CN106448795B - Sub- titanium oxide-metal composite conductive material and preparation method thereof - Google Patents
Sub- titanium oxide-metal composite conductive material and preparation method thereof Download PDFInfo
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- CN106448795B CN106448795B CN201610832758.0A CN201610832758A CN106448795B CN 106448795 B CN106448795 B CN 106448795B CN 201610832758 A CN201610832758 A CN 201610832758A CN 106448795 B CN106448795 B CN 106448795B
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- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
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- C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
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- C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
- C22C32/0015—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
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Abstract
Asia titanium oxide metal composite conductive material of the present invention, is made of, chemical formula Ti sub- titanium oxide and metal MnO2n‑1M, in the chemical formula, n=1,3,4,5,6,7,8 or 9, M is at least one of Co, Ni, Al, Cu, Pb, Ti, Fe, Zr, Mg, Ag, Zn, Cr, Mo, V, Mn, Nb, Ta, or M is at least one of Cu, Pb, Zr, Ag, Mo, Mn, Nb, Ta, the mass percent of the Asia titanium oxide is 40%~99.5%, and the mass percent of metal M is 0.5%~60%.The first method of the Asia titanium oxide metal composite conductive material uses discharge plasma sintering or hot pressed sintering, second method to use vacuum-sintering or low pressure sintering.The present invention can improve the toughness and post-production of prepared conductive material, and the conductivity and consistency for keeping conductive material excellent.
Description
Technical field
The invention belongs to conductive material field, more particularly to a kind of sub- titanium oxide-metal composite conductive material and its preparation
Method.
Background technology
The sub- titanium oxide of Magn é l phases, which has, is based on rutile TiO2The structure of lattice, conductivity is high, different under room temperature
It can reach 300~1500S/cm on the conductivity theory of sub- titanium oxide, and have the characteristics that chemical stability is good, this makes it can be at
To replace a kind of electrode material of carbon, fuel cell is solved due to the use of Pt/C and Pt-M/C catalyst, the corrosion of carrier carbon makes
The problem of platinum grain migration grows up or falls off, leads to stability test and service life reduction after the operation of battery through a long time.Therefore mesh
Before have become one of the hot spot studied in terms of battery material.It is that sub- titanium oxide powder is formed into sheet or blocky use in practical application
In making electrode, but it is good and maintain the sheet or bulk material of high conductivity to be difficult to obtain compactness, furthermore poor toughness, the later stage
Poor in processability.CN103303971 A, which are disclosed, a kind of using Ti4O7It is the method that powder prepares electrode material, the Ti4O7It is powder
Body includes Ti4O7It powder and metal V, Nb, W is added in the form of its oxide is formed by doping (Ti, M)4O7Solid solution
Although body powder, this method improve the conductivity and density of electrode material, but Ti4O7And with Ti4O7For the single phase solid solution of base
(Ti,M)4O7As other oxide ceramics, there is the problems such as poor toughness, post-production is poor in practical applications.
Invention content
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of sub- titanium oxide-metal composite conductive materials
And preparation method thereof, to improve the toughness and post-production of prepared conductive material, and the electricity for keeping conductive material excellent
Conductance and consistency.
Asia titanium oxide-metal composite conductive material of the present invention, is made of, chemical formula is sub- titanium oxide and metal M
TinO2n-1- M, in the chemical formula, n=1,3,4,5,6,7,8 or 9, M Co, Ni, Al, Cu, Pb, Ti, Fe, Zr, Mg, Ag, Zn,
At least one of Cr, Mo, V, Mn, Nb, Ta or M are at least one of Cu, Pb, Zr, Ag, Mo, Mn, Nb, Ta, the Asia
The mass percent of titanium oxide is 40%~99.5%, and the mass percent of metal M is 0.5%~60%.
The preparation method of Asia titanium oxide-metal composite conductive material of the present invention is divided into two according to the difference of sintering processing
Kind, first method uses discharge plasma sintering or hot pressed sintering, is suitable for the wider array of metal of range；Second method uses
Vacuum-sintering or low pressure sintering are only applicable to amount of activated lower metal, because when vacuum-sintering or the sintering of low pressure sintering
Between it is relatively long, the higher metal of activity is easy to react with Asia titanium oxide, and object is caused mutually to change.Both methods category
In a total inventive concept.
