CN116623030B - Preparation method of superfine cermet added with multi-element composite carbonitride - Google Patents
Preparation method of superfine cermet added with multi-element composite carbonitride Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 239000011195 cermet Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 73
- 238000005245 sintering Methods 0.000 claims abstract description 59
- 239000000919 ceramic Substances 0.000 claims abstract description 44
- 229910052751 metal Inorganic materials 0.000 claims abstract description 43
- 239000002184 metal Substances 0.000 claims abstract description 43
- 238000000498 ball milling Methods 0.000 claims abstract description 32
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 239000002002 slurry Substances 0.000 claims abstract description 20
- 238000001694 spray drying Methods 0.000 claims abstract description 20
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 14
- 239000011812 mixed powder Substances 0.000 claims abstract description 9
- 238000004537 pulping Methods 0.000 claims abstract description 9
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 238000007906 compression Methods 0.000 claims abstract description 4
- 230000006835 compression Effects 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims description 31
- 239000000463 material Substances 0.000 claims description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 229910052721 tungsten Inorganic materials 0.000 claims description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 13
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 10
- 239000012188 paraffin wax Substances 0.000 claims description 10
- 229910052735 hafnium Inorganic materials 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 229910052720 vanadium Inorganic materials 0.000 claims description 9
- -1 ammonia alcohol compound Chemical class 0.000 claims description 8
- 239000002270 dispersing agent Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000004615 ingredient Substances 0.000 claims description 2
- 239000010936 titanium Substances 0.000 abstract description 20
- 238000009792 diffusion process Methods 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 238000005121 nitriding Methods 0.000 abstract 1
- 238000005452 bending Methods 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000011218 binary composite Substances 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000013538 functional additive Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 229910003178 Mo2C Inorganic materials 0.000 description 1
- 229910009043 WC-Co Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 238000000879 optical micrograph Methods 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
- C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/02—Compacting only
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/1003—Use of special medium during sintering, e.g. sintering aid
- B22F3/1007—Atmosphere
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/005—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides comprising a particular metallic binder
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
- C22C29/04—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbonitrides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
Abstract
The invention relates to a preparation method of superfine cermet added with multi-component composite carbonitride, which comprises the following steps: s1, proportioning: proportioning according to a certain proportion; s2, pulping: adding the prepared mixture into a ball mill, and adding ball grinding balls for ball milling and mixing to obtain mixture slurry; s3, spray drying and granulating: drying and granulating the mixture slurry by adopting a spray drying process to obtain uniform raw material mixture granulating powder; s4, press forming and sintering: and (3) forming the spray-dried mixed powder into a strip-shaped sample by adopting a compression forming method, and placing the strip-shaped sample into a vacuum sintering path for sintering to obtain the novel metal ceramic product after sintering. The invention replaces partial traditional binary complex carbide, reduces diffusion reaction between binary complex carbide and titanium carbonitride ceramic phase, and restricts grain growth of ceramic components to realize tissue structure refinement by utilizing low diffusion capability of multi-element carbon nitriding, thereby improving comprehensive mechanical property and wear resistance of metal ceramic.
Description
Technical Field
The invention relates to the field of new materials, in particular to a preparation method of superfine cermet added with multi-element composite carbonitride.
Background
The metal ceramic is mainly a composite material composed of metal or alloy and one or more ceramic phases, a typical material system is a composite material which is composed of Ti (CN) and various carbides as ceramic phases and metal Ni and Co as bonding phases, and compared with WC-Co hard alloy, the metal ceramic composite material has the remarkable advantages of high hardness, high strength, high-temperature oxidation resistance, good red hardness, good adhesion resistance, low raw material price and the like, but the toughness is not high, and the abrasion resistance of the material is further improved; meanwhile, in the preparation process of the metal ceramic material, various carbide ceramics have complex diffusion reaction in the high-temperature sintering process to form a multi-layer core ring structure such as a black core/white inner ring/gray outer ring, and the like.
