阅读说明：本技术 一种高温结构用碳氮化钛基金属陶瓷材料及制备方法 (Titanium carbonitride base cermet material for high-temperature structure and preparation method thereof ) 是由 颜焰 鲁攀 刘毅 邱嵩 于 2020-12-24 设计创作，主要内容包括：本发明提供了一种高温结构用碳氮化钛基金属陶瓷材料及制备方法,解决了现有技术中炉内结构件所使用的耐高温材料,在高温下存在较明显的烧结收缩和变形,其结构精度以及结构件本身易出现裂纹/配合间隙,从而导致结构坍塌的技术问题。其通过原料TiCN、WC、Mo-2C、TaC、NbC、Co和Ni进行制备；Co和Ni的重量百分比含量之和为5-14%；原料中整体C的重量百分比含量为5.8-6.2%,且整体C与N的重量比为3-7:3-7。本发明提供的高温结构用碳氮化钛基金属陶瓷材料,能够良好满足高温工作环境炉内结构件的使用要求,在高温下烧结收缩和变形小,其结构精度以及结构件本身不易出现裂纹/配合间隙。(The invention provides a titanium carbonitride base cermet material for a high-temperature structure and a preparation method thereof, which solve the technical problems that high-temperature resistant materials used for furnace structural components in the prior art have obvious sintering shrinkage and deformation at high temperature, and the structural precision and the structural components are easy to crack/fit gaps, so that the structure collapses. It is prepared from TiCN, WC and Mo 2 C. Preparing TaC, NbC, Co and Ni; the sum of the weight percentage contents of Co and Ni is 5-14%; the weight percentage content of the whole C in the raw materials is 5.8-6.2%, and the weight of the whole C and the NThe ratio is 3-7: 3-7. The titanium carbonitride base cermet material for the high-temperature structure can well meet the use requirements of the structural component in a furnace in a high-temperature working environment, has small sintering shrinkage and deformation at high temperature, and has high structural precision and low possibility of crack/fit clearance of the structural component.)

1. A titanium carbonitride base cermet material for high temperature structures is characterized in that: the raw materials comprise TiCN, WC and Mo₂C. TaC, NbC, Co and Ni; wherein, the sum of the weight percentage contents of Co and Ni is 5-14%; the weight percentage content of the whole C in the raw material is 5.8-6.2%, and the weight ratio of the whole C to N in the raw material is 3-7: 3-7.

2. The titanium carbonitride-based cermet material for high temperature structures as set forth in claim 1, wherein: the sum of the weight percentage of Co and Ni is 8-10%, the weight percentage of C in the raw material is 5.8-6.2%, and the weight ratio of C to N is 5-6: 4-5.

3. The titanium carbonitride-based cermet material for high temperature structures as set forth in claim 2, wherein: the sum of the weight percentage contents of Co and Ni is 9%, the weight percentage content of C in the raw material is 6%, and the weight ratio of C to N is 5.5: 4.5.

4. A titanium carbonitride based cermet material for high temperature structures as set forth in any one of claims 1-3 characterized by: the weight percentage content of the TiCN is 55-65%; the weight percentage content of WC is 8-20%; mo₂Weight of CThe percentage content is 3-10%; the weight percentage content of TaC is 2-10%; the weight percentage content of NbC is 2-10%; and said TiCN, WC, Mo₂C. The sum of the contents of TaC, NbC, Co and Ni in percentage by weight is 100%.

5. The method for preparing a titanium carbonitride based cermet material for high temperature structures as set forth in any one of claims 1-4, characterized in that: the method comprises the following steps:

(1) RTP preparation: adding the raw materials into a ball mill according to the proportion, and simultaneously adding a dispersing agent, a forming agent and a forming auxiliary agent for ball milling; after ball milling, the ball milled material is placed in N₂Spray drying under the protection condition to obtain an RTP material for pressing;

(2) pressing: pressing the RTP material prepared in the step (1) into a blank in a mould at the pressure of 1.1-1.5T/cm²；

(3) Cold isostatic pressing: putting the blank pressed in the step (2) into a cold isostatic pressing soft sheath, and pressing to form a pressed blank under the pressing pressure of 175-185 MPa;

(4) pre-degreasing: putting the pressed compact in the step (3) in H₂Dewaxing and sintering are carried out in the atmosphere, the degreasing temperature is 780-820 ℃, the degreasing time is 11-13h, and then furnace cooling is carried out;

(5) and (3) sintering: and (4) sintering the pressed compact treated in the step (4) in an Ar gas protective atmosphere, preserving the heat for 1.5-2.5h at the sintering temperature of 1400-1600 ℃, and then cooling along with the furnace to obtain the finished product of the titanium carbonitride base metal ceramic material for the high-temperature structure.

