ O₃ as the rest of the raw materials, mix them into a ball mill jar, use absolute ethanol as the medium, and zirconia balls as the medium Grinding body, ball milled for 20-48 hours; the weight ratio of balls to zirconia balls is 1:2-10.

2、球磨后的浆料放入真空干燥箱，在100℃下连续干燥，惰性气流氮气中过筛，密封备用；2. The slurry after ball milling is put into a vacuum drying oven, dried continuously at 100°C, sieved in an inert gas flow of nitrogen, and sealed for later use;

3、将步骤（2）所得粉料装入石墨模具于热压炉中在氮气保护下热压烧结成型，即得。上述百分比为体积百分比。3. Put the powder obtained in step (2) into a graphite mold, heat press and sinter it in a hot-press furnace under the protection of nitrogen to form it. The above percentages are volume percentages.

上述步骤（3）中的热压烧结工艺是：热压温度1550℃～1750℃，热压压力20MPa～30MPa，保温时间15～30min。The hot pressing sintering process in the above step (3) is: hot pressing temperature 1550°C-1750°C, hot pressing pressure 20MPa-30MPa, holding time 15-30min.

本发明的优点：Advantages of the present invention:

本发明的纳米复合金属陶瓷模具材料，通过添加纳米Ti(C,N)硬质弥散相，提高了材料的硬度、强度，添加微米金属Mo、Ni、Cr使材料的韧性进一步加强，而氧化物Y₂O₃、TiO₂的加入活化了晶格、降低烧结温度，改善可烧结性，碳化物TaC、NbC可与Ti(C,N)形成固溶体，改善抗塑性能力，抑制晶粒长大，VC可提高金属陶瓷的抗剪切强度和耐磨性。本发明的金属陶瓷模具材料与以模具钢或硬质合金为材料的模具相比，具有更优异的耐磨性、抗氧化、抗热震性，良好的强度和韧性，除可用于制作模具外，在刀具、耐磨耐蚀零部件方面也有应用前景。The nano-composite cermet mold material of the present invention improves the hardness and strength of the material by adding nano-Ti (C, N) hard disperse phase, and the toughness of the material is further strengthened by adding micron metals Mo, Ni, and Cr, while the oxide The addition of Y₂ O₃ and TiO₂ activates the lattice, lowers the sintering temperature, and improves sinterability. Carbide TaC and NbC can form solid solutions with Ti(C,N), improve plastic resistance, and inhibit grain growth. VC can improve the shear strength and wear resistance of cermets. Compared with molds made of mold steel or cemented carbide, the cermet mold material of the present invention has more excellent wear resistance, oxidation resistance, thermal shock resistance, good strength and toughness, and can be used for making moulds. , It also has application prospects in cutting tools, wear-resistant and corrosion-resistant parts.

具体实施方式：Specific implementation methods :

实施例1：Example 1:

纳米复合金属陶瓷模具材料，各组分体积百分比为：α- Al₂O₃为63.5％，Ti(C,N)为30％，Mo为1.5％，Ni为1.5％，Cr为1％，Y₂O₃为0.2％，TaC为0.8％，NbC为1.5％。将各组分原料按上述比例称量混合放入球磨罐中，以无水乙醇为介质，以氧化锆球为研磨体，原料与氧化锆球的料球重量比为1：8，球磨24h，然后将浆料放入真空干燥箱，在100℃下连续干燥，惰性气流氮气中过筛后粉料装入石墨模具在热压炉中氮气保护下热压烧结成型。热压温度1600℃，热压压力20MPa，保温时间15min。热压后获得的试件经切割加工，测出其力学性能如下：抗弯强度为796MPa，断裂韧性为9.05Mpa·m^1/2，硬度为20.3 GPa。Nanocomposite cermet mold material, the volume percentage of each component is: α-Al₂ O₃ is 63.5%, Ti(C,N) is 30%, Mo is 1.5%, Ni is 1.5%, Cr is 1%, Y₂ O₃ is 0.2%, TaC is 0.8%, NbC is 1.5%. Weigh and mix the raw materials of each component according to the above ratio and put them into a ball mill jar, use absolute ethanol as the medium, use zirconia balls as the grinding body, and the weight ratio of raw materials to zirconia balls is 1:8, and mill for 24 hours. Then put the slurry into a vacuum drying oven, dry continuously at 100°C, sieve the powder in an inert gas flow of nitrogen, put the powder into a graphite mold, and heat-press and sinter it in a hot-press furnace under the protection of nitrogen. The hot pressing temperature is 1600°C, the hot pressing pressure is 20 MPa, and the holding time is 15 minutes. The specimen obtained after hot pressing was cut and processed, and its mechanical properties were measured as follows: the flexural strength was 796MPa, the fracture toughness was 9.05Mpa·m^1/2 , and the hardness was 20.3 GPa.