In order to improve the high-temperature performance and the wear resistance of the metal ceramic, a plurality of technical approaches are researched and explored, and the wear resistance and the high-temperature performance of the metal ceramic can be effectively improved by adding high-content high-melting-point high-hardness refractory metal carbide such as TaC, nbC, hfC and the like, but the manufacturing cost of the metal ceramic composite material is also improved; it is reported in literature that the addition of diamond micropowder can improve the hardness and wear resistance of the cermet, but the sintering process is difficult to control and the quality fluctuation is large.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of superfine cermet added with multi-element composite carbonitride, which adopts Ti (CN) powder with granularity smaller than 0.5 μm as a raw material, introduces part of multi-element composite carbonitride as a functional additive phase in a traditional cermet material system, replaces part of binary composite carbide, reduces diffusion reaction between the binary composite carbide and a titanium carbonitride ceramic phase, eases internal stress of a multi-layer core ring structure, and restricts grain growth of ceramic components to realize tissue structure refinement by utilizing low diffusion capability of multi-element carbonitride, thereby improving comprehensive mechanical property and wear resistance of the cermet.
The technical scheme adopted for solving the technical problems is as follows: the preparation method of the superfine cermet added with the multi-component composite carbonitride comprises the following steps:
s1, proportioning: the ingredients were dosed in the following proportions: 45-55wt% Ti (CN) powder, 6-8wt% (TiW) C powder, 6-8wt% WC powder, 6-9wt% Mo 2 C powder, 7-10wt% (Hf, V, nb, ta) (CN) powder, 2wt% TaC powder, 12wt% nickel powder and 6wt% cobalt powder;
s2, pulping: adding the prepared mixture into a ball mill, and adding ball grinding balls for ball milling and mixing to obtain mixture slurry;
s3, spray drying and granulating: drying and granulating the mixture slurry by adopting a spray drying process to obtain uniform raw material mixture granulating powder;
s4, press forming and sintering: and (3) forming the spray-dried mixed powder into a strip-shaped sample by adopting a compression forming method, and placing the strip-shaped sample into a vacuum sintering path for sintering to obtain the novel metal ceramic product after sintering.
According to the above scheme, in the step S1, the average particle diameter D of Ti (CN) powder 50 An average particle diameter D of the (Ti, W) C powder of 0.5 μm 50 The average particle diameter D of WC powder is 1.2 mu m 50 0.6 μm, mo 2 Average particle diameter D of powder C 50 1.2 μm, (Hf, V, nb, W) (CN) powder average particle diameter D 50 TaC powder average particle diameter D of 0.6 μm 50 1um, average particle diameter D of metal nickel powder and cobalt powder 50 Is 1um.
According to the scheme, in the step S2, 4 weight percent of paraffin binder and 2 weight percent of ammonia alcohol compound dispersing agent are added before ball milling and mixing, and the 4 weight percent of paraffin binder and the 2 weight percent of ammonia alcohol compound dispersing agent are calculated according to the total amount of various raw material powders.
According to the above scheme, in the step S2, the ball milling process parameters are as follows: the rotating speed of the ball mill is 200-300 r/min, and the ball-material ratio is 2:1, the ball milling time is 72 hours.
According to the scheme, in the step S2, the solid content of the mixture slurry is 40-50%.
According to the above scheme, in the step S3, the conditions of the spray drying process are as follows: the inlet temperature is controlled to be 170-180 ℃ and the outlet temperature is controlled to be 90-105 ℃.
According to the above scheme, in the step S4, the strip-shaped sample is 3X4X400mm.
According to the above scheme, in the step S4, sintering conditions are as follows: the sintering temperature is 1400-1460 ℃, the sintering time is 60 minutes, and the sintering atmosphere is high-purity nitrogen.
The preparation method of the superfine cermet added with the multi-element composite carbonitride has the following beneficial effects:
the multi-element compound carbonitride is a multi-element transition metal carbonitride, and the transition metal element types are more than three, namely multi-element compound carbonitride, and the multi-element compound carbonitride has high hardness, low diffusion coefficient, excellent wear resistance and high-temperature oxidation resistance, and can be used as a functional additive of metal ceramic to effectively improve the microstructure of the metal ceramic and relieve the internal stress of a multi-layer core ring structure; meanwhile, the polynary compound carbonitride with low diffusion coefficient is dispersed in the ceramic matrix, so that the grain growth of a ceramic phase is effectively limited, the refinement of a tissue structure is realized, and the comprehensive performance of the metal ceramic is improved.