6. The method for preparing a titanium carbonitride based cermet material for high temperature structures as set forth in claim 5, wherein: in the step (1), the dispersing agent is ethanol, and the addition amount of the dispersing agent is 5-7% of the total weight of the raw materials.

7. The method for preparing a titanium carbonitride based cermet material for high temperature structures as set forth in claim 5, wherein: in the step (1), the forming agent is paraffin or PEG, and the addition amount of the forming agent is 5-7% of the total weight of the raw materials.

8. The method for preparing a titanium carbonitride based cermet material for high temperature structures as set forth in claim 5, wherein: in the step (1), the forming auxiliary agent comprises SBP, etomine and ethyl cellulose, and the weight ratio of the SBP to the etomine to the ethyl cellulose is 1-3:0.5-1.5: 0.5-1.5; the additive is added in an amount of 0.08-1.2 per mill of the total weight of the raw materials.

9. The method for preparing a titanium carbonitride based cermet material for high temperature structures as set forth in claim 8, wherein: the weight ratio of SBP, etomine and ethyl cellulose is 2:1: 1.

10. The method for preparing a titanium carbonitride based cermet material for high temperature structures as set forth in any one of claims 5-9, characterized in that: the particle size of each raw material is 1.0-2.0 um.

Technical Field

The invention relates to a metal ceramic material, in particular to a titanium carbonitride base metal ceramic material for a high-temperature structure and a preparation method thereof.

Background

At present, in the preparation process of some high-purity non-metallic materials (such as high-purity monocrystalline silicon, high-transmittance inorganic glass and the like), the preparation temperature is relatively high, generally 800-₂O₃、ZrO₂The material is a high-temperature resistant material. However, as a high-temperature resistant material, there are two difficult problems to solve, first at this operating temperature, Al₂O₃、ZrO₂Also, the sintering shrinkage and deformation are obvious, so that the structural precision and the structural part are easy to crack/fit clearance, and the structure is collapsed; second Al₂O₃、ZrO₂Al, Zr and the like in common high-temperature resistant materials belong to light elements, and the heat migration of the elements is easily generated at the working temperature, so that the more obvious element detection and local enrichment of Al and Zr appear in the preparation environment, and great negative influence is generated in the preparation process of high-purity substances.

Among other commonly seen high-temperature resistant materials, materials such as W, Mo are the main materials, however, W, Mo and the like belong to scarce strategic reserve resources, and materials such as W, Mo and the like have high density and poor mechanical properties, so when the material is used as a structural member in a high-temperature working state, local deformation of a preparation furnace body is easily caused due to the extremely high density difference, and cracks are easily generated and cannot be effectively supported.

The modified partial metal-based high-temperature material has excellent mechanical properties, but the modified partial metal-based high-temperature material is easily volatile at working temperature, such as iron group elements of Co, Ni, Fe and the like, and the impurity components also can significantly influence the preparation process of high-purity substances.

The applicant has found that the prior art has at least the following technical problems:

1. high temperature resistant material (Al) used for furnace structural component in prior art₂O₃、ZrO₂Materials), which has obvious sintering shrinkage and deformation at high temperature, and the structure precision and the structural member are easy to have cracks/fit gaps, thereby causing the structure collapse;

2. high temperature resistant material (Al) used for furnace structural component in prior art₂O₃、ZrO₂Material), which is very easy to generate element heat transfer at working temperature, and generates great negative effect in the preparation process of high-purity substances;

3. in the prior art, other high-temperature resistant materials used for the structural parts in the furnace are easy to generate local deformation of the furnace body, and are easy to generate cracks, cannot be effectively supported or influence the preparation process of high-purity substances.

