CN106756168B - 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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- CN106756168B CN106756168B CN201611135714.9A CN201611135714A CN106756168B CN 106756168 B CN106756168 B CN 106756168B CN 201611135714 A CN201611135714 A CN 201611135714A CN 106756168 B CN106756168 B CN 106756168B
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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 a kind of method that Ti (C, N) based ceramic metal is prepared 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：It when preparing mixture, using molybdenum trioxide as molybdenum source, is directly appended in mixture, then in turn through batch mixing, adds in forming agent, compression moulding, removes forming agent and use special combination vacuum sintering method, obtain fine and close sintered cermet.Production cost can be greatly reduced in the present invention, and is effectively improved the microscopic structure of cermet, improve its mechanical property, have broad application prospects.
Description
Technical field
The present invention relates to a kind of methods that Ti (C, N) based ceramic metal is prepared 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
The advantages that ability is strong, low with intermetallic coefficient of friction, corrosion resistance is good, in cutter, mold, wear-resisting spare part, corrosion-resistant device
Etc. various fields gather around and have broad application prospects.Such as it is used as cutter material, compared with common hard alloy cutter, it can permit
Permitted to have higher cutting speed and the larger depth of cut, anti-crescent hollow abrasion ability higher, workpiece to be machined surface quality more preferable；
Such as it is used as mold materials, not only red hardness height, thermal stability and oxidation resistant, and good toughness；Such as it is used as wear-resisting and corrosion resistant
Corrosion material, service life compare similar other materials higher.In recent years, Ti (C, N) based ceramic metals are in the hair of countries in the world
Exhibition is all very rapid.
Main problem existing for Ti (C, the N) based ceramic metal developed at present is under conditions of certain degree of hardness is kept, and is resisted
Curved intensity and fracture toughness are still relatively low, and making it, theoretically due advantage is not not fully exerted, and are applied so as to cause it
Scope is subject to certain restrictions.In recent years, some researchers are by attempting to introduce all kinds of whiskers, carbon nanotubes 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 degree of raising.But the additives price such as whisker, carbon nanotubes is held high
It is expensive, and purity also needs to be further improved, and is easy to oxygen uptake and reunion.Before being added in mixture, it is necessary to be cleaned, taken off
Oxygen waits pre-treatments with scattered.Above-mentioned additive is not only very expensive, but also is difficult to be evenly distributed in mixture, makes cermet
Manufacturing cost significantly rise, preparation process complexity substantially increases, and in batch production, it is easy to form metallurgical lack
It falls into, substandard products occurs, thus be difficult in industrial circle obtain practical application so far.On the other hand, researcher also is burnt using hot pressing
The special sinterings 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 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 to make Ti (C, N) based ceramic metal that can be applied in more areas, it is necessary to such
Material conducts further research, 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.This method can prepare Ti (C, N) fund that comprehensive mechanical property is higher, performance is stablized
Belong to ceramics, and manufacture of low 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, is as follows：
1) mixture is prepared, includes the component of following mass fraction：Ti is that 31.5~39.7, C is 10.6~11, N 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；
It is raw materials used for Ti (C, N) solid solution powder, MoO when preparing the mixture of mentioned component3Powder, 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 in forming agent, shaping agent concentration be 7wt.% polyvinyl alcohol water solutions, additional proportion be mixture 3~
5wt%；
4) compression moulding under 150~200MPa of pressing pressure；
5) forming agent is removed in vacuum drying oven of the vacuum degree higher than 10Pa, the heating rate between 200~400 DEG C is
0.3~0.4 DEG C/min；
6) vacuum-sintering carries out in vacuum sintering furnace, and vacuum degree is higher than 1.0 × 10-2Pa；The vacuum-sintering is divided into
The green compact for removing forming agent is continuously heating to 600~800 DEG C by four-stage first, keeps the temperature 2~4h；Then raise temperature to 1200
~1240 DEG C, keep the temperature 1~2h；Then 1400~1440 DEG C are warming up to again, keep the temperature 0.5~1h；Finally with the cooling of 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, when preparing mixture in step 1) of the present invention, the Mo in mixture 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 made to become larger, reduces its wetability, so as to deteriorate materials microstructure and performance, so mesh
The preceding oxygen content all reduced as far as possible during prepare cermet in powder.The present invention is with MoO3The form of powder is by Mo
It is introduced into O elements in Ti (C, N) based ceramic metal mixture, while the C of corresponding content is introduced in the form of graphite powder, led to
Cross rationally control sintering process, MoO3With graphite powder following solid phase reaction occurs before 800 DEG C for powder：MoO3+C→MoO2+CO；
MoO2+2C→Mo+2CO；2Mo+C→Mo2C, it is in situ that O is removed and generates Mo with C chemical combination2C.And sintered body is still in preceding at this time
In the solid-phase sintering stage of phase, 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 subsequent 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, enhances the bond strength of boundary,
So as to reach the purpose for improving Ti (C, N) based ceramic metal obdurability.
To realize this purpose, preparation method has following features：Vacuum-sintering is divided into four-stage, is first molded removing
The green compact of agent is warming up to 600~800 DEG C, keeps the temperature 2~4h；1200~1240 DEG C are then raised temperature to, keeps the temperature 1~2h；Then rise again
Temperature keeps the temperature 0.5~1h to 1400~1440 DEG C；Finally with the cooling velocity of 20 DEG C/min make furnace temperature be quickly down to 1000 DEG C with
Under.It is to allow MoO that 2~4h are kept the temperature at 600~800 DEG C3Powder and graphite powder generate Mo by carbothermic reduction reaction in situ2C；With
After be warming up to 1200~1240 DEG C, 1~2h of heat preservation is to make the Mo of generation2C, the WC in mixture and Ti (C, N) solid solution
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 heat preservation is to make gold
Belong to ceramics and enter the liquid-phase sintering stage, complete densification and the microstructure homogenization of sintered body；Finally with the cooling speed of 20 DEG C/min
Degree makes furnace temperature quickly be down to less than 1000 DEG C, is in order to which sintered body is made quickly to solidify, prevents ceramic hard from mutually stopping in liquid phase stage
Overlong time is stayed too to grow up by crystallization of the dissolution and precipitation mechanism.
Advantageous effect of the present invention is：
1st, Ti (C, N) based ceramic metal provided by the invention prepared based on carbon thermal reduction molybdenum trioxide, is had higher
Comprehensive mechanical property, and its hardness, bending strength and fracture toughness can be adjusted 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, low with intermetallic coefficient of friction
The advantages that, 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..
2nd, Ti (C, N) based ceramic metal provided by the invention prepared based on carbon thermal reduction molybdenum trioxide is free of valuable member
Element, the MoO as Mo sources3Powder price is with respect to Mo powder or Mo2C powder is cheaper, and cost of material is cheaper.
3rd, Ti (C, N) based ceramic metal provided by the invention prepared based on carbon thermal reduction molybdenum trioxide uses the true of routine
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 save energy consumption, reduce production cost, improve productivity.
Specific embodiment
The technique effect further illustrated the present invention below in conjunction with example.Raw material is Ti (C, N) used by following instance
Powder, Ni powder, MoO3Powder, WC powder, graphite powder.
Table 1 is the mixture of 4 kinds of component prescriptions.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 measured respectively, wherein 1#With 2#Into
Metallic binding phase is relatively low in distribution side, and hardness is higher, suitable for cutting tool and wearing piece field, 3#With 4#It is golden in component prescription
Belong to bonding and compare height, obdurability is preferable, suitable for making the part needed for the fields such as mine, oil, coal mining.
The component prescription of 1 four kinds of mixtures of table
| Ingredient | 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 mixtures are prepared according to table 1；
2nd, mixture is placed in planetary ball mill and mixed, drum's speed of rotation 300rpm, time 36h；
3rd, forming agent is added：Forming agent uses polyvinyl alcohol water solution of the concentration for 7wt.%, and addition is mixture
3wt%；
4th, compression moulding：Pressure used in compression moulding is 150MPa；
5th, forming agent is removed：Removing forming agent process carries out in vacuum sintering furnace, and vacuum degree is higher than 10Pa, 200~
Heating rate between 400 DEG C is 0.3 DEG C/min；
6th, vacuum-sintering：It is carried out in vacuum sintering furnace, vacuum degree is higher than 1.0 × 10-2Pa.Vacuum-sintering is divided into four ranks
The green compact for removing forming agent is continuously heating to 600 DEG C by section first, keeps the temperature 4h；1240 DEG C are then raised temperature to, keeps the temperature 1h；Then
1440 DEG C are warming up to again, keep the temperature 30min；Finally with the cooling velocity of 20 DEG C/min furnace temperature is made quickly to be down to less than 1000 DEG C, obtained
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 for the different metal ceramics that table 2 is prepared using technique 1
| Ingredient | 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 mixtures are prepared according to table 1；
2nd, mixture is placed in planetary ball mill and mixed, drum's speed of rotation 350rpm, time 30h；
3rd, forming agent is added：Forming agent uses polyvinyl alcohol water solution of the concentration for 7wt.%, and addition is mixture
4wt%；
4th, compression moulding：Pressure used in compression moulding is 180MPa；
5th, forming agent is removed：Removing forming agent process carries out in vacuum sintering furnace, and vacuum degree is higher than 10Pa, 200~
Heating rate between 400 DEG C is 0.4 DEG C/min；
6th, vacuum-sintering：It is carried out in vacuum sintering furnace, vacuum degree is higher than 1.0 × 10-2Pa.Vacuum-sintering is divided into four ranks
The green compact for removing forming agent is continuously heating to 700 DEG C by section first, keeps the temperature 3h；1220 DEG C are then raised temperature to, keeps the temperature 1.5h；So
It is warming up to 1420 DEG C again afterwards, keeps the temperature 40min；Finally with the cooling velocity of 20 DEG C/min furnace temperature is made quickly to 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 for the different metal ceramics that table 3 is prepared using technique 2
| Ingredient | 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 mixtures are prepared according to table 1；
2nd, mixture is placed in planetary ball mill and mixed, drum's speed of rotation 400rpm, the time is for 24 hours；
3rd, forming agent is added：Forming agent uses polyvinyl alcohol water solution of the concentration for 7wt.%, and addition is mixture
5wt%；
4th, compression moulding：Pressure used in compression moulding is 200MPa；
5th, forming agent is removed：Removing forming agent process carries out in vacuum sintering furnace, and vacuum degree is higher than 10Pa, 200~
Heating rate between 400 DEG C is 0.4 DEG C/min；
6th, vacuum-sintering：It is carried out in vacuum sintering furnace, vacuum degree is higher than 1.0 × 10-2Pa.Vacuum-sintering is divided into four ranks
The green compact for removing forming agent is continuously heating to 800 DEG C by section first, keeps the temperature 2h；1200 DEG C are then raised temperature to, keeps the temperature 2h；Then
1400 DEG C are warming up to again, keep the temperature 1h；Finally with the cooling velocity of 20 DEG C/min furnace temperature is made quickly to 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 4.
The mechanical property for the different metal ceramics that table 4 is prepared using technique 3
| Ingredient | 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 value range, the technological parameter of sintering process first stage is relatively large on performance influence, 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 should be appropriately extended), the cermet of above-mentioned each component prescription can obtain relatively good comprehensive mechanical property.
In short, in claims value range, its influence to material mechanical performance of above-mentioned technological factor is limited.
The above embodiments are merely intended to illustrate the present invention rather than to limit it, therefore with the present invention's
Any change in the comparable meaning and scope of claims, should be construed as being included in the scope of the claims.
There are many concrete application approach of the present invention, and the above is only the preferred embodiment of the present invention, it is noted that for
For those skilled in the art, without departing from the principle of the present invention, several improvement can also be made, such as
Other constituent elements with corresponding oxide are substituted, and oxide is reduced by carbothermic method in situ in sintering process,
These improvement also should be regarded as protection scope of the present invention.
Claims (5)
1. the method that one kind prepares Ti (C, N) based ceramic metal based on carbon thermal reduction molybdenum trioxide, it is characterised in that including following
Step：
1）Mixture is prepared, includes the component of following mass fraction：Ti be 31.5~39.7, C be 10.6~11, N be 3.6~
4.6, O be 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 mixture of mentioned component, institute
It is Ti (C, N) solid solution powder with raw material, MoO3Powder, WC powder, Ni powder and graphite powder；
2）Batch mixing；
3）Add in forming agent；
4）Compression moulding；
5）Remove forming agent；
6）Vacuum-sintering carries out in vacuum sintering furnace, and vacuum degree is higher than 1.0 × 10-2Pa；The vacuum-sintering is divided into four
The green compact for removing forming agent is continuously heating to 600~800 DEG C by the stage first, keeps the temperature 2~4h；Then raise temperature to 1200~
1240 DEG C, keep the temperature 1~2h；Then 1400~1440 DEG C are warming up to again, keep the temperature 0.5~1h；Finally with the cooling speed of 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 according to claim 1 that Ti (C, N) based ceramic metal is prepared based on carbon thermal reduction molybdenum trioxide, special
Sign is：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.
3. the method according to claim 1 that Ti (C, N) based ceramic metal is prepared based on carbon thermal reduction molybdenum trioxide, special
Sign is：The step 3）In forming agent used be concentration for 7wt.% polyvinyl alcohol water solutions, additional proportion is the 3 of mixture
~5wt%.
4. the method according to claim 1 that Ti (C, N) based ceramic metal is prepared based on carbon thermal reduction molybdenum trioxide, special
Sign is：The step 4）Pressing pressure used in middle compression moulding process is 150~200MPa.
5. the method according to claim 1 that Ti (C, N) based ceramic metal is prepared based on carbon thermal reduction molybdenum trioxide, special
Sign is：The step 5）Middle removing forming agent process carries out in vacuum drying oven of the vacuum degree higher than 10Pa, at 200~400 DEG C
Between heating rate be 0.3~0.4 DEG C/min.
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| 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 |
| CN109487141B (en) * | 2018-12-12 | 2020-08-21 | 南京航空航天大学 | Preparation method of platy carbide solid solution toughened mixed crystal Ti (C, N) -based metal ceramic |
| CN110408830B (en) * | 2019-08-28 | 2020-09-15 | 三峡大学 | Ti (C, N) -based metal ceramic material and carbon balance control 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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| 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 |
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| 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 |
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| Title |
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