CN113373336A - Preparation of superfine multi-element Ti (C, N) -based metal ceramic - Google Patents
Preparation of superfine multi-element Ti (C, N) -based metal ceramic Download PDFInfo
- Publication number
- CN113373336A CN113373336A CN202110648974.0A CN202110648974A CN113373336A CN 113373336 A CN113373336 A CN 113373336A CN 202110648974 A CN202110648974 A CN 202110648974A CN 113373336 A CN113373336 A CN 113373336A
- Authority
- CN
- China
- Prior art keywords
- nano
- oxide
- metal ceramic
- improved
- nanometer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- C22C1/058—Mixtures of metal powder with non-metallic powder by reaction sintering (i.e. gasless reaction starting from a mixture of solid metal compounds)
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
- C22C2026/002—Carbon nanotubes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
- C22C2026/008—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes with additional metal compounds other than carbides, borides or nitrides
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Powder Metallurgy (AREA)
- Cutting Tools, Boring Holders, And Turrets (AREA)
Abstract
The synthesis and application of superfine multielement Ti (C, N) -based cermet are characterized by comprising the following steps: a. taking nano titanium oxide, nano tungsten oxide, nano cobalt oxide, nano vanadium oxide, nano chromium oxide, nano reducing agent carbon black and a multi-wall carbon nano tube according to mass percent, mixing, drying, and sintering by adopting discharge plasma sintering equipment to finally prepare the multielement Ti (C, N) -based metal ceramic. The fracture toughness of the metal ceramic is improved by 33-65%, the Hardness (HRA) is improved by 12-23%, and the bending strength is improved by 32-85%. The invention has the advantages of high production efficiency, low energy consumption and simple and convenient operation, and provides reference for metal ceramic products with excellent industrial production performance.
Description
Technical Field
The invention relates to preparation of superfine multi-element Ti (C, N) -based metal ceramic, belonging to the field of preparation technology and application of nano metal ceramic composite powder.
Background
Ti (C, N) -based cermet has excellent heat resistance, corrosion resistance, high hardness and wear resistance, and is widely used as a tool material. The cermet is usually synthesized by a powder metallurgy method by taking Ti (C, N) as a hard phase and Co as a binder phase. The Ti (C, N) -based cermet has higher hardness, wear resistance, and red hardness than high-speed steel. In addition, Ti (C, N) -based cermets may also be used to make complex tools such as drills, gear cutters, reamers, and the like. Compared with common Ti (C, N) -based cermet, the superfine and nanocrystalline Ti (C, N) -based cermet has the advantages of obviously improved bending strength, increased hardness, improved wear resistance and improved cutter durability by 3-10 times. Meanwhile, the thermal shock resistance and the oxidation resistance of the metal ceramic are obviously improved, and the temperature required for achieving complete densification is further reduced. The ultra-fine grain cermet has small mutual adsorption-diffusion effect with processing materials, and is widely applied to the fields of difficult-to-process materials, microelectronic industry, precise dies, medicine and the like. Therefore, ultra-fine and nano-crystalline Ti (C, N) -based cermet has become one of the development hotspots in the cermet industry today.
With the rapid development of the modern industrial technology, the performance requirements of the metal ceramic are higher and higher, and the smaller the crystal grain size of Ti (C, N) in the metal ceramic, the higher the comprehensive mechanical property of the metal ceramic. The carbon nano tube one-dimensional nano material has light weight, many excellent mechanical properties, extremely high strength, toughness and elastic modulus. The carbon nano tube is used as a reinforcing phase and doped in the multi-element Ti (C, N) based composite powder, and the strength of the hard alloy is obviously improved by applying the obdurability of the carbon nano tube and the excellent performance of the nano material. The Ti (C, N) -based cermet has the advantages that the effect of refining Ti (C, N) -based cermet grains is achieved by applying the carbon nanotubes, and the strength of the Ti (C, N) -based cermet is improved by cooperating with the mechanisms of pulling out, bridging, guiding crack bending, deflecting and the like of the carbon nanotubes and the fiber structure. In addition, the discharge plasma sintering process is adopted, the growth of Ti (C, N) crystal grains is further effectively inhibited, the sintering temperature and the sintering time are reduced, the production efficiency is improved, the energy consumption is reduced, and finally the multielement Ti (C, N) -based metal ceramic product with high density, fine crystal grains, uniform tissue and excellent comprehensive mechanical property is obtained.
Disclosure of Invention
The invention aims to provide synthesis and application of superfine multi-element Ti (C, N) -based metal ceramic, so as to better meet the requirements of Ti (C, N) -based metal ceramic on the manufacture of superfine/nano hard alloy and the application in the field of cutters. The carbothermic reduction method adopted by the invention has the advantages of simple required equipment, low price of reaction raw materials, simple and convenient preparation process, high production efficiency and low energy consumption, and ensures that the synthesized multi-element Ti (C, N) -based composite material meets the industrial requirements in the aspects of granularity, dispersibility, particle shape and the like.
The preparation method of the superfine multi-element Ti (C, N) -based metal ceramic comprises the following steps:
a. mixing and drying nanometer titanium oxide, nanometer tungsten oxide, nanometer cobalt oxide, nanometer vanadium oxide, nanometer chromium oxide, nanometer reducing agent carbon black and a multi-wall carbon nanotube according to different mass percentages;
b. and C, placing the raw material obtained in the step a into a spark plasma sintering device for sintering to finally obtain the superfine multi-element Ti (C, N) -based metal ceramic. The fracture toughness of the metal ceramic is improved by 33-65%, the Hardness (HRA) is improved by 12-23%, and the bending strength is improved by 32-85%.
The superfine multi-element Ti (C, N) -based metal ceramic prepared by the invention comprises the following raw materials in percentage by mass: 38-52% of nano titanium oxide, 26-32% of nano tungsten oxide, 8-15% of nano cobalt oxide, 0.2-1% of nano vanadium oxide, 0.2-1% of nano chromium oxide, 20-27% of nano carbon black and 0.2-0.8% of multi-walled carbon nano tube.
In the method for preparing the superfine multi-element Ti (C, N) -based metal ceramic, the sintering process for preparing the composite material is carried out under the condition of flowing nitrogen, the sintering temperature is 1300-1500 ℃, and the heat preservation time is 0.5-1 h.
In the method for preparing the superfine multi-element Ti (C, N) -based metal ceramic, mixing is carried out in any one of a high-energy ball mill, a rolling ball mill or a grinding mill.
In the method for preparing the superfine multi-element Ti (C, N) -based metal ceramic, the drying temperature is 50-80 ℃ after ball milling, and the drying time is 16-30 h.
The sintering for preparing the superfine multi-element Ti (C, N) -based metal ceramic is carried out under the condition of nitrogen, the heating rate is 50-150 ℃/min, and the temperature is 1300-1500 ℃.
Compared with the existing preparation method of the superfine hard alloy, the invention has the advantages that:
(1) effectively inhibit the growth of Ti (C, N) crystal grains. The multi-wall carbon nano tube serving as a novel reinforcing material has excellent mechanical properties, is doped into multi-element Ti (C, N) -based composite powder to achieve the effect of refining Ti (C, N) hard alloy grains, and improves the strength of Ti (C, N) -based metal ceramic by cooperating with the strength of the carbon nano tube and mechanisms of pulling out, bridging, guiding crack bending, deflecting and the like of a fiber structure.
(2) Low sintering temperature, short time, high efficiency and low energy consumption. Nano carbon black, nano oxide and multi-wall carbon nano tubes are used as raw materials, and the multi-element Ti (C, N) -based metal ceramic is obtained by directly combining discharge plasma sintering. The synthesis method can greatly reduce the reaction temperature, shorten the reaction time, improve the production efficiency and effectively save energy.
Detailed Description
Example 1:
according to the mass percentage, 38 percent of nano titanium oxide, 25 percent of nano tungsten oxide, 10 percent of nano cobalt oxide, 0.4 percent of nano vanadium oxide, 0.4 percent of nano chromium oxide, 26 percent of nano carbon black and 0.2 percent of multi-wall carbon nano tube are uniformly mixed (a high-energy ball mill), dried (the drying temperature is 50 ℃ and the drying time is 30 hours), and then placed in a discharge plasma sintering device for sintering (the heating rate is 50-150 ℃/min, the temperature is 1300 ℃ and 1500 ℃ and nitrogen), so as to prepare the Ti (C, N) -based cermet with fine grains and uniform tissues. The fracture toughness of the metal ceramic is improved by 33-65%, the Hardness (HRA) is improved by 12-23%, and the bending strength is improved by 32-85%.
Example 2:
according to the mass percentage, 39 percent of nano titanium oxide, 25 percent of nano tungsten oxide, 12 percent of nano cobalt oxide, 0.6 percent of nano vanadium oxide, 0.6 percent of nano chromium oxide, 22 percent of nano carbon black and 0.8 percent of multi-wall carbon nano tube are uniformly mixed (a high-energy ball mill), dried (the drying temperature is 80 ℃ and the drying time is 20 hours), and then placed in a discharge plasma sintering device for sintering (the heating rate is 50-150 ℃/min, the temperature is 1300 ℃ and 1500 ℃ and nitrogen), so as to prepare the Ti (C, N) -based cermet with fine grains and uniform tissues. The fracture toughness of the metal ceramic is improved by 33-65%, the Hardness (HRA) is improved by 12-23%, and the bending strength is improved by 32-85%.
Example 3:
according to the mass percentage, 40 percent of nano titanium oxide, 26 percent of nano tungsten oxide, 10 percent of nano cobalt oxide, 0.2 percent of nano vanadium oxide, 0.2 percent of nano chromium oxide, 23 percent of nano carbon black and 0.6 percent of multi-wall carbon nano tube are uniformly mixed (a high-energy ball mill), dried (the drying temperature is 60 ℃ and the drying time is 24 hours), and then placed in a discharge plasma sintering device for sintering (the heating rate is 50-150 ℃/min, the temperature is 1300 ℃ and 1500 ℃ and nitrogen), so as to prepare the Ti (C, N) -based cermet with fine grains and uniform tissues. The fracture toughness of the metal ceramic is improved by 33-65%, the Hardness (HRA) is improved by 12-23%, and the bending strength is improved by 32-85%.
Example 4:
according to the mass percentage, 42 percent of nano titanium oxide, 25 percent of nano tungsten oxide, 8 percent of nano cobalt oxide, 0.3 percent of nano vanadium oxide, 0.3 percent of nano chromium oxide, 24 percent of nano carbon black and 0.4 percent of multi-wall carbon nano tube are uniformly mixed (a high-energy ball mill), dried (the drying temperature is 70 ℃, the drying time is 20 hours), and then placed in a discharge plasma sintering device for sintering (the heating rate is 50-150 ℃/min, the temperature is 1300 ℃, 1500 ℃ and nitrogen), so as to prepare the Ti (C, N) -based cermet with fine grains and uniform tissues. The fracture toughness of the metal ceramic is improved by 33-65%, the Hardness (HRA) is improved by 12-23%, and the bending strength is improved by 32-85%.
Claims (6)
1. The preparation method of the superfine multi-element Ti (C, N) -based metal ceramic is characterized by comprising the following steps: the synthesis method comprises the following steps:
mixing and drying nanometer titanium oxide, nanometer tungsten oxide, nanometer cobalt oxide, nanometer vanadium oxide, nanometer chromium oxide, nanometer reducing agent carbon black and a multi-wall carbon nano tube according to the mass percentage;
b, placing the raw material obtained in the step a into a spark plasma sintering device for sintering to finally obtain the multi-element Ti (C, N) -based metal ceramic; the fracture toughness of the metal ceramic is improved by 33-65%, the Hardness (HRA) is improved by 12-23%, and the bending strength is improved by 32-85%.