Disclosure of Invention

The invention aims to provide a titanium carbonitride based cermet material for a high-temperature structure and a preparation method thereof, and aims to solve the technical problems that a high-temperature resistant material used for a structural member in a furnace in the prior art has obvious sintering shrinkage and deformation at high temperature, and the structural precision and the structural member are easy to crack/fit gaps, so that the structure collapses. The technical effects that can be produced by the preferred technical scheme in the technical schemes provided by the invention are described in detail in the following.

In order to achieve the purpose, the invention provides the following technical scheme:

the invention provides a titanium carbonitride base cermet material for high-temperature structures, which comprises TiCN, WC and Mo as raw materials₂C. TaC, NbC, Co and Ni; wherein, the sum of the weight percentage contents of Co and Ni is 5-14%; the weight percentage content of the whole C in the raw material is 5.8-6.2%, and the weight ratio of the whole C to N in the raw material is 3-7: 3-7.

Furthermore, the sum of the weight percentage contents of Co and Ni is 8-10%, the weight percentage content of C in the raw material is 5.8-6.2%, and the weight ratio of C to N is 5-6: 4-5.

Furthermore, the sum of the weight percentage contents of Co and Ni is 9%, the weight percentage content of C in the raw material is 6%, and the weight ratio of C to N is 5.5: 4.5.

Further, the weight percentage content of the TiCN is55-65％(ii) a The weight percentage content of WC is 8-20%; mo₂The weight percentage content of C is 3-10%;TaCthe content of the components is 2-10 percent by weight; the NbC content is2 to 10 percent; and saidTiCN、WC、Mo₂C. The sum of the contents of TaC, NbC, Co and Ni in percentage by weight is 100%.

The invention provides a preparation method of a titanium carbonitride based cermet material for a high-temperature structure, which comprises the following steps:

(1) RTP preparation: adding the raw materials into a ball mill according to the proportion, and simultaneously adding a dispersing agent, a forming agent and a forming auxiliary agent for ball milling; after ball milling, the ball milled material is placed in N₂Spray drying under the protection condition to obtain an RTP material for pressing;

(2) pressing: pressing the RTP material prepared in the step (1) into a blank in a mould at the pressure of 1.1-1.5T/cm²；

(3) Cold isostatic pressing: putting the blank pressed in the step (2) into a cold isostatic pressing soft sheath, and pressing to form a pressed blank under the pressing pressure of 175-185 MPa;

(4) pre-degreasing: putting the pressed compact in the step (3) in H₂Dewaxing and sintering are carried out in the atmosphere, the degreasing temperature is 780-820 ℃, the degreasing time is 11-13h, and then furnace cooling is carried out;

(5) and (3) sintering: and (4) sintering the pressed compact treated in the step (4) in an Ar gas protective atmosphere, preserving the heat for 1.5-2.5h at the sintering temperature of 1400-1600 ℃, and then cooling along with the furnace to obtain the finished product of the titanium carbonitride base metal ceramic material for the high-temperature structure.

Further, in the step (1), the dispersant is ethanol, and the addition amount of the dispersant is 5-7% of the total weight of the raw materials.

Further, in the step (1), the forming agent is paraffin or PEG, and the addition amount of the forming agent is 5-7% of the total weight of the raw materials.

Further, in the step (1), the forming auxiliary agent comprises SBP, etomine and ethyl cellulose, and the weight ratio of the SBP to the etomine to the ethyl cellulose is 1-3:0.5-1.5: 0.5-1.5; the additive is added in an amount of 0.08-1.2 per mill of the total weight of the raw materials.

Further, the weight ratio of SBP, etomine and ethyl cellulose is 2:1: 1.

Furthermore, the particle size of each raw material is 1.0-2.0 um.

Based on the technical scheme, the embodiment of the invention can at least produce the following technical effects:

(1) according to the titanium carbonitride based cermet material for the high-temperature structure, the main high-temperature volatile elements in the material components are binder phase metals such as Co, Ni and the like, and a partial liquefaction phenomenon exists in the high-temperature (800-; according to the method for modifying and strengthening the material, a large amount of refractory metal substances are dissolved in the bonding phase in a solid solution mode, so that a strong solid solution strengthening effect can be generated, meanwhile, the refractory metal elements can play a pinning role in the structure, the melting point/liquid point of the iron group elements is greatly improved, meanwhile, the refractory metal elements cannot obviously volatilize and dissipate, and the modification of the easily oxidized bonding phase is realized through solid solution strengthening; however, if a large degree of solid solution occurs, the iron group elements can also rapidly lose the good mechanical properties, and a large amount of eta phase is precipitated, and the integral strength and carrying capacity of the material can be obviously reduced due to the occurrence of the eta phase, so that the actual solid solubility in the binding phase is adjusted by selecting the proper component content, and the special phase structure is controlled, thereby realizing the performance improvement of the material in the aspect of high-temperature oxidation resistance; when the sum of the weight percentage contents of Co and Ni is 5-14%; the weight percentage content of the whole C in the raw materials is 5.8-6.2%, and the weight ratio of the whole C to N in the raw materials is 3-7:3-7, so that an ideal solid solution strengthening effect can be obtained; the invention researches and adjusts the preparation, pressing and forming processes of the mixture compared with the common pressing and sintering process to ensure that the density of the material is more than 99.5 percent, thereby ensuring the shape precision in the continuous heating use process.

(2) The titanium carbonitride base cermet material for the high-temperature structure can well meet the use requirements of structural components in a furnace in a high-temperature working environment, has small sintering shrinkage and deformation at high temperature, and has structure precision and less possibility of crack/fit clearance of the structural componentsThereby ensuring stable support of the structure; the heat migration of elements can not be generated at the high-temperature working temperature, so that the negative influence generated in the preparation process of high-purity substances can be avoided; the titanium carbonitride base cermet material for the high-temperature structure, which is prepared by the invention, can specifically achieve the following effects: firstly, under the high temperature environment of 1000-1300 ℃, the high temperature hardness of the material can reach more than 800 ℃ (HV10), so that the material can keep enough rigidity to achieve the effect of structural support; ② at above 800 ℃, the titanium carbonitride based cermet material for high temperature structure prepared by the invention has the oxidation weight gain of less than or equal to 0.015g/cm under the air environment with the high temperature oxidation speed of 100 hours²，N₂Under the environment or inert gas environment, the condition of reaction weight increment is avoided; thirdly, in the high temperature environment of 800-1400 ℃, the volatilization proportion of main metal components (iron group elements such as Co, Ni, Fe, Ti and the like and transition group elements) and the like in the material is less than 0.002 mg/kg-h; the compactness of the titanium carbonitride base cermet material for the high-temperature structure is more than 99.5 percent.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.

Description of raw materials:

the particle size of each raw material is 1.0-2.0 um.

The first embodiment is as follows:

1. raw materials:

the selection and content (weight percent) of each raw material in examples 1-7 are shown in table 1 below:

table 1 examples 1-7 raw material tables

Numbering	TiCN	WC	Mo2C	TaC	NbC	Co	Ni	C％	C：N	Co+Ni
											Example 1	60	12	5	10	5	5	3	5.85	5:5	8
Example 2	60	10	5	8	7	5	5	6.10	6:4	10
											Example 3	65	15	3	8	5	3	2	5.8	3:7	5
Example 4	57	7	10	2	10	7.5	6.5	6.2	7:3	14
											Example 5	59	17	3	8	4	5	4	6	5:5	9
Example 6	58	10	10	2	8	6.5	5.5	5.9	5.5:4.5	12

2. The preparation method comprises the following steps:

example 1:

the method comprises the following steps:

(1) RTP preparation: adding the raw materials into a ball mill according to the proportion, and simultaneously adding a dispersing agent, a forming agent and a forming auxiliary agent to perform ball milling for 56 hours; after ball milling, the ball milled material is placed in N₂Spray drying under the protection condition, wherein the outlet temperature is 100 ℃, and the RTP material for pressing is obtained after drying;

the dispersing agent is ethanol, and the addition amount of the dispersing agent is 6% of the total weight of the raw materials;

the forming agent is paraffin, and the addition amount of the forming agent is 6 percent of the total weight of the raw materials;

the forming auxiliary agent comprises SBP, etomine and ethyl cellulose, and the weight ratio of the SBP to the etomine to the ethyl cellulose is 2:1: 1; the additive is added in an amount of 1 per mill of the total weight of the raw materials;

(2) pressing: pressing the RTP material prepared in the step (1) into a blank in a mould at the pressing pressure of 1.3T/cm²；

(3) Cold isostatic pressing: putting the blank pressed in the step (2) into a cold isostatic pressing soft sheath, and pressing to form a pressed blank under the pressure of 180 Mpa;

(4) pre-degreasing: putting the pressed compact in the step (3) in H₂Dewaxing and sintering are carried out under the atmosphere, the degreasing temperature is 800 ℃, the degreasing time is 12 hours, and then furnace cooling is carried out;

(5) and (3) sintering: and (4) sintering the pressed compact treated in the step (4) in an Ar gas protective atmosphere, preserving heat for 2 hours at the sintering temperature of 1500 ℃, and then cooling along with the furnace to obtain the finished product of the titanium carbonitride base metal ceramic material for the high-temperature structure.

