CN109676127A - A kind of high performance Ti N based ceramic metal and preparation method thereof - Google Patents
A kind of high performance Ti N based ceramic metal and preparation method thereof Download PDFInfo
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- CN109676127A CN109676127A CN201910094134.7A CN201910094134A CN109676127A CN 109676127 A CN109676127 A CN 109676127A CN 201910094134 A CN201910094134 A CN 201910094134A CN 109676127 A CN109676127 A CN 109676127A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
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- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/1003—Use of special medium during sintering, e.g. sintering aid
- B22F3/1007—Atmosphere
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/1035—Liquid phase sintering
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- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
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- 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 present invention provides a kind of high performance Ti N based ceramic metals and preparation method thereof.Method includes the following steps: by TiN powder and WO3Powder is uniformly mixed, and is then placed in hydrogen furnace, is passed through water hydrogen, is reacted after heating, and W cladding TiN composite powder is obtained；The composite powder and carbon dust are uniformly mixed, is then placed in vacuum drying oven and is carbonized, obtains WC cladding TiN composite powder；WC is coated into TiN composite powder, metallic addition and forming agent after mixing, then is successively sieved, is pressed into base, degreasing, sintering, obtains TiN based ceramic metal.Have the characteristics that consistency is high, hardness is high, anti-bending strength is excellent, fracture toughness is good, coefficient of friction is low, wearability is good, anti-oxidant and excellent corrosion resistance using TiN based ceramic metal made from this method, possesses very vast market prospect.
Description
Technical field
The invention belongs to technical field of inorganic nonmetallic materials more particularly to a kind of high performance Ti N based ceramic metal and its
Preparation method.
Background technique
TiN (titanium nitride) ceramic material have low-density, high rigidity, high-melting-point, corrosion-resistant, thermostability is good, coefficient of friction
Low excellent properties, thus be considered as a kind of wear-and corrosion-resistant material with research and development and application prospect；In addition, TiN makes pottery
Ceramic material has beautiful golden colour lustre, the cash equivalent decorative effect having had, and is a kind of very promising ornament materials.But
It is that titanium nitride ceramic material plastic deformation ability itself is poor, toughness is low, it is difficult to obtain fine and close sintered body, these defects limit
Its development and application.TiN ceramic material is mainly used as coating material at present, but coating material exists in use
It easily peels off, the defects of service life is short, therefore prepare the high-densit TiN block materials of high-performance there is very high application value.
Cermet is a kind of composite material for having both ceramics and metal good characteristic, but TiN ceramic material and proof gold
Wetability between category is poor, is difficult to obtain the high-densit TiN base metal-ceramic material of high comprehensive performance after sintering, therefore, urgently
It need to be further improved process, reduce cost, improve the comprehensive performance of material.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the shortcomings of to mention in background above technology and defect, provide one
Kind high performance Ti N based ceramic metal, while the preparation method of the TiN based ceramic metal being also provided.
In order to solve the above technical problems, technical solution proposed by the present invention are as follows:
A kind of preparation method of high performance Ti N based ceramic metal, comprising the following steps:
(1) by TiN powder and WO3Powder is uniformly mixed, and is then placed in hydrogen furnace, is passed through water hydrogen, carries out after heating
It reacts, WO in reaction process3The hydronium(ion) tungsten oxide gas of preferential and steam reaction generation high volatile, then at high temperature by
Hydrogen reducing is adsorbed on TiN ceramic grain surface, obtains the W cladding TiN composite powder of prefabricated core-shell structure；
(2) W after step (1) is coated into TiN composite powder and carbon dust is uniformly mixed, be then placed in vacuum drying oven and carry out carbon
Change, obtains the WC cladding TiN composite powder of core-shell structure；
(3) after mixing by WC cladding TiN composite powder, metallic addition and the forming agent after step (2), then successively
It is sieved, is pressed into base, degreasing, sintering, TiN based ceramic metal is obtained after furnace cooling.