Compared with the traditional metal ceramic, the superfine metal ceramic composite material added with the multi-element composite carbonitride has high hardness, high strength and good toughness, and has better wear resistance and processing service performance, wherein TiCN, (TiW) C and WC are main hard phases, high hardness and wear resistance are provided for the metal ceramic, metal phases Ni and Co are used as binding phases, high strength is provided for the metal ceramic, the effect of TaC is mainly to further ensure the high-temperature oxidation resistance and wear resistance of the metal ceramic, mo2C can improve the wettability between TiCN and the metal binding phases to achieve the aim of improving the interfacial fracture strength, the addition of the multi-element composite carbonitride is mainly to limit the grain growth of the ceramic hard phases, realize the refinement of a tissue structure and improve the comprehensive performance of the metal ceramic.
Drawings
The invention will be further described with reference to the accompanying drawings and examples, in which:
FIG. 1 is an electron micrograph of a multi-component composite carbonitride added ultrafine cermet composite prepared in accordance with the present invention;
fig. 2 is an optical micrograph of an ultra-fine cermet composite with added multi-component composite carbonitride prepared according to the present invention.
Detailed Description
For a clearer understanding of technical features, objects and effects of the present invention, a detailed description of embodiments of the present invention will be made with reference to the accompanying drawings.
As shown in fig. 1-2, the present invention provides a method for preparing ultrafine cermet added with multi-component composite carbonitride, comprising the steps of: (1) batching: average particle diameter D 50 500 nm Ti (CN) powder, D 50 (Ti, W) C powder, D of 1.2 μm 50 WC powder of 0.6 μm, D 50 Mo of 1.2 μm 2 Powder C, D 50 (Hf, V, nb, W) (CN) powder of 0.6 μm, average particle diameter D 50 TaC powder of 1um and average particle diameter D 50 The metal nickel powder and cobalt powder with the thickness of 1um are prepared from the following raw materials in percentage by weight: 45-55wt% Ti (CN) powder, 6-8wt% (TiW) C powder, 6-8wt% WC powder, 6-9wt% Mo 2 C powder, 7-10wt% (Hf, V, nb, ta) (CN) powder, 2wt% TaC powder, 12wt% nickel powder and 6wt% cobalt powder. (2) pulping: adding the mixed material prepared in the step (1) into a ball mill, and adding a ball grinding ball; adding 4wt% of paraffin (calculated according to the total amount of the raw material powder) binder and 2wt% of an amino alcohol compound dispersing agent (calculated according to the total amount of the raw material powder), and performing ball milling and mixing; the ball milling process parameters are as follows: the rotating speed of the ball mill is 200-300 r/min, and the ball-material ratio is 2:1, ball milling time is 72 hours; and obtaining the mixture slurry with good fluidity and the solid content of 40-50%. (3) spray drying granulation: and (3) drying and granulating the slurry prepared in the step (2) by adopting a spray drying tower, controlling the inlet temperature to be 170-180 ℃ and the outlet temperature to be 90-105 ℃ to obtain uniform raw material mixture granulating powder. (4) press forming and sintering: and (3) forming the spray-dried mixed powder into a strip-shaped sample with the thickness of 3X4X400mm by adopting a compression forming method, and putting the sample into a vacuum sintering path for sintering. The sintering temperature is 1400-1460 ℃, the sintering time is 60 minutes, and the sintering atmosphere is high-purity nitrogen. And sintering to obtain the novel metal ceramic product.
Example 1
A preparation method of superfine cermet added with multi-element composite carbonitride comprises the following steps:
(1) Preparing ceramic raw materials: 45 g of average particle diameter D is weighed 50 Ti (CN) powder of 0.5 μm, 8 g D 50 1.2 μm (Ti, W) C powder, 8 g D 50 WC powder of 0.6 μm, 9g D 50 Mo of 1.2 μm 2 Powder C, 10 g D 50 0.6 μm (Hf, V, nb, W) (CN) powder, 2 g of average particle diameter D 50 TaC powder of 1um, 12 g average particle diameter D 50 1um metal nickel powder, 6g cobaltGrinding and mixing uniformly;
(2) Mixing and pulping: adding the mixed material prepared in the step (1) into a ball milling medium, 4 g of paraffin binder and 2 g of ammonia alcohol compound dispersing agent, and placing balls on a ball mill to perform ball milling and mixing. The ball milling process parameters comprise: the rotating speed of the ball mill is 200-300 r/min, and the ball-material ratio is 2:1, the ball milling time is 72 hours. Obtaining a mixture slurry with good fluidity and a solid content of 40-50%;
(3) Spray drying and granulating: spraying the slurry prepared in the step (2) into a spray drying tower directly, controlling the inlet temperature to 170 ℃, the outlet temperature to 90 ℃ and the nitrogen flow to 45m 3 And (h) obtaining uniform raw material mixture granulating powder;
(4) The spray-dried mixed powder is molded into a strip-shaped sample with the thickness of 3X4X400mm by a hydraulic molding machine, and the strip-shaped sample is placed into a vacuum sintering path for sintering. The sintering temperature is 1400 ℃, the sintering time is 60 minutes, and the sintering atmosphere is high-purity nitrogen. And sintering to obtain the novel metal ceramic product.
The superfine metal ceramic composite material added with the multi-element composite carbonitride prepared in the embodiment has uniform microstructure, fine grains, and the bending strength, the fracture toughness and the Vickers hardness of the material are 2310MPa and 9.45MPam respectively 1/2 、17.5GPa。
Example 2
A preparation method of superfine cermet added with multi-element composite carbonitride comprises the following steps:
(1) Preparing ceramic raw materials: weigh 55 grams of average particle size D 50 Ti (CN) powder of 0.5 μm, 6g D 50 1.2 μm (Ti, W) C powder, 6g D 50 WC powder of 0.6 μm, 6g D 50 Mo of 1.2 μm 2 Powder C, 7 g D 50 0.6 μm (Hf, V, nb, W) (CN) powder, 2 g of average particle diameter D 50 TaC powder of 1um, 12 g average particle diameter D 50 1um of metal nickel powder and 6g of cobalt powder, and grinding and mixing uniformly;
(2) Mixing and pulping: adding the mixed material prepared in the step (1) into a ball milling medium, 4 g of paraffin binder and 2 g of ammonia alcohol compound dispersing agent, and placing balls on a ball mill to perform ball milling and mixing. The ball milling process parameters comprise: the rotating speed of the ball mill is 200-300 r/min, and the ball-material ratio is 2:1, the ball milling time is 72 hours. Obtaining a mixture slurry with good fluidity and a solid content of 40-50%;
(3) Spray drying and granulating: spraying the slurry prepared in the step (2) into a spray drying tower directly, controlling the inlet temperature to be 180 ℃ and the outlet temperature to be 98 ℃ to obtain uniform raw material mixture granulating powder;
(4) The spray-dried mixed powder is molded into a strip-shaped sample with the thickness of 3X4X400mm by a hydraulic molding machine, and the strip-shaped sample is placed into a vacuum sintering path for sintering. The sintering temperature is 1460 ℃, the sintering time is 60 minutes, and the sintering atmosphere is high-purity nitrogen. And sintering to obtain the novel metal ceramic product.
The superfine metal ceramic composite material added with the multi-element composite carbonitride prepared in the embodiment has uniform microstructure, fine grains, and the bending strength, the fracture toughness and the Vickers hardness of the material are 2260MPa and 9.35MPam respectively 1/2 、18.6GPa。
Example 3
A preparation method of superfine cermet added with multi-element composite carbonitride comprises the following steps:
(1) Preparing ceramic raw materials: 50 g of the average particle diameter D is weighed 50 Ti (CN) powder of 0.5 μm, 7 g D 50 1.2 μm (Ti, W) C powder, 7 g D 50 WC powder of 0.6 μm, 7 g D 50 Mo of 1.2 μm 2 Powder C, 9g D 50 0.6 μm (Hf, V, nb, W) (CN) powder, 2 g of average particle diameter D 50 TaC powder of 1um, 12 g average particle diameter D 50 1um of metal nickel powder and 6g of cobalt powder, and grinding and mixing uniformly;
(2) Mixing and pulping: adding the mixed material prepared in the step (1) into a ball milling medium, 4 g of paraffin binder and 2 g of ammonia alcohol compound dispersing agent, and placing balls on a ball mill for ball milling and mixing; the ball milling process parameters comprise: the rotating speed of the ball mill is 200-300 r/min, and the ball-material ratio is 2:1, ball milling is carried out for 72 hours, and mixed material slurry with 40-50% of solid content and good fluidity is obtained;
(3) Spray drying and granulating: spraying the slurry prepared in the step (2) into a spray drying tower directly, controlling the inlet temperature to be 180 ℃ and the outlet temperature to be 95 ℃ to obtain uniform raw material mixture granulating powder;
(4) The spray-dried mixed powder is molded into a strip-shaped sample with the thickness of 3X4X400mm by a hydraulic molding machine, and the strip-shaped sample is placed into a vacuum sintering path for sintering. The sintering temperature is 1430 ℃, the sintering time is 60 minutes, and the sintering atmosphere is high-purity nitrogen. And sintering to obtain the novel metal ceramic product.