Example 2:

the method comprises the following steps:

(1) RTP preparation: adding the raw materials into a ball mill according to the proportion, and simultaneously adding a dispersing agent, a forming agent and a forming auxiliary agent to perform ball milling for 60 hours; after ball milling, the ball milled material is placed in N₂Spray drying is carried out under the protection condition, the outlet temperature is 95 ℃, and the RTP material for pressing is obtained after drying;

the dispersing agent is ethanol, and the addition amount of the dispersing agent is 5% of the total weight of the raw materials;

the forming agent is PEG4000, and the addition amount of the forming agent is 7 percent of the total weight of the raw materials;

the forming auxiliary agent comprises SBP, etomine and ethyl cellulose, and the weight ratio of the SBP to the etomine to the ethyl cellulose is 1:1.5: 0.5; the additive is added in an amount of 0.08 per mill of the total weight of the raw materials;

(2) pressing: pressing the RTP material prepared in the step (1) into a blank in a mould at the pressing pressure of 1.5T/cm²；

(3) Cold isostatic pressing: putting the blank pressed in the step (2) into a cold isostatic pressing soft sheath, and pressing the blank into a pressed blank under the pressure of 175 Mpa;

(4) pre-degreasing: putting the pressed compact in the step (3) in H₂Dewaxing and sintering at 820 deg.CThe fat time is 11h, and then the mixture is cooled along with the furnace;

(5) and (3) sintering: and (4) sintering the pressed compact treated in the step (4) in an Ar gas protective atmosphere, preserving heat for 2.5 hours at the sintering temperature of 1400 ℃, and then cooling along with the furnace to obtain the finished product of the titanium carbonitride base metal ceramic material for the high-temperature structure.

Example 3:

the method comprises the following steps:

(1) RTP preparation: adding the raw materials into a ball mill according to the proportion, and simultaneously adding a dispersing agent, a forming agent and a forming auxiliary agent to perform ball milling for 50 hours; after ball milling, the ball milled material is placed in N₂Spray drying is carried out under the protection condition, the outlet temperature is 105 ℃, and the RTP material for pressing is obtained after drying;

the dispersing agent is ethanol, and the addition amount of the dispersing agent is 7% of the total weight of the raw materials;

the forming agent is PEG1500, and the addition amount of the forming agent is 5 percent of the total weight of the raw materials;

the forming auxiliary agent comprises SBP, etomine and ethyl cellulose, and the weight ratio of the SBP to the etomine to the ethyl cellulose is 3:0.5: 1.5; the additive is added in an amount of 1.2 per mill of the total weight of the raw materials;

(2) pressing: pressing the RTP material prepared in the step (1) into a blank in a mould at the pressing pressure of 1.1T/cm²；

(3) Cold isostatic pressing: putting the blank pressed in the step (2) into a cold isostatic pressing soft sheath, and pressing to obtain a pressed blank with the pressing pressure of 185 Mpa;

(4) pre-degreasing: putting the pressed compact in the step (3) in H₂Dewaxing and sintering are carried out under the atmosphere, the degreasing temperature is 780 ℃, the degreasing time is 13 hours, and then furnace cooling is carried out;

(5) and (3) sintering: and (4) sintering the pressed compact treated in the step (4) in an Ar gas protective atmosphere, preserving heat for 1.5h at the sintering temperature of 1600 ℃, and then cooling along with the furnace to obtain the finished product of the titanium carbonitride base metal ceramic material for the high-temperature structure.

Examples 4 to 7:

the preparation method is the same as example 1.

Second, performance detection

The finished products prepared in examples 1 to 7 were individually subjected to performance tests. The test results are shown in table 2 below:

table 2 results of performance testing

The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention.