WO2016101156A1

WO2016101156A1 - Ceramic steel material and preparation method thereof

Info

Publication number: WO2016101156A1
Application number: PCT/CN2014/094719
Authority: WO
Inventors: 颜嘉林; 张颜彬
Original assignee: 湖北宝德隆商贸有限公司
Priority date: 2014-12-23
Filing date: 2014-12-23
Publication date: 2016-06-30
Also published as: EP3192887A1; US20160348219A1; CN105917014A

Abstract

Disclosed is a ceramic steel material, which comprises a ceramic phase and a metallic phase. The ceramic phase is a boride of Fe, Co and Ni and any one or more of metallic elements of the fourth, fifth and sixth periods of Groups IVB, VB and VIB; the metallic phase is an alloy composed of Mo and one or more elements of Fe, Co and Ni. The ceramic material has the characteristics of high hardness, wear resistance, corrosive resistance and high temperature resistance and is applicable to manufacturing of cutters, cutting tools as well as a wide variety of wear-resistant, corrosion-resistant and high-temperature-resistance materials and various structural parts composed thereof. In addition, the ceramic steel material has excellent welding performance when welded with metallic materials such as steel, can better meet the demands of people during daily life, and is applied in the fields like industry, agriculture, machining, medical instruments, etc.; also provided is a preparation method of the ceramic steel material.

Description

Ceramic steel material and preparation method thereof

Technical field

The invention relates to a composite material, in particular to a ceramic steel material and a preparation method thereof.

Background technique

With the development of social science and technology and the continuous improvement of people's living standards, people's requirements for daily necessities are getting higher and higher. People have not only been limited to the quality and function of the products, but also put forward higher requirements on the appearance of their appearance. As one of the must-have tools in the kitchen, knives and cutting tools are always in the environment of water, steam, salt, acid, etc., which is a great test for the corrosion resistance of materials. At the same time, tools and cutting tools are used to cut food. Therefore, the requirements for the strength and hardness of the material are higher.

At present, materials commonly used in the market for manufacturing tools and cutting tools are stainless steel, ceramics and the like. Since the advent of stainless steel in 1913, it has been favored by people for its high toughness and corrosion resistance, laying a material and technical foundation for the development of modern industry and the advancement of science and technology. Therefore, it plays an important role in the production of cutting tools and cutting tools. However, due to its low hardness and poor wear resistance, the cutting edge is easy to be blunt during use, and the edge is not sharp, requiring frequent grinding. Zirconium dioxide ceramic knives and cutting tools have been developed in recent years as a new type of cutting tool and cutting tool with high hardness, wear resistance and high temperature resistance. However, the zirconia ceramic cutter and cutting tool have a fatal defect that is brittle and has poor impact resistance. The cutting edge of the cutting tool and the cutting tool is very thin, and it is easy to chip and cause a gap when used, thereby affecting the zirconium dioxide. The service life of ceramic tools and cutting tools. To this end, in order to better meet the needs of people in their daily lives, researchers are keen to study a composite material with high hardness, wear resistance, corrosion resistance and high temperature resistance.

technical problem

The technical problem to be solved by the present invention is to provide a ceramic steel material having high hardness, wear resistance, corrosion resistance, high temperature resistance and good toughness and a preparation method thereof.

Technical solution

The technical solution adopted to solve the technical problem of the present invention is to provide a ceramic steel material including a ceramic phase and a metal phase, the ceramic phase being Fe, Co, Ni, and IVB, VB, and VIB a boride of any one or more of the metal elements of the fourth, fifth, and sixth cycles; the metal phase is an alloy of Mo and one or more of Fe, Co, and Ni.

Preferably, the ceramic steel material further comprises an additive, wherein the additive is One or more of C and V, Cr, Mn, and Cu.

Preferably, the mass percentage of each constituent element in the ceramic steel material is 5 to 10% of B, 0 to 50% of Ti, 0 to 50% of V, 0 to 50% of Cr, and 0 to 50%. Zr, 0~50% Nb, 20~60% Mo, 10~40% Fe, 0~15% Ni, 0~20% Co; the mass percentage of each element in the additive No more than 5%.

The technical solution adopted to solve another technical problem of the present invention is to provide a method for preparing a ceramic steel material, characterized in that the steps of the preparation method include:

The ratio of the raw materials (ceramic phase raw material and metal phase raw material) powder and the grinding medium are wet-mixed for 20 to 100 hours, and a molding agent with a mass ratio of 2 to 6% is added, and the grinding ball is made of a hard alloy ball or a stainless steel ball. And one of the corundum balls, the ball mass ratio is (3~10): 1;

The slurry obtained after mixing is dried, and the obtained powder is sieved through 200 to 400 mesh, at 100 to 400 Pressed into a compact under MPa pressure;

After the compact is sintered at 1200 to 1500 ° C, a ceramic steel material is obtained.

Preferably, the ball milling medium is one of anhydrous ethanol, gasoline, acetone, hexane, carbon tetrachloride, and benzene.

Preferably, the molding agent is one of paraffin wax, zinc stearate, polyvinyl butyral anhydrous ethanol solution, and rubber gasoline solution composed of n-alkane.

Preferably, the drying method is one of vacuum drying, steam drying, and atomization drying.

Preferably, the sintering is one of vacuum sintering, hot isostatic pressing sintering, activation sintering, and discharge plasma sintering.

Beneficial effect

Compared with the prior art, the ceramic steel material of the present invention comprises a ceramic phase and a metal phase, wherein the ceramic phase is Fe, Co, Ni, and any one of the fourth, fifth, and sixth periodic metal elements of the IVB, VB, and VIB families. Or a boride of a plurality of metal elements, the metal phase being an alloy of Mo and one or more of Fe, Co, and Ni. The ceramic steel material of the invention has the characteristics of high hardness, wear resistance, corrosion resistance and high temperature resistance, and can be used for making tools, cutting tools, and various structural parts of various wear-resistant, corrosion-resistant, high-temperature resistant materials and their compositions. Moreover, ceramic steel materials and metal materials such as steel have good welding performance, can better meet the needs of people in daily life, and are used in the fields of industry, agriculture, mechanical processing and medical equipment. Further, with the preparation method of the present invention, the raw material reacts during the sintering process to form boride or polyboride in situ, which provides high hardness to the ceramic steel material.

DRAWINGS

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a microstructural view of a ceramic steel material of the present invention under a scanning electron microscope.

Embodiments of the invention

The present invention will be further described in detail below with reference to the accompanying drawings and embodiments. It is understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

The boride of any one or more of the metal elements of the fourth, fifth, and sixth cycles of Fe, Co, Ni, and IVB, VB, and VIB is a ceramic phase, and one of Mo and Fe, Co, and Ni Alloys of various compositions are used as the metal phase and a small amount of additives are added. The raw material may be added in the form of an alloy or a compound, or may be added in a simple form, and the accurately proportioned raw materials (ceramic phase raw material and metal phase raw material) powder are wet-ground mixed with the ball milling medium for 20 to 100 hours, and the mass ratio is added. 2~6% of molding agent, grinding ball is selected from one of cemented carbide ball, stainless steel ball and corundum ball. The mass ratio of the ball material is (3~10):1; the slurry obtained after mixing is dried, and the obtained powder is obtained. After screening from 200 to 400 mesh, at 100~400 The compact is made under MPa pressure; after the compact is sintered at 1200~1500 °C, the ceramic steel material is obtained.

With the above preparation method, the raw material reacts during the sintering process to form boride or polyboride in situ, which provides high hardness to the ceramic steel material. The in-situ precipitated ceramic phase has a better bonding strength with the metal phase, so the ceramic steel material also has higher toughness. Therefore, ceramic steel materials have excellent comprehensive mechanical properties. The ceramic steel material of the invention has a hardness of 50~75 HRC, comparable to zirconia ceramics, and flexural strength up to 1200~2300 MPa, much higher than zirconia ceramics. Compared with the widely used stainless steel, ceramic steel has higher hardness, more than double the wear resistance, and it has excellent chemical stability, so it is suitable for water, steam, and water all year round. Tools, cutting tools in the working environment such as salt, acid and alkali, as well as various structural parts of various wear-resistant, corrosion-resistant, high-temperature resistant materials and their compositions. In addition, ceramic steel materials have good welding properties with steel, so only a small amount of ceramic steel material can be welded to stainless steel, which can achieve reasonable control of ceramic steel cutting tools, cutting tools, and various wear and corrosion resistance. The production cost of high temperature resistant materials and various structural parts of the composition is easy to realize and widely used.

The ceramic steel material of the invention has the characteristics of high hardness, wear resistance, corrosion resistance and high temperature resistance, and can be used for making tools, cutting tools, and various structural parts of various wear-resistant, corrosion-resistant, high-temperature resistant materials and their compositions. Moreover, ceramic steel materials and metal materials such as steel have good welding performance, can better meet the needs of people in daily life, and are used in the fields of industry, agriculture, mechanical processing and medical equipment. The ceramic steel material comprises a ceramic phase and a metal phase, wherein the ceramic phase is Fe, Co, Ni, and a boride of any one or more metal elements of the fourth, fifth, and sixth periodic metal elements of the IVB, VB, and VIB groups, The metal phase is an alloy of Mo and one or more of Fe, Co, and Ni. The raw materials can be added in the form of alloys or compounds, and can be added in the form of simple substances. After accurately mixing the raw materials by ball milling, drying, sieving, pressing and sintering, ceramic steel materials are obtained.

The tool and cutting tool made of ceramic steel have the advantages of stainless steel cutter, cutting tool and zirconia ceramic cutter and cutting tool, so as to avoid the disadvantages of both, ceramic steel cutter and cutting tool can be used to replace the existing stainless steel. Cutting tools, cutting tools and zirconia ceramic knives and cutting tools are not only durable, but also cost-effective and easy to implement.

In order to explain the technical solution described in the present invention, the following description will be made by way of specific embodiments:

Example 1:

A method for preparing a ceramic steel material, the method comprising the steps of: 20 wt.% (mass ratio: 20%) NiB, 40 wt.% Mo, 5 wt.% Cr, 10 wt.% Ni, 1 wt.% C and Fe powder (balance) and an additional 2.5 wt.% paraffin ball mill mix. The mass ratio of the cemented carbide ball to the mixed powder (NiB, Mo, Cr, Ni, C, and Fe powder) was 8:1, and anhydrous ethanol was added as a ball milling medium, and wet-milled in a ball mill for 100 hours (h). Then, it was vacuum dried at 70 ° C for 7 hours, and the obtained powder was passed through. The 325 mesh was sieved and pressed to form. Finally, the press-formed sample was vacuum sintered at 1220 ° C for 15 hours to obtain a ceramic steel material.

Example 2:

A method for preparing a ceramic steel material, the method comprising: 20 wt.% of FeB, 60 wt.% of Mo, 5 wt.% of Cr, 10 wt.% of Ni, 1 wt.% of C and Fe powder (balance), and 2.2 wt.% of paraffin ball mill were mixed. The mass ratio of the cemented carbide ball to the mixed powder (FeB, Mo, Cr, Ni, C and Fe powder) was 6:1, acetone was added as a ball milling medium, and wet-milled in a ball mill for 85 hours. Then dried under vacuum at 80 ° C for 6 h. The powder was sieved through 325 mesh and pressed to form. Finally, the pressed sample was vacuum sintered at 1250 ° C for 14 h to obtain a ceramic steel material.

Example 3:

A method for preparing a ceramic steel material, the method comprising: 20 wt.% of CoB, 40 wt.% W, 20 wt.% Co, 10 wt.% Ni, 1 wt.% C and Fe powder (balance) and plus 2 wt.% of the rubber gasoline solution was ball milled and mixed. The mass ratio of the stainless steel ball to the mixed powder (CoB, W, Co, Ni, C, and Fe powder) was 5:1, and hexane was added as a ball milling medium, and wet-milled in a ball mill for 65 hours. Then, it was vacuum dried at 60 ° C for 10 h, and the obtained powder was sieved through 300 mesh and then press-molded. Finally, the pressed sample was hot isostatically pressed at 1280 ° C for 12 h to obtain a ceramic steel material.