Above-mentioned preparation method, it is preferred that in the step (1), TiN powder and WO3The mass ratio of powder be 20:1~
5:1 is conducive to be evenly coated on the surface TiN, fine and close and with certain thickness (10nm~500nm) W stratum granulosum；The step
(2) in, it is 20:1~15:1 that W, which coats TiN composite powder and the mass ratio of carbon dust, is conducive to completely change the W particle of cladding
For WC, simultaneous reactions consume the oxygen participated in system, purification systems；In the step (3), WC coats TiN composite powder, gold
The mass ratio for belonging to additive and forming agent three is that WC coats TiN composite powder: metallic addition: forming agent=(60~90):
(10~40): (1~3), by the way that the adding proportion control of this three within the scope of the invention, is conducive to obtain comprehensive performance
High TiN based ceramic metal.
Above-mentioned preparation method, it is preferred that in the step (1), the dew point of water hydrogen is -25 DEG C~-30 DEG C.The present invention
Preparation method, within the scope of the invention by the control of the dew point of water hydrogen, it is ensured that the partial size of the W particle of generation is appropriate
In range, to coat W particle in the surface TiN even compact；If beyond the scope of this invention, W particle growth will be promoted,
Clad is blocked up；If being lower than the scope of the present invention, the W particle generated is tiny, it is difficult to be evenly coated.
Above-mentioned preparation method, it is preferred that in the step (1), temperature is risen to 800~1000 DEG C, the reaction time 1
~2h.By in step (1) reaction temperature and the reaction time control within the scope of the invention, be conducive to adjust W particle in TiN
The growth conditions on powder surface obtain the W cladding TiN composite powder of clad uniformly, fine and close.
Above-mentioned preparation method, it is preferred that in the step (2), the temperature for controlling carbonization is 1000 DEG C~1250 DEG C, when
Between be 0.5~1.5h, the vacuum degree < 10Pa in vacuum drying oven.State modulator will be carbonized within the scope of the invention, it is ensured that
Reaction sufficiently carries out, and the W particle of cladding is completely transformed into WC.
Above-mentioned preparation method, it is preferred that in the step (1), (2) and (3), mixed using planetary ball mill equal
Even, control ratio of grinding media to material is 6:1~10:1, and revolving speed is 100~180r/min, and Ball-milling Time is 12~30h, and ball-milling medium is anhydrous
Ethyl alcohol, forming agent are paraffin；Need for mixed material to be put into after mixing in vacuum oven in 75 DEG C~85 DEG C dryings 6~
8h obtains dry mixed material and carries out subsequent processing again.It is mixed using planetary ball mill, and by hybrid parameter control at this
In the range of invention, it is ensured that be uniformly mixed powder, while not destroying the special core-shell structure of coated powder, avoid influencing
The comprehensive performance of TiN based ceramic metal.
Above-mentioned preparation method, it is preferred that in the step (3), the pressure for being pressed into base is 150~200Mpa；Degreasing
It is carried out in hydrogen tube furnace, control heating rate is 1~3 DEG C/min, and skimming temp is 400 DEG C~500 DEG C, and soaking time is
40min~120min.
Above-mentioned preparation method, it is preferred that in the step (3), be sintered to vacuum-sintering or gas pressure sintering；It is described true
Sky sintering control heating rate is 4~5 DEG C/min, and sintering temperature is 1450 DEG C~1550 DEG C, and soaking time is 1h~2h, vacuum
Degree is 10~20Pa；The gas pressure sintering control heating rate is 5 DEG C/min, and sintering temperature is 1450 DEG C~1550 DEG C, heat preservation
Time is 1h~2h, and sintering atmosphere is argon gas, and sintering air pressure is 3~20MPa.Method of the invention, using the side of liquid-phase sintering
Formula, sintering process are the process that molten metal carries out particle re-arrangement with respect to ceramic particle and dissolution is precipitated again, and composite wood can be improved
The consistency and comprehensive performance of material.
Above-mentioned preparation method, it is preferred that in the step (1), the partial size of TiN powder is 5~20 μm, WO3Powder
Partial size is 1~5 μm；In the step (2), the partial size of carbon dust is 500nm~3 μm；In the step (3), metallic addition is
Nickel powder and/or cobalt powder, the partial size of nickel powder are 1~5 μm, and the partial size of cobalt powder is 1~5 μm.Metallic addition selects nickel powder and cobalt powder,
Mainly since metallic nickel, cobalt are cheap and easy to get, and it is good with the wetability of WC, metal that is fine and close and improving is easy by follow-up sintering
The comprehensive performance of ceramics.