2. The method for preparing the superfine multi-element Ti (C, N) -based cermet according to claim 1 comprises the following raw materials in percentage by mass: 38-52% of nano titanium oxide, 26-32% of nano tungsten oxide, 8-15% of nano cobalt oxide, 0.2-1% of nano vanadium oxide, 0.2-1% of nano chromium oxide, 20-27% of nano carbon black and 0.2-0.8% of multi-walled carbon nano tube.
3. The method as claimed in claim 1, wherein the sintering process is carried out under flowing nitrogen at 1300-1500 deg.C for 0.5-1 h.
4. The method for preparing an ultrafine multi-Ti (C, N) -based cermet according to claim 1, wherein the mixing is performed in any one of a high energy ball mill, a roller ball mill, or a milling machine.
5. The method of preparing an ultrafine poly-Ti (C, N) -based cermet according to claim 1, wherein the drying temperature after ball milling is 50 to 80 ℃ and the drying time is 16 to 30 hours.
6. The method as claimed in claim 1, wherein the sintering is performed under nitrogen atmosphere at a heating rate of 50-150 ℃/min and at a temperature of 1300-1500 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110648974.0A CN113373336A (en) | 2021-06-10 | 2021-06-10 | Preparation of superfine multi-element Ti (C, N) -based metal ceramic |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110648974.0A CN113373336A (en) | 2021-06-10 | 2021-06-10 | Preparation of superfine multi-element Ti (C, N) -based metal ceramic |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113373336A true CN113373336A (en) | 2021-09-10 |
Family
ID=77573726
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110648974.0A Pending CN113373336A (en) | 2021-06-10 | 2021-06-10 | Preparation of superfine multi-element Ti (C, N) -based metal ceramic |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113373336A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115386777A (en) * | 2022-09-02 | 2022-11-25 | 石家庄铁道大学 | Transition metal carbonitride based high-entropy metal ceramic and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6124040A (en) * | 1993-11-30 | 2000-09-26 | Widia Gmbh | Composite and process for the production thereof |
| CN103834842A (en) * | 2014-03-25 | 2014-06-04 | 龙具硬质合金（苏州）有限公司 | TiCN-based metal ceramic numerical control tool material with nanocrystalline grain size and preparation method thereof |
| CN106756388A (en) * | 2016-12-26 | 2017-05-31 | 苏州新锐合金工具股份有限公司 | Toughness reinforcing Ti（C, N）The preparation technology of based ceramic metal composite |
| CN107099723A (en) * | 2017-05-02 | 2017-08-29 | 四川大学 | Surface self-lubricating Ti (C, N) based ceramic metal preparation method based on metal hydride |
| CN107552802A (en) * | 2017-09-26 | 2018-01-09 | 中南大学 | A kind of cermet titanium carbonitride based solid solution powder and preparation method |
| CN108637268A (en) * | 2018-04-24 | 2018-10-12 | 海南大学 | A kind of method that microwave carbon thermal reduction prepares composite Ti (C, N) cermet powder |
| CN110102752A (en) * | 2019-04-29 | 2019-08-09 | 四川轻化工大学 | A kind of cermet solid solution alloy powder and preparation method |
| CN111378888A (en) * | 2020-01-02 | 2020-07-07 | 四川轻化工大学 | Nano particle interface reinforced Ti (C, N) -based metal ceramic material with high nitrogen content and preparation method thereof |
-
2021
- 2021-06-10 CN CN202110648974.0A patent/CN113373336A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6124040A (en) * | 1993-11-30 | 2000-09-26 | Widia Gmbh | Composite and process for the production thereof |
| CN103834842A (en) * | 2014-03-25 | 2014-06-04 | 龙具硬质合金（苏州）有限公司 | TiCN-based metal ceramic numerical control tool material with nanocrystalline grain size and preparation method thereof |
| CN106756388A (en) * | 2016-12-26 | 2017-05-31 | 苏州新锐合金工具股份有限公司 | Toughness reinforcing Ti（C, N）The preparation technology of based ceramic metal composite |