实施例2：Example 2:

纳米复合金属陶瓷模具材料，各组分体积百分比为：α- Al₂O₃为62％，Ti(C,N)为32.5％，Mo为0.8％，Ni为1％，Cr为1.5％，Y₂O₃为0.5％，TaC为0.5％，VC为1.2％。将各组分原料按上述比例称量混合放入球磨罐中，以无水乙醇为介质，以氧化锆球为研磨体，原料与氧化锆球的料球重量比为1：8，球磨24h，然后将浆料放入真空干燥箱，在100℃下连续干燥，惰性气流氮气中过筛后粉料装入石墨模具在热压炉中氮气保护下热压烧结成型。热压温度1650℃，热压压力20MPa，保温时间15min。热压后获得的试件经切割加工，测出其力学性能如下：抗弯强度为782MPa，断裂韧性为8.74Mpa·m^1/2，硬度为21.6 GPa。Nanocomposite cermet mold material, the volume percentage of each component is: α-Al₂ O₃ is 62%, Ti(C,N) is 32.5%, Mo is 0.8%, Ni is 1%, Cr is 1.5%, Y_2O3 is 0.5%, TaC is 0.5%,_and VC is 1.2%. Weigh and mix the raw materials of each component according to the above ratio and put them into a ball mill jar, use absolute ethanol as the medium, use zirconia balls as the grinding body, and the weight ratio of raw materials to zirconia balls is 1:8, and mill for 24 hours. Then put the slurry into a vacuum drying oven, dry continuously at 100°C, sieve the powder in an inert gas flow of nitrogen, put the powder into a graphite mold, and heat-press and sinter it in a hot-press furnace under the protection of nitrogen. The hot-pressing temperature is 1650°C, the hot-pressing pressure is 20 MPa, and the holding time is 15 minutes. The specimen obtained after hot pressing was cut and processed, and its mechanical properties were measured as follows: the flexural strength was 782MPa, the fracture toughness was 8.74Mpa·m^1/2 , and the hardness was 21.6 GPa.

实施例3：Example 3:

纳米复合金属陶瓷模具材料，各组分体积百分比为：α- Al₂O₃为61.5％，Ti(C,N)为31.5％，Mo为1.4％，Ni为0.8％，Cr为2％，Y₂O₃为0.8％，NbC为1％，VC为0.8％。将各组分原料按上述比例称量混合放入球磨罐中，以无水乙醇为介质，以氧化锆球为研磨体，原料与氧化锆球的料球重量比为1：9，球磨36h，然后将浆料放入真空干燥箱，在100℃下连续干燥，惰性气流氮气中过筛后粉料装入石墨模具在热压炉中氮气保护下热压烧结成型。热压温度1650℃，热压压力25MPa，保温时间15min。热压后获得的试件经切割加工，测出其力学性能如下：抗弯强度为807MPa，断裂韧性为9.7Mpa·m^1/2，硬度为24.6 GPa。Nanocomposite cermet mold material, the volume percentage of each component is: α-Al₂ O₃ is 61.5%, Ti(C,N) is 31.5%, Mo is 1.4%, Ni is 0.8%, Cr is 2%, Y_2O3 is 0.8%, NbC is 1%_, and VC is 0.8%. Weigh and mix the raw materials of each component according to the above ratio and put them into a ball mill jar, use absolute ethanol as the medium, use zirconia balls as the grinding body, and the weight ratio of raw materials to zirconia balls is 1:9, and mill for 36 hours. Then put the slurry into a vacuum drying oven, dry continuously at 100°C, sieve the powder in an inert gas flow of nitrogen, put the powder into a graphite mold, and heat-press and sinter it in a hot-press furnace under the protection of nitrogen. The hot-pressing temperature is 1650°C, the hot-pressing pressure is 25 MPa, and the holding time is 15 minutes. The specimen obtained after hot pressing was cut and processed, and its mechanical properties were measured as follows: the flexural strength was 807MPa, the fracture toughness was 9.7Mpa·m^1/2 , and the hardness was 24.6 GPa.