The inventive concept total as one, the present invention also provides a kind of high property being prepared according to above-mentioned preparation method
It can TiN based ceramic metal.TiN based ceramic metal of the invention has core-shell structure, and WC is coated on TiN particle surface, and WC packet
The TiN particle covered is evenly distributed in the three-dimensional net structure of metal phase formation；Since WC phase can occur admittedly during the sintering process
Mutually diffusion and solution modeling, shell phase are complicated solid solution (Ti, W) (C, N).Wetting had both can be improved in core-shell structure of the invention
Property, and crystal grain can be inhibited to grow up, shell phase thickness will not it is blocked up will not be excessively thin, the comprehensive performance of gained TiN based ceramic metal
It is excellent.
Compared with the prior art, the advantages of the present invention are as follows:
(1) preparation method of the present invention makes to generate the better mistake of toughness between TiN and Ni/Co by coating WC on the surface TiN
The characteristics of crossing a layer WC, while utilizing good liquid-phase sintering metal wetability, easy-sintering, improves the wetting between TiN and Ni/Co metal
Property, the consistency of material is promoted, the TiN based ceramic metal of excellent combination property is prepared.
(2) preparation method of the invention, easy to operate, process costs are low, are suitable for large-scale production.
(3) TiN base metal-ceramic material of the invention, TiN matrix are uniformly distributed in Ni, Co composition metal phase, have
Consistency is high, hardness is high, anti-bending strength is excellent, fracture toughness is good, coefficient of friction is low, wearability is good, anti-oxidant and anti-corruption
Erosion the characteristics of haveing excellent performance, also there is extraordinary cash equivalent decorative effect, can be widely applied to cutter material, wear-resistant material,
The fields such as bearing material, mold materials possess very vast market prospect.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is the present invention
Some embodiments for those of ordinary skill in the art without creative efforts, can also basis
These attached drawings obtain other attached drawings.
Fig. 1 is the SEM photograph of TiN based ceramic metal in the embodiment of the present invention 1；
Fig. 2 is the SEM photograph of TiN based ceramic metal in the embodiment of the present invention 2；
Fig. 3 is the SEM photograph of TiN based ceramic metal in the embodiment of the present invention 3；
Fig. 4 is the SEM photograph of TiN based ceramic metal in the embodiment of the present invention 4；
Fig. 5 is the SEM photograph of TiN based ceramic metal in the embodiment of the present invention 5.
Specific embodiment
To facilitate the understanding of the present invention, invention herein is done below in conjunction with Figure of description and preferred embodiment more complete
Face meticulously describes, but protection scope of the present invention is not limited to following specific embodiments.
Unless otherwise defined, all technical terms used hereinafter are generally understood meaning phase with those skilled in the art
Together.Technical term used herein is intended merely to the purpose of description specific embodiment, and it is of the invention to be not intended to limitation
Protection scope.
Unless otherwise specified, various raw material, reagent, the instrument and equipment etc. used in the present invention can pass through city
Field is commercially available or can be prepared by existing method.
Embodiment 1:
A kind of preparation method of high performance Ti N based ceramic metal of the invention, comprising the following steps:
(1) TiN powder that average partial size is 5 μm and the WO that average grain diameter is 3 μm are taken3Powder is that 10:1 exists according to mass ratio
It carries out wet-milling in planetary ball mill to be uniformly mixed, control ratio of grinding media to material is 8:1, revolving speed 130r/min, Ball-milling Time 12h, ball
Grinding media is dehydrated alcohol, and forming agent is paraffin；Mixed material is put into vacuum oven in 80 DEG C of dryings after mixing
6h, then the mixed-powder after drying is put into hydrogen furnace, the water hydrogen that dew point is -30 DEG C is then passed to, temperature is risen to 800
It DEG C is reacted, reaction time 60min, obtains W cladding TiN composite powder；
(2) by after step (1) W cladding TiN composite powder and partial size be 1 μm carbon dust according to mass ratio be that 20:1 is expert at
It carries out wet-milling in celestial body grinding machine to be uniformly mixed, control ratio of grinding media to material is 8:1, revolving speed 130r/min, Ball-milling Time 12h, ball milling
Medium is dehydrated alcohol, and forming agent is paraffin；Mixed material is put into vacuum oven in 80 DEG C of dry 6h after mixing,
Then the mixed-powder after drying is put into vacuum drying oven and is carbonized, the temperature of carbonization is 1000 DEG C, time 1h, vacuum drying oven
Interior vacuum degree < 10Pa obtains WC cladding TiN composite powder；
(3) by WC cladding TiN composite powder, metallic addition and forming agent, (three's mass ratio is that WC coats TiN composite powder
End: metallic addition: forming agent=70:30:2, wherein metallic addition is Ni powder and Co powder, and the mass ratio of Ni powder and Co powder is
2:1, Ni powder diameter are 2 μm and Co powder diameter is 1 μm) progress wet-milling is uniformly mixed in planetary ball mill, and control ratio of grinding media to material is
8:1, revolving speed 130r/min, Ball-milling Time 12h, ball-milling medium are dehydrated alcohol, and forming agent is paraffin；After mixing will
Mixed material is put into vacuum oven in 80 DEG C of dry 6h, and then the mixed-powder after drying is sieved, and is suppressed in 200MPa
At base, green compact, which are placed in hydrogen furnace, carries out degreasing, and control heating rate is 2 DEG C/min, 500 DEG C of degreasing 2h is warming up to, after degreasing
Vacuum-sintering is carried out in vacuum drying oven, control heating rate is 5 DEG C/min, and sintering temperature is 1480 DEG C, soaking time 1h, vacuum
Degree is 10Pa, and furnace cooling obtains TiN based ceramic metal after the completion of sintering.
The SEM photograph of the TiN based ceramic metal of the present embodiment is as shown in Figure 1, as seen from the figure, metal phase forms three-dimensional network
The TiN particle of structure, WC cladding is uniformly distributed in Ni/Co composition metal phase, it is seen that the TiN based ceramic metal of the present embodiment has
There is core-shell structure, and since solid-state diffusion and solution modeling can occur during the sintering process for WC phase, shell phase is complicated solid solution
(Ti,W)(C,N).Through detecting, the porosity of TiN based ceramic metal made from the present embodiment is A04B00, hardness 88HRA, is resisted
Curved intensity is 2320MPa, fracture toughness 15.6MPam1/2；It is hard with YG10 in the dry grinding of ring block type frictional wear experiment
Matter alloy opposite grinding, measuring its coefficient of friction is 0.396, and wear rate is 2.77x 10-7mm3/mm。
Embodiment 2:
A kind of preparation method of high performance Ti N based ceramic metal of the invention, comprising the following steps:
(1) TiN powder that average partial size is 5 μm and the WO that average grain diameter is 3 μm are taken3Powder is that 5:1 exists according to mass ratio
It carries out wet-milling in planetary ball mill to be uniformly mixed, control ratio of grinding media to material is 8:1, revolving speed 160r/min, Ball-milling Time 12h, ball
Grinding media is dehydrated alcohol, and forming agent is paraffin；Mixed material is put into vacuum oven in 80 DEG C of dryings after mixing
6h, then the mixed-powder after drying is put into hydrogen furnace, the water hydrogen that dew point is -30 DEG C is then passed to, temperature is risen to 800
It DEG C is reacted, reaction time 60min, obtains W cladding TiN composite powder；
(2) by after step (1) W cladding TiN composite powder and partial size be 1 μm carbon dust according to mass ratio be that 20:1 is expert at
It carries out wet-milling in celestial body grinding machine to be uniformly mixed, control ratio of grinding media to material is 8:1, revolving speed 130r/min, Ball-milling Time 12h, ball milling
Medium is dehydrated alcohol, and forming agent is paraffin；Mixed material is put into vacuum oven in 80 DEG C of dry 6h after mixing,
Then the mixed-powder after drying is put into vacuum drying oven and is carbonized, the temperature of carbonization is 1000 DEG C, time 1h, vacuum drying oven
Interior vacuum degree < 10Pa obtains WC cladding TiN composite powder；
(3) by WC cladding TiN composite powder, metallic addition and forming agent, (three's mass ratio is that WC coats TiN composite powder
End: metallic addition: forming agent=80:20:2, wherein metallic addition is Ni powder and Co powder, and the mass ratio of Ni powder and Co powder is
1:1, Ni powder diameter are 2 μm and Co powder diameter is 1 μm) progress wet-milling is uniformly mixed in planetary ball mill, and control ratio of grinding media to material is
8:1, revolving speed 130r/min, Ball-milling Time 12h, ball-milling medium are dehydrated alcohol, and forming agent is paraffin；After mixing will
Mixed material is put into vacuum oven in 80 DEG C of dry 6h, and then the mixed-powder after drying is sieved, and is suppressed in 200MPa
At base, green compact, which are placed in hydrogen furnace, carries out degreasing, and control heating rate is 2 DEG C/min, 500 DEG C of degreasing 2h is warming up to, after degreasing
Vacuum-sintering is carried out in vacuum drying oven, control heating rate is 5 DEG C/min, and sintering temperature is 1480 DEG C, soaking time 1h, vacuum
Degree is 10Pa, and furnace cooling obtains TiN based ceramic metal after the completion of sintering.
The SEM photograph of the TiN based ceramic metal of the present embodiment is as shown in Fig. 2, as seen from the figure, metal phase forms three-dimensional network
The TiN particle of structure, WC cladding is uniformly distributed in Ni/Co composition metal phase, it is seen that the TiN based ceramic metal of the present embodiment has
There is core-shell structure, and since solid-state diffusion and solution modeling can occur during the sintering process for WC phase, shell phase is complicated solid solution
(Ti,W)(C,N).Through detecting, the porosity of TiN based ceramic metal made from the present embodiment is A04B00, hardness 91HRA, is resisted
Curved intensity is 2020MPa, fracture toughness 13.6MPam1/2；It is hard with YG10 in the dry grinding of ring block type frictional wear experiment
Matter alloy opposite grinding, measuring its coefficient of friction is 0.402, and wear rate is 0.86x 10-7mm3/mm。
Embodiment 3:
A kind of preparation method of high performance Ti N based ceramic metal of the invention, comprising the following steps:
(1) TiN powder that average partial size is 5 μm and the WO that average grain diameter is 3 μm are taken3Powder is that 10:1 exists according to mass ratio
It carries out wet-milling in planetary ball mill to be uniformly mixed, control ratio of grinding media to material is 8:1, revolving speed 130r/min, Ball-milling Time 12h, ball
Grinding media is dehydrated alcohol, and forming agent is paraffin；Mixed material is put into vacuum oven in 80 DEG C of dryings after mixing
6h, then the mixed-powder after drying is put into hydrogen furnace, the water hydrogen that dew point is -30 DEG C is then passed to, temperature is risen to 800
It DEG C is reacted, reaction time 60min, obtains W cladding TiN composite powder；
(2) by after step (1) W cladding TiN composite powder and partial size be 1 μm carbon dust according to mass ratio be that 20:1 is expert at
It carries out wet-milling in celestial body grinding machine to be uniformly mixed, control ratio of grinding media to material is 8:1, revolving speed 140r/min, Ball-milling Time 12h, ball milling
Medium is dehydrated alcohol, and forming agent is paraffin；Mixed material is put into vacuum oven in 80 DEG C of dry 6h after mixing,
Then the mixed-powder after drying is put into vacuum drying oven and is carbonized, the temperature of carbonization is 1100 DEG C, time 1h, vacuum drying oven
Interior vacuum degree < 10Pa obtains WC cladding TiN composite powder；
(3) by WC cladding TiN composite powder, metallic addition and forming agent, (three's mass ratio is that WC coats TiN composite powder
End: metallic addition: forming agent=70:30:2, wherein metallic addition is Ni powder and Co powder, and the mass ratio of Ni powder and Co powder is
1:2, Ni powder diameter are 2 μm and Co powder diameter is 1 μm) progress wet-milling is uniformly mixed in planetary ball mill, and control ratio of grinding media to material is
8:1, revolving speed 130r/min, Ball-milling Time 12h, ball-milling medium are dehydrated alcohol, and forming agent is paraffin；After mixing will
Mixed material is put into vacuum oven in 80 DEG C of dry 6h, and then the mixed-powder after drying is sieved, and is suppressed in 200MPa
At base, green compact, which are placed in hydrogen furnace, carries out degreasing, and control heating rate is 2 DEG C/min, 500 DEG C of degreasing 2h is warming up to, after degreasing
Vacuum-sintering is carried out in vacuum drying oven, control heating rate is 5 DEG C/min, and sintering temperature is 1500 DEG C, soaking time 1h, vacuum
Degree is 10Pa, and furnace cooling obtains TiN based ceramic metal after the completion of sintering.
The SEM photograph of the TiN based ceramic metal of the present embodiment is as shown in figure 3, as seen from the figure, metal phase forms three-dimensional network
The TiN particle of structure, WC cladding is uniformly distributed in Ni/Co composition metal phase, it is seen that the TiN based ceramic metal of the present embodiment has
There is core-shell structure, and since solid-state diffusion and solution modeling can occur during the sintering process for WC phase, shell phase is complicated solid solution
(Ti,W)(C,N).Through detecting, the porosity of TiN based ceramic metal made from the present embodiment is A04B00, hardness 89HRA, is resisted
Curved intensity is 2620MPa, fracture toughness 19.6MPam1/2；It is hard with YG10 in the dry grinding of ring block type frictional wear experiment
Matter alloy opposite grinding, measuring its coefficient of friction is 0.462, and wear rate is 2.06x 10-7mm3/mm。
Embodiment 4:
A kind of preparation method of high performance Ti N based ceramic metal of the invention, comprising the following steps:
(1) TiN powder that average partial size is 10 μm and the WO that average grain diameter is 3 μm are taken3Powder is 15:1 according to mass ratio
In planetary ball mill carry out wet-milling be uniformly mixed, control ratio of grinding media to material be 8:1, revolving speed 160r/min, Ball-milling Time 16h,
Ball-milling medium is dehydrated alcohol, and forming agent is paraffin；Mixed material is put into vacuum oven after mixing dry in 80 DEG C
Dry 6h, then the mixed-powder after drying is put into hydrogen furnace, the water hydrogen that dew point is -30 DEG C is then passed to, temperature is risen to
800 DEG C are reacted, reaction time 60min, obtain W cladding TiN composite powder；
(2) by after step (1) W cladding TiN composite powder and partial size be 1 μm carbon dust according to mass ratio be that 15:1 is expert at
It carries out wet-milling in celestial body grinding machine to be uniformly mixed, control ratio of grinding media to material is 8:1, revolving speed 130r/min, Ball-milling Time 12h, ball milling
Medium is dehydrated alcohol, and forming agent is paraffin；Mixed material is put into vacuum oven in 80 DEG C of dry 6h after mixing,
Then the mixed-powder after drying is put into vacuum drying oven and is carbonized, the temperature of carbonization is 1100 DEG C, time 1h, vacuum drying oven
Interior vacuum degree < 10Pa obtains WC cladding TiN composite powder；
(3) by WC cladding TiN composite powder, metallic addition and forming agent, (three's mass ratio is that WC coats TiN composite powder
End: metallic addition: forming agent=80:20:2, wherein metallic addition is Ni powder and Co powder, and the mass ratio of Ni powder and Co powder is
1:1, Ni powder diameter are 2 μm and Co powder diameter is 1 μm) progress wet-milling is uniformly mixed in planetary ball mill, and control ratio of grinding media to material is
8:1, revolving speed 130r/min, Ball-milling Time 12h, ball-milling medium are dehydrated alcohol, and forming agent is paraffin；After mixing will
Mixed material is put into vacuum oven in 80 DEG C of dry 6h, and then the mixed-powder after drying is sieved, and is suppressed in 200MPa
At base, green compact, which are placed in hydrogen furnace, carries out degreasing, and control heating rate is 2 DEG C/min, 500 DEG C of degreasing 2h is warming up to, after degreasing
Vacuum-sintering is carried out in vacuum drying oven, control heating rate is 5 DEG C/min, and sintering temperature is 1480 DEG C, soaking time 1h, vacuum
Degree is 10Pa, and furnace cooling obtains TiN based ceramic metal after the completion of sintering.
The SEM photograph of the TiN based ceramic metal of the present embodiment is as shown in figure 4, as seen from the figure, metal phase forms three-dimensional network
The TiN particle of structure, WC cladding is uniformly distributed in Ni/Co composition metal phase, it is seen that the TiN based ceramic metal of the present embodiment has
There is core-shell structure, and since solid-state diffusion and solution modeling can occur during the sintering process for WC phase, shell phase is complicated solid solution
(Ti,W)(C,N)；WC content is relatively high in the present embodiment, and metal phase content is relatively low, can preferably inhibit crystal grain long
Greatly, crystal grain obviously refines.Through detecting, the porosity of TiN based ceramic metal made from the present embodiment is A04B00, and hardness is
90HRA, bending strength 2220MPa, fracture toughness 17.6MPam1/2；In the dry grinding of ring block type frictional wear experiment,
With YG10 hard alloy opposite grinding, measuring its coefficient of friction is 0.426, and wear rate is 1.37x 10-7mm3/mm。
Embodiment 5:
A kind of preparation method of high performance Ti N based ceramic metal of the invention, comprising the following steps:
(1) TiN powder that average partial size is 10 μm and the WO that average grain diameter is 3 μm are taken3Powder is 10:1 according to mass ratio
In planetary ball mill carry out wet-milling be uniformly mixed, control ratio of grinding media to material be 8:1, revolving speed 160r/min, Ball-milling Time 16h,
Ball-milling medium is dehydrated alcohol, and forming agent is paraffin；Mixed material is put into vacuum oven after mixing dry in 80 DEG C
Dry 6h, then the mixed-powder after drying is put into hydrogen furnace, the water hydrogen that dew point is -30 DEG C is then passed to, temperature is risen to
800 DEG C are reacted, reaction time 60min, obtain W cladding TiN composite powder；
(2) by after step (1) W cladding TiN composite powder and partial size be 1 μm carbon dust according to mass ratio be that 15:1 is expert at
It carries out wet-milling in celestial body grinding machine to be uniformly mixed, control ratio of grinding media to material is 8:1, revolving speed 150r/min, Ball-milling Time 12h, ball milling
Medium is dehydrated alcohol, and forming agent is paraffin；Mixed material is put into vacuum oven in 80 DEG C of dry 6h after mixing,
Then the mixed-powder after drying is put into vacuum drying oven and is carbonized, the temperature of carbonization is 1100 DEG C, time 1h, vacuum drying oven
Interior vacuum degree < 10Pa obtains WC cladding TiN composite powder；
(3) by WC cladding TiN composite powder, metallic addition and forming agent, (three's mass ratio is that WC coats TiN composite powder
End: metallic addition: forming agent=80:20:2, wherein metallic addition is Ni powder and Co powder, and the mass ratio of Ni powder and Co powder is
1:1, Ni powder diameter are 2 μm and Co powder diameter is 1 μm) progress wet-milling is uniformly mixed in planetary ball mill, and control ratio of grinding media to material is
8:1, revolving speed 150r/min, Ball-milling Time 12h, ball-milling medium are dehydrated alcohol, and forming agent is paraffin；After mixing will
Mixed material is put into vacuum oven in 80 DEG C of dry 6h, and then the mixed-powder after drying is sieved, and is suppressed in 200MPa
At base, green compact, which are placed in hydrogen furnace, carries out degreasing, and control heating rate is 2 DEG C/min, 500 DEG C of degreasing 2h is warming up to, after degreasing
Gas pressure sintering is carried out in air pressure furnace, atmosphere is argon gas, and control heating rate is 5 DEG C/min, and sintering temperature is 1490 DEG C, heat preservation
Time is 1h, and sintering air pressure is 5MPa, and furnace cooling obtains TiN based ceramic metal after the completion of sintering.
The SEM photograph of the TiN based ceramic metal of the present embodiment is as shown in figure 5, as seen from the figure, metal phase forms three-dimensional network
The TiN particle of structure, WC cladding is uniformly distributed in Ni/Co composition metal phase, it is seen that the TiN based ceramic metal of the present embodiment has
There is core-shell structure, and since solid-state diffusion and solution modeling can occur during the sintering process for WC phase, shell phase is complicated solid solution
(Ti,W)(C,N)；The TiN based ceramic metal crystal grain of the present embodiment is tiny.Through detecting, the pottery of TiN Base Metal made from the present embodiment
The porosity of porcelain is A04B00, hardness 90.6HRA, bending strength 2680MPa, fracture toughness 18.6MPam1/2；In ring
In the case of the dry grinding of block formula frictional wear experiment, with YG10 hard alloy opposite grinding, measuring its coefficient of friction is 0.401, and wear rate is
1.24x 10-7mm3/mm。
Claims (10)
1. a kind of preparation method of high performance Ti N based ceramic metal, which comprises the following steps:
(1) by TiN powder and WO3Powder is uniformly mixed, and is then placed in hydrogen furnace, is passed through water hydrogen, is reacted after heating,
Obtain W cladding TiN composite powder；
(2) W after step (1) is coated into TiN composite powder and carbon dust is uniformly mixed, be then placed in vacuum drying oven and be carbonized,
Obtain WC cladding TiN composite powder；
(3) WC after step (2) is coated into TiN composite powder, metallic addition and forming agent after mixing, then successively mistake
It sieves, be pressed into base, degreasing, sintering, TiN based ceramic metal is obtained after furnace cooling.
2. preparation method according to claim 1, which is characterized in that in the step (1), TiN powder and WO3Powder
Mass ratio is 20:1~5:1；In the step (2), it is 20:1~15:1 that W, which coats TiN composite powder and the mass ratio of carbon dust,；Institute
It states in step (3), it is that WC coats TiN composite powder that WC, which coats TiN composite powder, metallic addition and the mass ratio of forming agent three,
End: metallic addition: forming agent=(60~90): (10~40): (1~3).
3. preparation method according to claim 1 or 2, which is characterized in that in the step (1), the dew point of water hydrogen is-
25 DEG C~-30 DEG C.
4. preparation method according to claim 1 or 2, which is characterized in that in the step (1), temperature is risen to 800~
1000 DEG C, the reaction time is 1~2h.
5. preparation method according to claim 1 or 2, which is characterized in that in the step (2), control the temperature of carbonization
It is 1000 DEG C~1250 DEG C, the time is 0.5~1.5h, the vacuum degree < 10Pa in vacuum drying oven.
6. preparation method according to claim 1 or 2, which is characterized in that in the step (1), (2) and (3), using row
Planetary ball mill is uniformly mixed, and control ratio of grinding media to material is 6:1~10:1, and revolving speed is 100~180r/min, Ball-milling Time for 12~
30h, ball-milling medium are dehydrated alcohol, and forming agent is paraffin；Need for mixed material to be put into after mixing in vacuum oven in
75 DEG C~85 DEG C dry 6~8h, obtain dry mixed material and carry out subsequent processing again.
7. preparation method according to claim 1 or 2, which is characterized in that in the step (3), be pressed into the pressure of base
For 150~200Mpa；Degreasing carries out in hydrogen tube furnace, and control heating rate is 1~3 DEG C/min, and skimming temp is 400 DEG C
~500 DEG C, soaking time is 40min~120min.
8. preparation method according to claim 1 or 2, which is characterized in that in the step (3), be sintered to vacuum-sintering
Or gas pressure sintering；The vacuum-sintering control heating rate is 4~5 DEG C/min, and sintering temperature is 1450 DEG C~1550 DEG C, is protected
The warm time is 1~2h, and vacuum degree is 10~20Pa；The gas pressure sintering control heating rate is 5 DEG C/min, and sintering temperature is
1450 DEG C~1550 DEG C, soaking time is 1h~2h, and sintering atmosphere is argon gas, and sintering air pressure is 3~20MPa.
9. preparation method according to claim 1 or 2, which is characterized in that in the step (1), the partial size of TiN powder is
5~20 μm, WO3The partial size of powder is 1~5 μm；In the step (2), the partial size of carbon dust is 500nm~3 μm；The step
(3) in, metallic addition is nickel powder and/or cobalt powder, and the partial size of nickel powder is 1~5 μm, and the partial size of cobalt powder is 1~5 μm.
10. it is a kind of according to claim 1~any one of 9 described in the high performance Ti N Base Metal pottery that is prepared of preparation method
Porcelain.
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