CN106756168A - The method that one kind prepares Ti (C, N) based ceramic metal based on carbon thermal reduction molybdenum trioxide - Google Patents
The method that one kind prepares Ti (C, N) based ceramic metal based on carbon thermal reduction molybdenum trioxide Download PDFInfo
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- CN106756168A CN106756168A CN201611135714.9A CN201611135714A CN106756168A CN 106756168 A CN106756168 A CN 106756168A CN 201611135714 A CN201611135714 A CN 201611135714A CN 106756168 A CN106756168 A CN 106756168A
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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
- C22C1/053—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor with in situ formation of hard compounds
- C22C1/055—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor with in situ formation of hard compounds using carbon
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- 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
Abstract
The invention discloses the method that one kind prepares Ti (C, N) based ceramic metal based on carbon thermal reduction molybdenum trioxide, the cermet composition mass fraction is as follows：Ti is that 31.5~39.7, C is that 10.6~11, N is that 3.6~4.6, O is that 5.4~6.6, Ni is that 22~31, Mo is that 10~12.4, W is 4.2~7.7.Preparation method feature is：When compound is prepared, with molybdenum trioxide as molybdenum source, it is directly appended in compound, then in turn through batch mixing, adds forming agent, compressing, removing forming agent and use special combination vacuum sintering method, is obtained the sintered cermet of densification.The present invention can be greatly reduced production cost, and be effectively improved the microscopic structure of cermet, improve its mechanical property, have broad application prospects.
Description
Technical field
The present invention relates to the method that one kind prepares Ti (C, N) based ceramic metal based on carbon thermal reduction molybdenum trioxide, belong to powder
Last metallurgical technology field.
Background technology
Ti (C, N) based ceramic metal has that density is low, red hardness is high, wearability is high, high temperature and creep resistance ability and anti-oxidant
Ability is strong and the advantages of intermetallic coefficient of friction is low, corrosion resistance is good, in cutter, mould, wear-resisting spare part, corrosion-resistant device
Gathered around etc. various fields and had broad application prospects.Such as it is used as cutter material, compared with conventional hard alloy cutter, it can permit
Permitted to have cutting speed higher and the larger depth of cut, anti-crescent hollow abrasion ability be higher, workpiece to be machined surface quality is more preferable；
Such as it is used as mold materials, not only red hardness is high, heat endurance and oxidation resistant, and good toughness；Such as it is used as wear-resisting and corrosion resistant
Corrosion material, its service life is higher compared to similar other materials.In recent years, hair of Ti (C, the N) based ceramic metals in countries in the world
Exhibition is all very rapid.
The subject matter that Ti (C, N) based ceramic metal of exploitation is present at present is under conditions of certain degree of hardness is kept, to resist
Curved intensity and fracture toughness are still relatively low, make its in theory due advantage be not not fully exerted, so as to cause it to apply
Scope is subject to certain restrictions.In the last few years, some researchers by attempt introducing all kinds of whiskers, CNT wait until Ti (C,
N) in based ceramic metal, the activeness and quietness of cermet is realized.The above method makes although obtaining relatively good experimental result
The obdurability of Ti (C, N) based ceramic metal has a certain degree of raising.But, the additive such as whisker, CNT price is held high
It is expensive, and purity also needs further raising, is easy to oxygen uptake and reunion.Before being added in compound, it is necessary to carry out removal of impurities, take off
The pre-treatment such as oxygen and dispersion.Above-mentioned additive is not only very expensive, and is difficult to be evenly distributed in compound, makes cermet
Preparation cost significantly rise, preparation technology complexity substantially increases, and in batch production, it is easy to form metallurgical lacking
Fall into, substandard products occur, thus be difficult in industrial circle obtain practical application so far.On the other hand, researcher also is burnt using hot pressing
The special sintering method such as knot, low pressure-HIP sintering, discharge plasma sintering prepares Ti (C, N) Base Metal pottery of fine grain
Porcelain, makes the performance of material obtain a certain degree of raising, but these special sintering methods are higher to equipment requirement, early investment
It is larger, and production cost significantly improves.