实施例4：Example 4:

纳米复合金属陶瓷模具材料，各组分体积百分比为：α- Al₂O₃为63％，Ti(C,N)为30％，Mo为1％，Ni为1％，Cr为1.5％，Y₂O₃为0.5％、TiO₂为0.5％，TaC为1％，NbC为1％，VC为0.5％。将各组分原料按上述比例称量混合放入球磨罐中，以无水乙醇为介质，以氧化锆球为研磨体，原料与氧化锆球的料球重量比为1：10，球磨48h，然后将浆料放入真空干燥箱，在100℃下连续干燥，惰性气流氮气中过筛后粉料装入石墨模具在热压炉中氮气保护下热压烧结成型。热压温度1550℃，热压压力30MPa，保温时间15min。热压后获得的试件经切割加工，测出其力学性能如下：抗弯强度为810MPa，断裂韧性为9.85Mpa·m^1/2，硬度为25.3 GPa。Nanocomposite cermet mold material, the volume percentage of each component is: α-Al₂ O₃ is 63%, Ti(C,N) is 30%, Mo is 1%, Ni is 1%, Cr is 1.5%, Y₂ O₃ is 0.5%, TiO₂ is 0.5%, TaC is 1%, NbC is 1%, and VC is 0.5%. Weigh and mix the raw materials of each component according to the above ratio and put them into a ball mill jar, use absolute ethanol as the medium, use zirconia balls as the grinding body, and the weight ratio of raw materials to zirconia balls is 1:10, and mill for 48 hours. Then put the slurry into a vacuum drying oven, dry continuously at 100°C, sieve the powder in an inert gas flow of nitrogen, put the powder into a graphite mold, and heat-press and sinter it in a hot-press furnace under the protection of nitrogen. The hot-pressing temperature is 1550°C, the hot-pressing pressure is 30 MPa, and the holding time is 15 minutes. The specimen obtained after hot pressing was cut and processed, and its mechanical properties were measured as follows: the flexural strength was 810MPa, the fracture toughness was 9.85Mpa·m^1/2 , and the hardness was 25.3 GPa.

Claims (7)

1. an Al₂o₃/ Ti (C, N) nano composite ceramic die material, is characterized in that, is with nanometer Al₂o₃for matrix, nanometer Ti (C, N) is as hard disperse phase, and micron metal Mo, Ni, Cr are Binder Phase, adds oxide compound Y₂o₃and TiO₂in one or both and carbide TaC, NbC and two or more in VC as sintering aid hot pressed sintering, form.

2. a kind of Al according to claim 1₂o₃/ Ti (C, N) nano composite ceramic die material, is characterized in that, this material component is as follows: Ti (C, N) is that 20%～60%, Mo is that 0.5%～5%, Ni is that 0.5%～5%, Cr is 1%～5%, Y₂o₃be 0.2%～2%, TiO₂be that 0.2%～2%, TaC, NbC and VC are 0.5%～5%, all the other are Al₂o₃, above component is volume percent.

3. a kind of Al according to claim 1 and 2₂o₃/ Ti (C, N) nano composite ceramic die material, is characterized in that, the volume percent of described dispersed phase Ti (C, N) is 30%～40%.

4. a kind of Al according to claim 1 and 2₂o₃/ Ti (C, N) nano composite ceramic die material, is characterized in that, the volume percent of described each metallic binding phase is:

Mo is 0.5%～2%;

Ni is 0.5%～2%;

Cr is 1%～3%.

5. a kind of Al according to claim 1 and 2₂o₃/ Ti (C, N) nano composite ceramic die material, is characterized in that, described oxide compound Y₂o₃and TiO₂in one or both per-cents that account for material cumulative volume be 0.2%～1%.

6. a kind of Al according to claim 1 and 2₂o₃/ Ti (C, N) nano composite ceramic die material, is characterized in that, the per-cent that two or more in described carbide TaC, NbC and VC accounts for material cumulative volume is 1.5%～3%.

7. a kind of Al according to claim 1 and 2₂o₃/ Ti (C, N) nano composite ceramic die material, is characterized in that: comprise following processing step:

1. by volume per-cent meter to get Ti (C, N) be that 20%～60%, Mo is that 0.5%～5%, Ni is that 0.5%～5%, Cr is 1%～5%, Y₂o₃be 0.2%～2%, TiO₂be that 0.2%～2%, TaC, NbC and VC are 0.5%～5%, surplus is Al₂o₃raw material mix put into ball grinder, take dehydrated alcohol as medium, take zirconia ball as grinding element, ball milling 20～48h;

The pellet weight ratio of raw material and zirconia ball is 1:2～10;

2. the slurry after ball milling is put into vacuum drying oven, and successive drying at 100 ℃ sieves in inert gas nitrogen, seals standby;

3. by step 2. gained powder pack graphite jig Thermocompressed sintering and forming under nitrogen protection in hot pressing furnace into, obtain;

1550 ℃～1750 ℃ of hot pressing temperatures, hot pressing pressure 20MPa～30MPa, soaking time 15～30min.