| CN107099723A (en) * | 2017-05-02 | 2017-08-29 | 四川大学 | Surface self-lubricating Ti (C, N) based ceramic metal preparation method based on metal hydride |
| CN107552802A (en) * | 2017-09-26 | 2018-01-09 | 中南大学 | A kind of cermet titanium carbonitride based solid solution powder and preparation method |
| CN108637268A (en) * | 2018-04-24 | 2018-10-12 | 海南大学 | A kind of method that microwave carbon thermal reduction prepares composite Ti (C, N) cermet powder |
| CN110102752A (en) * | 2019-04-29 | 2019-08-09 | 四川轻化工大学 | A kind of cermet solid solution alloy powder and preparation method |
| CN111378888A (en) * | 2020-01-02 | 2020-07-07 | 四川轻化工大学 | Nano particle interface reinforced Ti (C, N) -based metal ceramic material with high nitrogen content and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115386777A (en) * | 2022-09-02 | 2022-11-25 | 石家庄铁道大学 | Transition metal carbonitride based high-entropy metal ceramic and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107475548B (en) | A kind of preparation method of nanometer of toughening superfine WC-Co cemented carbide | |
| CN100507038C (en) | Preparation process of tungsten carbide/inhibitor composite powder and superfine hard alloy thereof | |
| Li et al. | Effect of Mo addition mode on the microstructure and mechanical properties of TiC–high Mn steel cermets | |
| CN110102752B (en) | Solid solution alloy powder for metal ceramic and preparation method thereof | |
| WO2021027824A1 (en) | Tungsten-base alloy material and preparation method therefor | |
| WO2004029313A1 (en) | Nano-crystal austenitic metal bulk material having high hardness, high strength and toughness , and method for production thereof | |
| JP4403286B2 (en) | Cemented carbide tool material and manufacturing method thereof | |
| CN109338193B (en) | Coreless-ring structure metal ceramic alloy and preparation method thereof | |
| CN103924111A (en) | Preparation method of hard alloy nanoparticle powder and high-performance sintered block material | |
| WO2013080390A1 (en) | α+β OR β TITANIUM ALLOY AND METHOD FOR PRODUCING SAME | |
| CN113337746A (en) | Preparation method of carbide-reinforced high-entropy alloy composite material | |
| CN108543952A (en) | A kind of method of precursor process synthesis WC base nano composite powders | |
| CN106141197B (en) | Preparation method of fine-particle tungsten powder | |
| CN114318039B (en) | Element alloying preparation method of metal matrix composite material with three-peak grain structure | |
| CN113373336A (en) | Preparation of superfine multi-element Ti (C, N) -based metal ceramic | |
| JP2006274323A (en) | Nanocrystal alloy steel powder having high hardness and excellent corrosion resistance and nanocrystal alloy steel bulk material having high strength/toughness and excellent corrosion resistance and production method thereof | |
| CN106756390A (en) | A kind of hard alloy containing slab-shaped tungsten carbide crystal grain and preparation method thereof | |
| WO2019169744A1 (en) | (wmo)c-based cemented carbide material and preparation method therefor | |
| CN110066952B (en) | Preparation method of zirconium oxide reinforced molybdenum alloy bar | |
| CN111893339A (en) | Method for preparing high-performance WC-8Co-Y2O3 hard alloy by wet chemical method | |
| CN113355579A (en) | Novel preparation method of superfine multi-element Ti (C, N) -based metal ceramic | |
| WO2005092542A1 (en) | High carbon nano crystalline iron alloy powder and bulk material having high hardness, and method for production thereof | |
| JP2004142993A (en) | Hexagonal composite carbide, and production method therefor | |
| JP4281857B2 (en) | Sintered tool steel and manufacturing method thereof | |
| JP3063340B2 (en) | Production method of fine tungsten carbide powder |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210910 |
|
| RJ01 | Rejection of invention patent application after publication |