CN106048357B - A kind of MoSiC2 base metal-ceramic materials and preparation method thereof - Google Patents
A kind of MoSiC2 base metal-ceramic materials and preparation method thereof Download PDFInfo
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- CN106048357B CN106048357B CN201610422442.4A CN201610422442A CN106048357B CN 106048357 B CN106048357 B CN 106048357B CN 201610422442 A CN201610422442 A CN 201610422442A CN 106048357 B CN106048357 B CN 106048357B
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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
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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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Abstract
The invention discloses a kind of MoSiC2Cermet and preparation method thereof, using Mo powder, Si powder and graphite powder as raw material, according to mass ratio Mo:Si:C=(0.83~0.76):(0.12~0.17):(0.05~0.07), Mo powder, Si powder and graphite powder are fitted into ball grinder, is filled with after inert gas and carries out mechanical alloying, obtain mixed powder；Mixed powder is subjected to hot pressed sintering, sintering temperature is 1400 DEG C~1750 DEG C, and then furnace cooling obtains MoSiC2Base metal-ceramic material.This method short preparation period, process are simple, stock utilization is high, cost is low, obtained MoSiC2Base metal-ceramic material compact structure, good mechanical properties have a good application prospect.
Description
Technical field
The invention belongs to cermet material and powder metallurgical technology, it is related to one kind by ceramic hard phase (MoSiC2
Percentage by volume is about 50%~75%) cermet material preparation method of the Dispersed precipitate in molybdenum base Binder Phase, specifically relate to
And a kind of MoSiC2Base metal-ceramic material and preparation method thereof.
Background technology
Refractory metal ceramics have high wearability, high temperature resistant and chemical resistance of concrete ability, the development pair of cermet
The development of the industrial circle such as space flight, aero-engine and smelting, the energy plays very important effect.At present in propeller for turboprop
Widely used high-temperature structural material is high temperature single crystal alloy, dispersion-strengtherning in the products such as machine, jet engine and heat exchanger
Superalloy and intermetallic compound etc., and Thermal Barrier Coating Technologies are widely used, make hot-end component using temperature
Degree brings up to 1100~1200 DEG C, close to the 85% of this kind of alloy melting point, although can further be carried by various cooling technologies
High turbine inlet temperature (TIT), but the thermal efficiency is reduced as cost, structural complexity and manufacture difficulty are added, and to small and thin
The hot-end component of type is difficult to cooling, thus the potentiality improved again are extremely limited.
Therefore scientists from all over the world accelerate grinding for pair high-temperature structural material of future generation that can bear more elevated operating temperature environment
Study carefully progress, current result of study shows, MoSiC2Based ceramic metal is (by hard phase MoSiC2Constituted with Binder Phase Mo, wherein firmly
Matter phase volume percentage general control is between 50%~75%) have excellent abrasion and corrosion resistance, heat-resisting quantity and compared with
High hardness and conductance, has broad application prospects in the field such as wear-resisting, corrosion-resistant, resistance to high temperature oxidation, can such as be used in boat
Deposited in the industrial machineries such as empty engine, metallurgy, oil, chemical industry and bear big load, severe friction abrasion and heat at high temperature
Mechanical movement parts under percussion, meet material same with stronger impact flexibility and intensity under the high temperature conditions
When, with more excellent wearability and inoxidizability.But MoSiC2The generation temperature of ceramic phase is high, narrow into phase temperature range,
It is difficult to the MoSiC that corresponding proportion is synthesized by dispensing stoichiometric proportion in actual fabrication process2Ceramic phase.
At present, using mechanical alloying plus reaction in-situ high temperature hot pressing sintering generation MoSiC2Base metal-ceramic material is ground
Study carefully and there is no report.
The content of the invention
It is an object of the invention to provide a kind of MoSiC2Base metal-ceramic material and preparation method thereof, this method technique mistake
Journey is simple, obtained MoSiC2The Main Mechanical index of base metal-ceramic material is excellent, can be used for wearing and tearing, corrode and grinding
Lose interactive severe service.
To reach above-mentioned purpose, the technical solution adopted by the present invention is：
A kind of MoSiC2The preparation method of base metal-ceramic material, comprises the following steps：
1) according to mass ratio Mo:Si:C=(0.83~0.76):(0.12~0.17):(0.05~0.07), by Mo powder, Si
Powder and graphite powder are fitted into ball grinder, are filled with after inert gas and carry out mechanical alloying, and Ball-milling Time is 15~40h, is mixed
Close powder；
2) by mixed powder from room temperature to 1400~1750 DEG C of sintering temperature, and at a sintering temperature carry out 30~
Vacuum≤10 during 120min hot pressed sintering, wherein hot pressed sintering-2Pa, pressure are 40~50MPa, hot pressed sintering mistake
Journey terminate after with stove natural cooling, that is, obtain the MoSiC of reaction in-situ generation2Base metal-ceramic material.
Described Mo powder and granularity≤20 μm of graphite powder, granularity≤50 μm of Si powder.
Purity >=99.9% of described Mo powder, Si powder and graphite powder.
Described inert gas is argon gas.
The step 1) in ball milling when ratio of grinding media to material be (5~10):1, rotational speed of ball-mill is 250~400r/min.
The step 2) in mixed powder be put into graphite jig carry out hot pressed sintering.
The step 2) in programming rate be 5~10 DEG C/min.
Obtained MoSiC2Base metal-ceramic material, its consistency reaches 98.1~98.98%, and bending strength reaches 1660
~1820 MPa, fracture toughness reaches 27.2~28.6MPam1/2, hardness reaches 85.1~88HRA, 800~1000 DEG C of antioxygens
It is completely anti-oxidant to change performance.
Relative to prior art, beneficial effects of the present invention are：
The MoSiC that the present invention is provided2The preparation method of base metal-ceramic material, using between Mo powder, Si powder and graphite powder
Reaction in-situ obtain MoSiC2Base metal-ceramic material.This method short preparation period, technical process are simple, stock utilization
It is high, with low cost, obtained MoSiC2Base metal-ceramic material compact structure, Main Mechanical index is excellent, can be used for
Wear and tear, corrode and denude interactive severe service.MoSiC made from this method2Base metal-ceramic material need not or only
A small amount of following process is needed, is very suitable for industrial production, is expected to realize MoSiC2The engineer applied of base metal-ceramic material.
MoSiC produced by the present invention2The Main Mechanical index of base metal-ceramic material is excellent, and (highest consistency reaches
98.98%, highest bending strength reaches 1820MPa, and highest fracture toughness reaches 28.6MPam1/2, maximum hardness reaches
88HRA), 800~1000 DEG C of antioxygenic properties be assessed as completely it is anti-oxidant, can be used for wearing and tearing, corrode and denuding reciprocation
Severe service, have a good application prospect.
Embodiment
The present invention is described in further details below.
The MoSiC that the present invention is provided2The preparation method of base metal-ceramic material, specifically includes following steps：
1) the Mo powder, Si powder, graphite powder for being not less than 99.9% from purity are primary raw material, it is desirable to Mo powder and graphite powder
Granularity≤20 μm, granularity≤50 μm of Si powder.According to mass ratio Mo:Si:C=(0.83~0.76):(0.12~0.17):
(0.05~0.07) dispensing, Mo powder, Si powder and graphite powder are fitted into high-energy ball milling tank, is filled with after argon gas and carries out mechanical alloy
Change, Ball-milling Time is 15~40h, obtains mixed powder；Wherein ball milling when ratio of grinding media to material be (5~10):1, rotational speed of ball-mill is 250
~400r/min；
2) take out mixed powder to be put into graphite jig and carries out hot pressed sintering, with 5~10 DEG C/min programming rate from room
Temperature is warming up to 1400~1750 DEG C of sintering temperature, the vacuum in sintering temperature 30~120min of heat preservation sintering, sintering process
≤10-2Pa, pressure is 40~50MPa, with stove natural cooling after the completion of sintering, that is, obtains the MoSiC of reaction in-situ generation2Base
Cermet material.
MoSiC produced by the present invention2The Main Mechanical index of base metal-ceramic material is excellent, and its consistency reaches
98.1~98.98%, bending strength reaches 1660~1820MPa, and fracture toughness reaches 27.2~28.6MPam1/2, hardness reaches
To 85.1~88HRA, (highest consistency reaches 98.98%, and highest bending strength reaches 1820MPa, and highest fracture toughness reaches
28.6MPa·m1/2, maximum hardness reaches 88HRA), 800~1000 DEG C of antioxygenic properties are assessed as completely anti-oxidant.
Embodiment 1：
1) the Mo powder, Si powder, graphite powder for being not less than 99.9% from purity are primary raw material, it is desirable to Mo powder and graphite powder
Granularity≤20 μm, granularity≤50 μm of Si powder.According to mass ratio Mo:Si:C=0.83:0.12:0.05 dispensing, by Mo powder, Si powder
It is fitted into graphite powder in high-energy ball milling tank, is filled with after argon gas and carries out mechanical alloying, Ball-milling Time is 25h, obtains mixed powder；
Wherein ball milling when ratio of grinding media to material be 10:1, rotating speed is 300r/min.
2) take out mixed powder to be put into graphite jig and carries out hot pressed sintering, with 10 DEG C/min programming rate from room temperature liter
Temperature is to 1550 DEG C of sintering temperature, vacuum≤10 in sintering temperature heat preservation sintering 60min, sintering process-2Pa, pressure is
Furnace cooling after the completion of 40MPa, sintering, that is, obtain the MoSiC of reaction in-situ generation2Base metal-ceramic material.
To MoSiC made from embodiment 12Base metal-ceramic material carries out performance test, and its consistency is 98.1%, 3 points
Bending strength is 1820MPa, and fracture toughness is 28.6MPam1/2, hardness is 85.1HRA, and 800 DEG C of antioxygenic properties are assessed as
It is completely anti-oxidant.
Embodiment 2：
1) the Mo powder, Si powder, graphite powder for being not less than 99.9% from purity are primary raw material, it is desirable to Mo powder and graphite powder
Granularity≤20 μm, granularity≤50 μm of Si powder.According to mass ratio Mo:Si:C=0.76:0.17:0.07 dispensing, by Mo powder, Si powder
It is fitted into graphite powder in high-energy ball milling tank, is filled with after argon gas and carries out mechanical alloying, Ball-milling Time is 25h, obtains mixed powder；
Wherein ball milling when ratio of grinding media to material be 5:1, rotating speed is 250r/min.
2) take out mixed powder to be put into graphite jig and carries out hot pressed sintering, with 10 DEG C/min programming rate from room temperature liter
Temperature is to 1750 DEG C of sintering temperature, vacuum≤10 in sintering temperature heat preservation sintering 60min, sintering process-2Pa, pressure is
Furnace cooling after the completion of 50MPa, sintering, that is, obtain the MoSiC of reaction in-situ generation2Base metal-ceramic material.
To MoSiC made from embodiment 22Base metal-ceramic material carries out performance test, and its consistency is 98.6%, 3 points
Bending strength is 1660MPa, and fracture toughness is 27.2MPam1/2, hardness is 87.9HRA, and 800 DEG C of antioxygenic properties are assessed as
It is completely anti-oxidant.
Embodiment 3：
1) the Mo powder, Si powder, graphite powder for being not less than 99.9% from purity are primary raw material, it is desirable to Mo powder and graphite powder
Granularity≤20 μm, granularity≤50 μm of Si powder.According to mass ratio Mo:Si:C=0.78:0.155:0.065 dispensing, by Mo powder, Si
Powder and graphite powder are fitted into high-energy ball milling tank, are filled with after argon gas and carry out mechanical alloying, and Ball-milling Time is 15h, obtains mixed powder
Body；Wherein ball milling when ratio of grinding media to material be 5:1, rotating speed is 400r/min.
2) take out mixed powder to be put into graphite jig and carries out hot pressed sintering, with 5 DEG C/min programming rate from room temperature liter
Temperature is to 1600 DEG C of sintering temperature, vacuum≤10 in sintering temperature heat preservation sintering 120min, sintering process-2Pa, pressure is
Furnace cooling after the completion of 45MPa, sintering, that is, obtain the MoSiC of reaction in-situ generation2Base metal-ceramic material.
Embodiment 4：
1) the Mo powder, Si powder, graphite powder for being not less than 99.9% from purity are primary raw material, it is desirable to Mo powder and graphite powder
Granularity≤20 μm, granularity≤50 μm of Si powder.According to mass ratio Mo:Si:C=0.8:0.14:0.06 dispensing, by Mo powder, Si powder
It is fitted into graphite powder in high-energy ball milling tank, is filled with after argon gas and carries out mechanical alloying, Ball-milling Time is 30h, obtains mixed powder；
Wherein ball milling when ratio of grinding media to material be 6:1, rotating speed is 320r/min.
2) take out mixed powder to be put into graphite jig and carries out hot pressed sintering, with 8 DEG C/min programming rate from room temperature liter
Temperature is to 1400 DEG C of sintering temperature, vacuum≤10 in sintering temperature heat preservation sintering 80min, sintering process-2Pa, pressure is
Furnace cooling after the completion of 42MPa, sintering, that is, obtain the MoSiC of reaction in-situ generation2Base metal-ceramic material.
Embodiment 5：
1) the Mo powder, Si powder, graphite powder for being not less than 99.9% from purity are primary raw material, it is desirable to Mo powder and graphite powder
Granularity≤20 μm, granularity≤50 μm of Si powder.According to mass ratio Mo:Si:C=0.82:0.125:0.055 dispensing, by Mo powder, Si
Powder and graphite powder are fitted into high-energy ball milling tank, are filled with after argon gas and carry out mechanical alloying, and Ball-milling Time is 20h, obtains mixed powder
Body；Wherein ball milling when ratio of grinding media to material be 8:1, rotating speed is 350r/min.
2) take out mixed powder to be put into graphite jig and carries out hot pressed sintering, with 7 DEG C/min programming rate from room temperature liter
Temperature is to 1700 DEG C of sintering temperature, vacuum≤10 in sintering temperature heat preservation sintering 100min, sintering process-2Pa, pressure is
Furnace cooling after the completion of 48MPa, sintering, that is, obtain the MoSiC of reaction in-situ generation2Base metal-ceramic material.
Embodiment 6：
1) the Mo powder, Si powder, graphite powder for being not less than 99.9% from purity are primary raw material, it is desirable to Mo powder and graphite powder
Granularity≤20 μm, granularity≤50 μm of Si powder.According to mass ratio Mo:Si:C=0.79:0.15:0.06 dispensing, by Mo powder, Si powder
It is fitted into graphite powder in high-energy ball milling tank, is filled with after argon gas and carries out mechanical alloying, Ball-milling Time is 40h, obtains mixed powder；
Wherein ball milling when ratio of grinding media to material be 7:1, rotating speed is 280r/min.
2) take out mixed powder to be put into graphite jig and carries out hot pressed sintering, with 9 DEG C/min programming rate from room temperature liter
Temperature is to 1500 DEG C of sintering temperature, vacuum≤10 in sintering temperature heat preservation sintering 30min, sintering process-2Pa, pressure is
Furnace cooling after the completion of 46MPa, sintering, that is, obtain the MoSiC of reaction in-situ generation2Base metal-ceramic material.
One embodiment of the present invention is the foregoing is only, is not all of or unique embodiment, this area is common
Technical staff, by any equivalent conversion read description of the invention and taken technical solution of the present invention, is the present invention
Claim covered.
Claims (4)
1. a kind of MoSiC2The preparation method of base metal-ceramic material, it is characterised in that comprise the following steps：
1) according to mass ratio Mo:Si:C=(0.83~0.76):(0.12~0.17):(0.05~0.07), by Mo powder, Si powder and
Graphite powder is fitted into ball grinder, is filled with after inert gas and carries out mechanical alloying, and Ball-milling Time is 15~40h, obtains mixed powder
Body；Wherein ball milling when ratio of grinding media to material be (5~10):1, rotational speed of ball-mill is 250~400r/min；The granularity of Mo powder and graphite powder≤
20 μm, granularity≤50 μm of Si powder；Purity >=99.9% of Mo powder, Si powder and graphite powder；
2) by mixed powder with 5~10 DEG C/min programming rate from room temperature to 1400~1750 DEG C of sintering temperature, and
30~120min hot pressed sintering, wherein vacuum≤10 during hot pressed sintering are carried out at a sintering temperature-2Pa, pressure are
40~50MPa, hot pressed sintering process terminate after with stove natural cooling, that is, obtain the MoSiC of reaction in-situ generation2Based ceramic metal
Material.
2. MoSiC according to claim 12The preparation method of base metal-ceramic material, it is characterised in that：Described inertia
Gas is argon gas.
3. MoSiC according to claim 12The preparation method of base metal-ceramic material, it is characterised in that：The step 2)
Middle mixed powder is put into graphite jig carries out hot pressed sintering.
4. the MoSiC in claim 1-3 described in any one2MoSiC made from the preparation method of base metal-ceramic material2Base
Cermet material, it is characterised in that：Its consistency reaches 98.1~98.98%, and bending strength reaches 1660~1820MPa,
Fracture toughness reaches 27.2~28.6MPam1/2, hardness reaches 85.1~88HRA, and 800~1000 DEG C of antioxygenic properties have been
It is complete anti-oxidant.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103320638A (en) * | 2013-06-30 | 2013-09-25 | 成都易态科技有限公司 | Preparation method of sintered porous material |
| CN104451325A (en) * | 2014-12-12 | 2015-03-25 | 西安交通大学 | Process for preparing Mo2FeB2-based metal ceramic |
| CN104532041A (en) * | 2014-12-12 | 2015-04-22 | 西安交通大学 | Preparation process of Mo2NiB2 based metal ceramic |
| CN104911434A (en) * | 2015-06-01 | 2015-09-16 | 陕西理工学院 | Carbide-reinforced Mo2NiB2 metal ceramic and preparation method thereof |
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2016
- 2016-06-13 CN CN201610422442.4A patent/CN106048357B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103320638A (en) * | 2013-06-30 | 2013-09-25 | 成都易态科技有限公司 | Preparation method of sintered porous material |
| CN104451325A (en) * | 2014-12-12 | 2015-03-25 | 西安交通大学 | Process for preparing Mo2FeB2-based metal ceramic |
| CN104532041A (en) * | 2014-12-12 | 2015-04-22 | 西安交通大学 | Preparation process of Mo2NiB2 based metal ceramic |
| CN104911434A (en) * | 2015-06-01 | 2015-09-16 | 陕西理工学院 | Carbide-reinforced Mo2NiB2 metal ceramic and preparation method thereof |
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