Example 4:

A method for preparing a ceramic steel material, the method comprising: 50 wt.% of TiB ₂ , 20 wt.% of Mo, 5 wt.% of Cr, 15 wt.% of Ni, 1 wt.% of C and Fe powder (balance) And a 2.5 wt.% rubber gasoline solution was ball milled and mixed. The mass ratio of the stainless steel ball to the mixed powder (TiB ₂ , Mo, Cr, Ni, C and Fe powder) was 3:1, carbon tetrachloride was added as a ball milling medium, and wet grinding was carried out in a ball mill for 80 h. Then, it was atomized and dried at 90 ° C for 8 hours, and the obtained powder was sieved through 200 mesh and then press-molded. Finally, the pressed sample was hot isostatically pressed at 1300 ° C for 12 h to obtain a ceramic steel material.

Example 5:

A method for preparing a ceramic steel material, the method comprising: 50 wt.% of ZrB ₂ , 20 wt.% of Mo, 5 wt.% of Cr, 15% by weight of Ni, 1 wt.% of C and Fe powder (remaining And) plus 3wt.% zinc stearate ball mill mixing. The mass ratio of corundum ball to mixed powder (ZrB ₂ , Mo, Cr, Ni, C and Fe powder) was 5:1, benzene was added as a ball milling medium, and wet-milled in a ball mill for 90 h. Then, it was atomized and dried at 70 ° C for 5 hours, and the obtained powder was sieved through 400 mesh and then press-molded. Finally, the pressed sample was sintered by a discharge plasma at 1280 ° C for 2 h to obtain a ceramic steel material.

Example 6

A method for preparing a ceramic steel material, the method comprising: 50 wt.% of NbB ₂ , 20 wt.% of Mo, 5 wt.% of Cr, 15 wt.% of Ni, 1 wt.% of C and Fe powder (balance) And a 3 wt.% polyvinyl butyral anhydrous ethanol solution was ball milled and mixed. The mass ratio of corundum ball to mixed powder (NbB ₂ , Mo, Cr, Ni, C and Fe powder) was 5:1, gasoline was added as a ball milling medium, and wet-milled in a ball mill for 75 h. Then, it was steam-dried at 90 ° C for 8 hours, and the obtained powder was sieved through 400 mesh and press-molded. Finally, the pressed sample was activated and sintered at 1250 ° C for 15 h to obtain a ceramic steel material.

Example 7

A method for preparing a ceramic steel material, the method comprising: 25 wt.% of FeB, 35 wt.% of Mo, 10 wt.% of Cr, 5 wt.% of Ni, 0.6 wt.% of C, 2 wt.% of V, 5 wt.% of Cu and Fe powder (balance), and 3 wt.% of paraffin ball mill were mixed. The mass ratio of corundum ball to mixed powder (FeB, Mo, Cr, Ni, C, V, Cu and Fe powder) was 6:1, gasoline was added as a ball milling medium, and wet-milled in a ball mill for 60 h. Then, it was vacuum-dried at 90 ° C for 8 hours, and the obtained powder was sieved through 400 mesh and then press-molded. Finally, the pressed sample was vacuum sintered at 1300 ° C for 15 h to obtain a ceramic steel material.

Table 1 Hardness and flexural strength of ceramic steel materials

Example	Hardness (HRC)	Bending strength (MPa)
1	65	2017
2	68	2278
3	67	1882
4	72	1635
5	75	1340
6	71	1390
7	70	1720

The above is only the preferred embodiment of the present invention, and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection of the present invention. Within the scope.

Claims

A ceramic steel material, characterized in that the ceramic steel material comprises a ceramic phase and a metal phase, and the ceramic phase is Fe, Co, Ni and a boride of any one or more of the metal elements of the fourth, fifth, and sixth cycles of the IVB, VB, and VIB groups; the metal phases are Mo and Fe, Co, Ni An alloy composed of one or more elements.
The ceramic steel material according to claim 1, wherein said ceramic steel material further comprises an additive, said additive being One or more of C and V, Cr, Mn, and Cu.
The ceramic steel material according to any one of claims 1 to 2, wherein the mass percentage of each constituent element in the ceramic steel material is 5 to 10% of B, 0 to 50% of Ti, and 0 to 50%. V, 0~50% Cr, 0~50% Zr, 0~50% Nb, 20~60% Mo, 10~40% Fe, 0~15% Ni, 0~20% Co; the content of each element in the additive is not more than 5% by mass.
A ceramic steel material according to any one of claims 1 to 3 for use in the manufacture of tools, cutting tools, and various structural members of various wear resistant, corrosion resistant, high temperature resistant materials and compositions thereof.