In view of the foregoing, in order that Ti (C, N) based ceramic metal can be applied in more areas, it is necessary to this kind of
Material is further studied, and develops a kind of Ti of high-performance and low-cost (C, N) based ceramic metal.
The content of the invention
For above-mentioned technical problem, Ti is prepared based on carbon thermal reduction molybdenum trioxide it is an object of the invention to provide one kind
The method of (C, N) based ceramic metal.The method can prepare that comprehensive mechanical property is higher, stable performance Ti (C, N) fund
Category ceramics, and it is cheap for manufacturing cost.
Realizing the technical solution of the object of the invention is：
The method that one kind prepares Ti (C, N) based ceramic metal based on carbon thermal reduction molybdenum trioxide, comprises the following steps that：
1) component of preparation compound, including following mass fraction：Ti is 31.5~39.7, C for 10.6~11, N is 3.6
~4.6, O are that 5.4~6.6, Ni is that 22~31, Mo is that 10~12.4, W is 4.2~7.7；
When preparing the compound of mentioned component, raw materials used is Ti (C, N) solid solution powder, MoO3Powder, WC powder, Ni powder, powder
The granularity at end is micron order；
2) batch mixing is carried out in planetary ball mill, drum's speed of rotation is 300~400rpm, and the time is 24~36h；
3) add forming agent, shaping agent concentration be 7wt.% polyvinyl alcohol water solutions, additional proportion be compound 3~
5wt%；
4) it is compressing under 150~200MPa of pressing pressure；
5) forming agent is removed in vacuum drying oven of the vacuum higher than 10Pa, the programming rate between 200~400 DEG C is
0.3~0.4 DEG C/min；
6) vacuum-sintering, is carried out in vacuum sintering furnace, and vacuum is higher than 1.0 × 10-2Pa；Described vacuum-sintering is divided into
Four-stage, is continuously heating to 600~800 DEG C by the pressed compact for removing forming agent first, is incubated 2~4h；Then raise temperature to 1200
~1240 DEG C, it is incubated 1~2h；Then 1400~1440 DEG C are warming up to again, are incubated 0.5~1h；The last cooling with 20 DEG C/min
Speed makes furnace temperature quickly be down to less than 1000 DEG C, obtains Ti (C, N) based ceramic metal.
To realize this purpose, step 1 of the present invention) in prepare compound when, the Mo in compound is with MoO3The form of powder is drawn
Enter.In general, in Ti (C, N) based ceramic metal, oxygen is considered as harmful element, because their meetings in liquid sintering process
The angle of wetting between hard phase and Binder Phase is become big, reduce its wetability, so that deteriorate materials microstructure and performance, so mesh
The preceding oxygen content in all powder is reduced as far as possible during preparing cermet.The present invention is with MoO3The form of powder is by Mo
It is incorporated into Ti (C, N) based ceramic metal compound with O elements, while introducing the C of corresponding content in the form of graphite powder, is led to
Cross rationally control sintering process, MoO3There is following solid phase reaction before 800 DEG C with graphite powder in powder：MoO3+C→MoO2+CO；
MoO2+2C→Mo+2CO；2Mo+C→Mo2C, it is in situ that O is removed and Mo is generated with C chemical combination2C.And now sintered body is still in preceding
The solid-phase sintering stage of phase, its relative density is relatively low, and hole is in perforate state, and the gas for reacting generation under vacuum can
Smoothly effusion, will not have a negative impact to follow-up liquid-phase sintering.Meanwhile, introduced a large amount of graphite powders and MoO3Powder occurs
The reducibility gas CO discharged in carbothermic reduction process can make more thorough, the purification of the absorption oxygen removal on other original powder surfaces
Interface between ceramic phase and metallic binding phase, is effectively improved the microscopic structure of cermet, strengthens the bond strength of boundary,
The purpose of Ti (C, N) based ceramic metal obdurability is improved so as to reach.