The superfine metal ceramic composite material added with the multi-element composite carbonitride, which is prepared in the embodiment, has uniform microstructure and fine grains, and the bending strength, the fracture toughness and the Vickers hardness of the material are 2360MPa, 9.57MPam1/2 and 17.9GPa respectively.
Comparative example 1:
(1) Preparing ceramic raw materials: 50 g of the average particle diameter D is weighed 50 Ti (CN) powder of 0.8 μm, 15 g D 50 1.2 μm (Ti, W) C powder, 7 g D 50 WC powder of 0.6 μm, 8 g D 50 Mo of 1.2 μm 2 Powder C, 2 g average particle diameter D 50 TaC powder of 1um, 12 g average particle diameter D 50 1um of metal nickel powder and 6g of cobalt powder, and grinding and mixing uniformly;
(2) Mixing and pulping: adding the mixed material prepared in the step (1) into a ball milling medium and 4 g of paraffin binder, and placing balls on a ball mill for ball milling and mixing; the ball milling process parameters comprise: the rotating speed of the ball mill is 200-300 r/min, and the ball-material ratio is 2:1, ball milling is carried out for 72 hours, and mixed material slurry with 40-50% of solid content and good fluidity is obtained;
(3) Spray drying and granulating: spraying the slurry prepared in the step (2) into a spray drying tower directly, controlling the inlet temperature to be 180 ℃ and the outlet temperature to be 95 ℃ to obtain uniform raw material mixture granulating powder;
(4) The spray-dried mixed powder is molded into a strip-shaped sample with the thickness of 3X4X400mm by a hydraulic molding machine, and the strip-shaped sample is placed into a vacuum sintering path for sintering. The sintering temperature is 1450 ℃, the sintering time is 60 minutes, and the sintering atmosphere is high-purity nitrogen.And sintering to obtain the novel metal ceramic product. The bending strength, fracture toughness and Vickers hardness of the material are respectively 1970MPa and 9.15MPam 1 /2 、16.8GPa。
Comparative example 2:
(1) Preparing ceramic raw materials: 55 g of Ti (CN) powder with an average particle diameter D50 of 0.8 mu m, 13 g of (Ti, W) C powder with a D50 of 1.2 mu m, 6g of WC powder with a D50 of 0.6 mu m, 6g of Mo2C powder with a D50 of 1.2 mu m, 2 g of TaC powder with an average particle diameter D50 of 1 mu m, 12 g of metal nickel powder with an average particle diameter D50 of 1 mu m and 6g of cobalt powder are weighed and uniformly mixed by grinding;
(2) Mixing and pulping: adding the mixed material prepared in the step (1) into a ball milling medium and 4 g of paraffin binder, and placing balls on a ball mill for ball milling and mixing; the ball milling process parameters comprise: the rotating speed of the ball mill is 200-300 r/min, and the ball-material ratio is 2:1, ball milling is carried out for 72 hours, and mixed material slurry with 40-50% of solid content and good fluidity is obtained;
(3) Spray drying and granulating: spraying the slurry prepared in the step (2) into a spray drying tower directly, controlling the inlet temperature to be 180 ℃ and the outlet temperature to be 95 ℃ to obtain uniform raw material mixture granulating powder;
(4) The spray-dried mixed powder is molded into a strip-shaped sample with the thickness of 3X4X400mm by a hydraulic molding machine, and the strip-shaped sample is placed into a vacuum sintering path for sintering. The sintering temperature is 1450 ℃, the sintering time is 60 minutes, and the sintering atmosphere is high-purity nitrogen. And sintering to obtain the novel metal ceramic product. The bending strength, fracture toughness and Vickers hardness of the material are 1860MPa, 8.55MPam1/2 and 17.3GPa respectively.