The preparation method of the first sub- titanium oxide-metal composite conductive material of the present invention, processing step are as follows：
(1) dispensing
Using sub- titanium oxide powder and metal powder or sub- titanium oxide powder and alloyed powder as raw material, the Asia titanium oxide powder is
TiO powders, Ti3O5Powder, Ti4O7Powder, Ti5O9Powder, Ti6O11Powder, Ti7O13Powder, Ti8O15Powder, Ti9O17In powder
One kind, the metal powder be Co powder, Ni powder, Al powder, Cu powder, Pb powder, Ti powder, Fe powder, Zr powder, Mg powder, Ag powder, Zn powder, Cr
At least one of powder, Mo powder, V powder, Mn powder, Nb powder, Ta powder, the alloyed powder be Co, Ni, Al, Cu, Pb, Ti, Fe, Zr,
The alloyed powder that at least two elements in Mg, Ag, Zn, Cr, Mo, V, Mn, Nb, Ta are formed, according to the matter of following components and component
It measures percentage and measures each raw material：
Sub- titanium oxide powder：40%~99.5%,
Metal powder or alloyed powder：0.5%~60%；
(2) batch mixing
The raw material that step (1) is measured carries out wet ball grinding, and raw material is made to be sufficiently mixed uniformly, dry after wet ball grinding
To mixed powder；
(3) it is sintered
Mixed powder obtained by step (2) is packed into mold, and mold is put into discharge plasma sintering stove or hot pressed sintering
In stove, 1 × 10-1~1 × 103It pressurizes to the mixed powder in mold under the vacuum condition of Pa and is warming up to 500~1200 DEG C
5~25min of heat preservation sintering, cools to room temperature with the furnace after sintering, release is come out of the stove up to sub- titanium oxide-metal composite conduction material
Material, the amount that the mixed powder is packed into mold are limited with the maximum capacity no more than mold, the heating, sintering and furnace cooling
Pressing force is 10~50MPa in the process, and keeps same pressure during heating, sintering and furnace cooling.
Above-mentioned first method, the mold are one kind in graphite jig, sintered-carbide die, steel die.
Above-mentioned first method, the operation of wet method abrading-ball described in step (1) are：The raw material measured is packed into ball mill
In, abrading-ball is added and wet grinding media ball milling obtains mixing wet feed for 12~72 hours, the abrading-ball presses ball material mass ratio (6~10):1
It is added, the wet grinding media is alcohol, acetone or deionized water, and the addition of wet grinding media is to submerge the raw material and mill ball
Body is limited.
Above-mentioned first method, the heating rate of temperature-rise period is 70~100 DEG C/min when step (3) is sintered.
The preparation method of second of the present invention sub- titanium oxide-metal composite conductive material, processing step are as follows：
(1) dispensing
Using sub- titanium oxide powder and metal powder or sub- titanium oxide powder and alloyed powder as raw material, the Asia titanium oxide powder is
TiO powders, Ti3O5Powder, Ti4O7Powder, Ti5O9Powder, Ti6O11Powder, Ti7O13Powder, Ti8O15Powder, Ti9O17In powder
One kind, the metal powder is Cu powder, Pb powder, Zr powder, Ag powder, Mo powder, Mn powder, Nb powder, at least one of Ta powder, the conjunction
Bronze is the alloyed powder that at least two elements in Cu, Pb, Zr, Ag, Mo, Mn, Nb, Ta are formed, according to following components and component
Mass percent meter feedstock：
Sub- titanium oxide powder：40%~99.5%,
Metal powder or alloyed powder：0.5%~60%；
(2) batch mixing and granulation
The raw material that step (1) is measured carries out wet ball grinding, so that raw material is sufficiently mixed uniformly, obtains mixed slurry, will
Gained mixed slurry is dried, adds forming agent and be uniformly mixed, be granulated successively, forms granular mixture, obtains pellet；
(3) it is molded
Pellet obtained by step (2) is pressed into base sample；
(4) it is sintered
Degumming 4~8 hours, degumming at 0.1~1Pa of vacuum degree, 350~600 DEG C by the base sample prepared in step (2)
End is cooled to room temperature, and then carries out vacuum-sintering or low pressure sintering to the base sample after degumming；
Vacuum-sintering：1 × 10-1~1 × 103Be warming up under the vacuum condition of Pa 500~1400 DEG C of heat preservation sinterings 1~
4h cools to room temperature with the furnace after sintering, obtains the multiple conductive condensation material of sub- titanium oxide-metal；
Low pressure sintering：1 × 10-1~1 × 103Be warming up under the vacuum condition of Pa 500~1400 DEG C of heat preservation sinterings 1~
2h, after soaking time expires, it is 1~6MPa to be passed through argon gas to Ar Pressure at such a temperature, then in the temperature and the Ar Pressure
Under continue 1~2h of sintering, cool to room temperature after sintering with the furnace, release comes out of the stove to obtain sub- titanium oxide-metal composite conduction material
Material.