To realize this purpose, preparation method has following features：Vacuum-sintering is divided into four-stage, is first molded removing
The pressed compact of agent is warming up to 600~800 DEG C, is incubated 2~4h；1200~1240 DEG C are then raised temperature to, 1~2h is incubated；Then rise again
Temperature is incubated 0.5~1h to 1400~1440 DEG C；The last cooling velocity with 20 DEG C/min make furnace temperature be quickly down to 1000 DEG C with
Under.It is to allow MoO that 2~4h is incubated at 600~800 DEG C3Powder and graphite powder pass through carbothermic reduction reaction in situ and generate Mo2C；With
After be warming up to 1200~1240 DEG C, 1~2h of insulation is in order that the Mo of generation2WC and Ti (C, N) solid solution in C, compound
Annular phase is formed in ceramic hard phase particle surface by solid phase reaction, to improve following liquid-phase sintering stage metal adhesive phase
To the wetability of ceramic phase, and prevent crystal grain agglomeration；1400~1440 DEG C are warming up to, 0.5~1h of insulation is in order that gold
Category ceramics enter the liquid-phase sintering stage, complete densification and the microstructure homogenization of sintered body；The last cooling speed with 20 DEG C/min
Degree makes furnace temperature quickly be down to less than 1000 DEG C, is in order that sintered body rapid solidification, prevents ceramic hard from stopping in liquid phase stage
Overlong time is stayed too to be grown up by crystallization of the dissolution and precipitation mechanism.
Beneficial effect of the present invention is：
1st, Ti (C, N) based ceramic metal prepared based on carbon thermal reduction molybdenum trioxide that the present invention is provided, with higher
Comprehensive mechanical property, and its hardness, bending strength and fracture toughness can adjust according to the performance requirement in different application field.Institute
The cermet material of preparation is not only with red hardness is good, wearability is high, oxidation resistance is strong and intermetallic coefficient of friction is low
The advantages of, and obdurability and stability significantly improve, and cannot be only used for Tool in Cutting field, be equally applicable to mine,
The fields such as oil, coal mining, can also be widely used as wearing piece, high temperature resistant part, corrosion barrier etc..
What the 2nd, the present invention was provided is free of valuable unit based on Ti (C, N) based ceramic metal prepared by carbon thermal reduction molybdenum trioxide
Element, the MoO as Mo sources3Powder price is with respect to Mo powder or Mo2C powder is cheaper, and cost of material is cheaper.
What the 3rd, the present invention was provided uses the true of routine based on Ti (C, N) based ceramic metal prepared by carbon thermal reduction molybdenum trioxide
Prepared by empty sintering process, to production equipment without particular/special requirement, be conducive to commercial introduction application；Technical process is simple, complete at one
Thermal cycle in complete, can significantly saving energy consumption, reduce production cost, improve productivity ratio.
Specific embodiment
Technique effect of the invention is further illustrated below in conjunction with example.The raw material that following instance is used is Ti (C, N)
Powder, Ni powder, MoO3Powder, WC powder, graphite powder.
Table 1 is 4 kinds of compounds of component prescription.It is prepared by three kinds of different technical parameters that embodiment 1-3 is respectively adopted
Into Ti (C, N) based ceramic metal, and its hardness, bending strength and palmqvist fracture toughnesses are determined respectively, wherein 1#With 2#Into
Metallic binding phase is relatively low in distribution side, and hardness is higher, it is adaptable to cutting tool and wearing piece field, 3#With 4#Gold in component prescription
Category Binder Phase is higher, and obdurability is preferable, it is adaptable to the part needed for making the fields such as mine, oil, coal mining.
1 four kinds of component prescriptions of compound of table
| Composition | Ti | C | N | O | Ni | Mo | W |
| 1# | 39.7 | 10.6 | 4.6 | 5.4 | 22 | 10 | 7.7 |
| 2# | 37.2 | 11 | 4.3 | 5.8 | 25 | 10.8 | 5.9 |
| 3# | 33.2 | 10.8 | 3.9 | 6.4 | 28 | 11.6 | 6.1 |
| 4# | 31.5 | 10.7 | 3.6 | 6.6 | 31 | 12.4 | 4.2 |
Embodiment 1：
1st, 4 kinds of compounds are prepared according to table 1；
2nd, compound is placed in planetary ball mill and is mixed, drum's speed of rotation is 300rpm, the time is 36h；
3rd, forming agent is added：It is the polyvinyl alcohol water solution of 7wt.% that forming agent uses concentration, and addition is compound
3wt%；
4th, it is compressing：Compressing pressure used is 150MPa；
5th, forming agent is removed：Removing forming agent operation is carried out in vacuum sintering furnace, and vacuum is higher than 10Pa, 200~
Programming rate between 400 DEG C is 0.3 DEG C/min；
6th, vacuum-sintering：Carried out in vacuum sintering furnace, vacuum is higher than 1.0 × 10-2Pa.Vacuum-sintering is divided into four ranks
Section, is continuously heating to 600 DEG C by the pressed compact for removing forming agent first, is incubated 4h；1240 DEG C are then raised temperature to, 1h is incubated；Then
1440 DEG C are warming up to again, are incubated 30min；The last cooling velocity with 20 DEG C/min makes furnace temperature quickly be down to less than 1000 DEG C, obtains
To Ti (C, N) based ceramic metal.
Under above-mentioned preparation process condition, the mechanical property of the cermet of heterogeneity formula is shown in Table 2.
The mechanical property of the different metal ceramics that table 2 is prepared using technique 1
| Composition | 1# | 2# | 3# | 4# |
| Bending strength σb(MPa) | 1715 | 1938 | 2217 | 2461 |
| Hardness (HRA) | 92.3 | 91.1 | 89.7 | 88.0 |
| Fracture toughness (MNm-3/2) | 12.4 | 14.6 | 17.9 | 22.3 |
Embodiment 2：
1st, 4 kinds of compounds are prepared according to table 1；
2nd, compound is placed in planetary ball mill and is mixed, drum's speed of rotation is 350rpm, the time is 30h；
3rd, forming agent is added：It is the polyvinyl alcohol water solution of 7wt.% that forming agent uses concentration, and addition is compound
4wt%；
4th, it is compressing：Compressing pressure used is 180MPa；
5th, forming agent is removed：Removing forming agent operation is carried out in vacuum sintering furnace, and vacuum is higher than 10Pa, 200~
Programming rate between 400 DEG C is 0.4 DEG C/min；
6th, vacuum-sintering：Carried out in vacuum sintering furnace, vacuum is higher than 1.0 × 10-2Pa.Vacuum-sintering is divided into four ranks
Section, is continuously heating to 700 DEG C by the pressed compact for removing forming agent first, is incubated 3h；1220 DEG C are then raised temperature to, 1.5h is incubated；So
It is warming up to 1420 DEG C again afterwards, is incubated 40min；The last cooling velocity with 20 DEG C/min makes furnace temperature quickly be down to less than 1000 DEG C,
Obtain Ti (C, N) based ceramic metal.
Under above-mentioned preparation process condition, the performance of the cermet of heterogeneity proportioning is shown in Table 3.
The mechanical property of the different metal ceramics that table 3 is prepared using technique 2
| Composition | 1# | 2# | 3# | 4# |
| Bending strength σb(MPa) | 1724 | 2017 | 2256 | 2473 |
| Hardness (HRA) | 92.1 | 91.0 | 89.5 | 88.2 |
| Fracture toughness (MNm-3/2) | 11.8 | 14.3 | 18.1 | 22.5 |
Embodiment 3：
1st, 4 kinds of compounds are prepared according to table 1；
2nd, compound is placed in planetary ball mill and is mixed, drum's speed of rotation is 400rpm, the time is 24h；
3rd, forming agent is added：It is the polyvinyl alcohol water solution of 7wt.% that forming agent uses concentration, and addition is compound
5wt%；
4th, it is compressing：Compressing pressure used is 200MPa；
5th, forming agent is removed：Removing forming agent operation is carried out in vacuum sintering furnace, and vacuum is higher than 10Pa, 200~
Programming rate between 400 DEG C is 0.4 DEG C/min；
6th, vacuum-sintering：Carried out in vacuum sintering furnace, vacuum is higher than 1.0 × 10-2Pa.Vacuum-sintering is divided into four ranks
Section, is continuously heating to 800 DEG C by the pressed compact for removing forming agent first, is incubated 2h；1200 DEG C are then raised temperature to, 2h is incubated；Then
1400 DEG C are warming up to again, are incubated 1h；The last cooling velocity with 20 DEG C/min makes furnace temperature quickly be down to less than 1000 DEG C, obtains Ti
(C, N) based ceramic metal.
Under above-mentioned preparation process condition, the performance of the cermet of heterogeneity proportioning is shown in Table 4.
The mechanical property of the different metal ceramics that table 4 is prepared using technique 3
| Composition | 1# | 2# | 3# | 4# |
| Bending strength σb(MPa) | 1709 | 1997 | 2233 | 2469 |
| Hardness (HRA) | 92.0 | 91.2 | 89.4 | 88.1 |
| Fracture toughness (MNm-3/2) | 12.1 | 14.1 | 18.3 | 21.9 |
In this letter of authorization span, the technological parameter of sintering process first stage is relatively large to performance impact, only
Have when this stage sintering temperature and soaking time collocation it is reasonable when (when holding temperature is higher, the time accordingly shortens；Holding temperature
When relatively low, the time answers proper extension), the cermet of above-mentioned each component prescription can obtain relatively good comprehensive mechanical property.
In a word, in claims span, its influence to material mechanical performance of above-mentioned technological factor is limited.
The above embodiments are intended to illustrate the present invention, rather than limitation, therefore with it is of the invention
Any change in claims suitable implication and scope, is all considered as being included within the scope of the claims.
Concrete application approach of the present invention is a lot, and the above is only the preferred embodiment of the present invention, it is noted that for
For those skilled in the art, under the premise without departing from the principles of the invention, some improvement can also be made, such as
Other constituent elements are substituted with corresponding oxide, and oxide are reduced by carbothermic method in situ in sintering process,
These improvement also should be regarded as protection scope of the present invention.
Claims (6)
1. it is a kind of to be based on the method that carbon thermal reduction molybdenum trioxide prepares Ti (C, N) based ceramic metal, it is characterised in that including following
Step：
1) component of preparation compound, including following mass fraction：Ti be 31.5~39.7, C be 10.6~11, N be 3.6~
4.6, O is that 5.4~6.6, Ni is that 22~31, Mo is that 10~12.4, W is 4.2~7.7；
2) batch mixing；
3) forming agent is added；
4) it is compressing；
5) forming agent is removed；
6) vacuum-sintering, is carried out in vacuum sintering furnace, and vacuum is higher than 1.0 × 10-2Pa；Described vacuum-sintering is divided into four
In the stage, the pressed compact removed after forming agent is continuously heating to 600~800 DEG C first, is incubated 2~4h；Then raise temperature to 1200~
1240 DEG C, it is incubated 1~2h；Then 1400~1440 DEG C are warming up to again, are incubated 0.5~1h；The last cooling speed with 20 DEG C/min
Degree makes furnace temperature quickly be down to less than 1000 DEG C, obtains Ti (C, N) based ceramic metal.
2. the method that Ti (C, N) based ceramic metal is prepared based on carbon thermal reduction molybdenum trioxide according to claim 1, it is special
Levy and be：When preparing the compound of mentioned component, raw materials used is Ti (C, N) solid solution powder, MoO3Powder, WC powder, Ni powder, powder
Granularity be micron order.
3. the method that Ti (C, N) based ceramic metal is prepared based on carbon thermal reduction molybdenum trioxide according to claim 1, it is special
Levy and be：The step 2) in compounding process carried out in planetary ball mill, drum's speed of rotation be 300~400rpm, when
Between be 24~36h.
4. the method that Ti (C, N) based ceramic metal is prepared based on carbon thermal reduction molybdenum trioxide according to claim 1, it is special
Levy and be：Described step 3) in forming agent used be concentration be 7wt.% polyvinyl alcohol water solutions, additional proportion is compound
3~5wt%.
5. the method that Ti (C, N) based ceramic metal is prepared based on carbon thermal reduction molybdenum trioxide according to claim 1, it is special
Levy and be：Described step 4) in pressing pressure used by compressing operation be 150~200MPa.
6. the method that Ti (C, N) based ceramic metal is prepared based on carbon thermal reduction molybdenum trioxide according to claim 1, it is special
Levy and be：Described step 5) in removing forming agent operation carried out in vacuum drying oven of the vacuum higher than 10Pa, 200~
Programming rate between 400 DEG C is 0.3~0.4 DEG C/min.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109487141A (en) * | 2018-12-12 | 2019-03-19 | 南京航空航天大学 | A kind of preparation method of plate carbide solid solution toughening mixed crystal Ti (C, N) based ceramic metal |
| CN109576545A (en) * | 2018-12-12 | 2019-04-05 | 南京航空航天大学 | A kind of Ti (C, N) based ceramic metal and preparation method thereof with duplex grain structure |
| CN110408830A (en) * | 2019-08-28 | 2019-11-05 | 三峡大学 | A kind of Ti (C, N) base metal-ceramic material and its Carbon balance control method |
| CN114752835A (en) * | 2022-03-18 | 2022-07-15 | 南京航空航天大学 | Ti (C, N) -based metal ceramic with honeycomb structure and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5756410A (en) * | 1997-02-27 | 1998-05-26 | The Dow Chemical Company | Method for making submicrometer transition metal carbonitrides |
| CN1410575A (en) * | 2002-12-02 | 2003-04-16 | 株洲硬质合金集团有限公司 | Metal ceramic and its preparation method |
| CN104131192A (en) * | 2014-07-25 | 2014-11-05 | 常熟市鼎丰金属材料科技有限公司 | Ti(C,N)-based metal ceramic with gradient structure and plasma-nitriding preparation method thereof |
-
2016
- 2016-12-12 CN CN201611135714.9A patent/CN106756168B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5756410A (en) * | 1997-02-27 | 1998-05-26 | The Dow Chemical Company | Method for making submicrometer transition metal carbonitrides |
| CN1410575A (en) * | 2002-12-02 | 2003-04-16 | 株洲硬质合金集团有限公司 | Metal ceramic and its preparation method |
| CN104131192A (en) * | 2014-07-25 | 2014-11-05 | 常熟市鼎丰金属材料科技有限公司 | Ti(C,N)-based metal ceramic with gradient structure and plasma-nitriding preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| ASAO OYA ET AL.: "Carbothermal Reduction of the Molybdenum Oxide/Phenanthroline Complex", 《JOURNAL OF THE AMERICAN CERAMIC SOCIETY》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109487141A (en) * | 2018-12-12 | 2019-03-19 | 南京航空航天大学 | A kind of preparation method of plate carbide solid solution toughening mixed crystal Ti (C, N) based ceramic metal |
| CN109576545A (en) * | 2018-12-12 | 2019-04-05 | 南京航空航天大学 | A kind of Ti (C, N) based ceramic metal and preparation method thereof with duplex grain structure |
| CN109576545B (en) * | 2018-12-12 | 2020-09-25 | 南京航空航天大学 | Ti (C, N) -based metal ceramic with mixed crystal structure and preparation method thereof |
| CN110408830A (en) * | 2019-08-28 | 2019-11-05 | 三峡大学 | A kind of Ti (C, N) base metal-ceramic material and its Carbon balance control method |
| CN114752835A (en) * | 2022-03-18 | 2022-07-15 | 南京航空航天大学 | Ti (C, N) -based metal ceramic with honeycomb structure and preparation method thereof |
| CN114752835B (en) * | 2022-03-18 | 2022-10-25 | 南京航空航天大学 | Ti (C, N) -based metal ceramic with honeycomb structure and preparation method thereof |
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