In summary, the ultrafine metal ceramic composite materials prepared in examples 1 to 3 have a flexural strength, fracture toughness and Vickers hardness of 2260 to 2360MPa and 9.35 to 9.57MPam, respectively 1/2 17.5-18.6 GPa, compared with the metal ceramic material without adding the multi-component composite carbonitride, the metal ceramic prepared by the invention has greatly improved comprehensive performance.
The embodiments of the present invention have been described above with reference to the accompanying drawings, but the present invention is not limited to the above-described embodiments, which are merely illustrative and not restrictive, and many forms may be made by those having ordinary skill in the art without departing from the spirit of the present invention and the scope of the claims, which are to be protected by the present invention.
Claims (1)
1. The preparation method of the superfine cermet added with the multi-element composite carbonitride is characterized by comprising the following steps of:
s1, proportioning: the ingredients were dosed in the following proportions: 45-55wt% Ti (CN) powder, 6-8wt% (Ti, W) C powder, 6-8wt% WC powder, 6-9wt% Mo 2 C powder, 7-10wt% (Hf, V, nb, W) (CN) powder, 2wt% TaC powder, 12wt% nickel powder and 6wt% cobalt powder;
s2, pulping: adding the prepared mixture into a ball mill, and adding ball grinding balls for ball milling and mixing to obtain mixture slurry;
s3, spray drying and granulating: drying and granulating the mixture slurry by adopting a spray drying process to obtain uniform raw material mixture granulating powder;
s4, press forming and sintering: forming the spray-dried mixed powder into a strip sample by adopting a compression forming method, and placing the strip sample into a vacuum sintering furnace for sintering to obtain a novel metal ceramic product after sintering; in the step S1, the average grain diameter D of Ti (CN) powder 50 An average particle diameter D of the (Ti, W) C powder of 0.5 μm 50 The average particle diameter D of WC powder is 1.2 mu m 50 0.6 μm, mo 2 Average particle diameter D of powder C 50 1.2 μm, (Hf, V, nb, W) (CN) powder average particle diameter D 50 TaC powder average particle diameter D of 0.6 μm 50 1um, average particle diameter D of metal nickel powder and cobalt powder 50 Is 1um; in the step S2, 4 weight percent of paraffin binder and 2 weight percent of ammonia alcohol compound dispersing agent are added before ball milling and mixing, and the 4 weight percent of paraffin binder and 2 weight percent of ammonia alcohol compound dispersing agent are calculated according to the total amount of various raw material powders; in the step S2, the ball milling process parameters are as follows: the rotating speed of the ball mill is 200-300 r/min, and the ball-material ratio is 2:1, ball milling time is 72 hours; in the step S2, the solid content of the mixture slurry is 40-50%; in the step S3 of the above-mentioned process,the conditions of the spray drying process are as follows: controlling the inlet temperature to be 170-180 ℃ and the outlet temperature to be 90-105 ℃; in the step S4, the strip-shaped sample is 3X4X400mm; in the step S4, sintering conditions are as follows: the sintering temperature is 1400-1460 ℃, the sintering time is 60 minutes, and the sintering atmosphere is high-purity nitrogen.
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| CN112853187A (en) * | 2021-01-07 | 2021-05-28 | 中南大学 | Weak core ring structure fine-grain homogeneous TiCN-based metal ceramic and preparation method thereof |
| CN113025861A (en) * | 2021-03-08 | 2021-06-25 | 昆山长鹰硬质材料科技股份有限公司 | Mixed crystal Ti (C, N) -based metal ceramic material and preparation method thereof |
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| CN102383019A (en) * | 2011-10-18 | 2012-03-21 | 李海坤 | Superfine crystalline Ti(C,N)-based cermet and preparation method thereof |
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