Above-mentioned second method, step (3) molding mode are in compression molding, cold isostatic compaction, injection moulding
It is a kind of.
Above-mentioned second method, step (2) described forming agent are one kind in polyethylene glycol, paraffin, SD glue, and forming agent adds
Enter 0.5%~10% that amount is gained mixed powder quality after drying.
Above-mentioned second method, the operation of wet method abrading-ball described in step (2) are：The raw material measured is packed into ball mill
In, abrading-ball is added and wet grinding media ball milling obtains mixing wet feed for 12~72 hours, the abrading-ball presses ball material mass ratio (6~10):1
It is added, the wet grinding media is alcohol, acetone or deionized water, and the addition of wet grinding media is to submerge the raw material and mill ball
Body is limited.
Above-mentioned second method, in step (3) vacuum-sintering and low pressure sintering the heating rate of temperature-rise period be 4~8 DEG C/
min。
Using the method for the invention, since raw material is sub- titanium oxide powder, metal powder or alloyed powder, in sintering process
Metal powder or alloyed powder generate plastic deformation or partial melting, the hole being filled between sub- titan oxide particles and in conductive material
Sub- titanium oxide-metal composite the conductive material for being uniformly distributed, thus preparing, institutional framework are metal, sub- titanium oxide ceramics two
Phase.The synergistic effect of metal phase and sub- titanium oxide phase makes sub- titanium oxide-metal composite conductive material of the present invention be aoxidized with sub-
Titanium ceramic material is compared, and toughness and post-production significantly improve, and maintains excellent conductivity and consistency.
Compared with prior art, the invention has the advantages that：
1. the present invention provides a kind of sub- titanium oxide-metal composite conductive material, the type of conductive material is enriched.
2. Asia titanium oxide-metal composite conductive material of the present invention, not only has excellent conductivity and consistency, and
And compared with sub- titanium oxide ceramics material, toughness and post-production significantly improve.
3, sub- titanium oxide-metal composite conductive material preparation method of the present invention, raw material are easily obtained, it is simple for process and
Industrialized production is convenient in environmental protection.
Description of the drawings
Fig. 1 is the Ti prepared by embodiment 14O7The SEM of-Ni composite conducting materials schemes；
Fig. 2 is the energy spectrum diagram at D2-2 points in Fig. 1；
Fig. 3 is the Ti prepared by embodiment 135O9The SEM of-Co composite conducting materials schemes；
Fig. 4 is the energy spectrum diagram at D1-1 points in Fig. 3.
Specific implementation mode
Sub- titanium oxide-metal composite conductive material of the present invention and preparation method thereof is done below by specific embodiment
It further illustrates.
In following embodiments, raw material Asia titanium oxide powder uses CN201510313691.5 or CN201510312287.6 institutes
Method preparation is stated, metal powder, alloyed powder powder and the sintering furnace that uses are bought from market.
Embodiment 1
The preparation method of sub- titanium oxide-metal composite conductive material described in the present embodiment is as follows：
(1) dispensing
With Ti4O7Powder, nickel powder are raw material, and each raw material is measured according to the following mass percent of each raw material:
Ti4O7Powder：90%
Nickel powder：10%
(2) dispensing
The raw material measured is fitted into ball mill, abrading-ball is added and wet grinding media ball milling obtains mixed slurry in 12 hours,
The abrading-ball is 6 by ball material mass ratio:1 is added, and the wet grinding media is acetone, and the addition of wet grinding media is to submerge the original
Material and grinding sphere are limited, and drying obtains mixed powder at 50 DEG C after wet ball grinding；
(3) it is sintered
Mixed powder obtained by step (2) is packed into graphite jig, mixed powder is packed into the amount of mold with no more than mold
Maximum capacity is limited, and mold is put into discharge plasma sintering stove, is evacuated to after 1Pa sintering furnace to mixed in mold
It closes powder and applies continuous sintering pressure 50MPa, while with the heating rate of 80 DEG C/min to 1250 DEG C, keeping vacuumizing, protect
Heat preservation sintering 15min under sintering pressure is held, cools to room temperature after sintering with the furnace, release is come out of the stove up to Ti4O7- Ni composite guides
Electric material.
The SEM figures of gained composite conducting material section are shown in Fig. 1, and the fracture mode of material is grain boundary fracture as seen from the figure,
Ti after fracture4O7Crystal grain is high-visible, fine particle in figure, and Momentum profiles analysis is it is found that it is metallic nickel.
It is tested through Archimedes's drainage, the consistency of gained composite conducting material is 98.9%, through four-point probe
The conductivity of test, gained composite conducting material is 1150S/cm, is tested through Vickers, hardness 1032HV, through meter
It calculates, toughness 7.32MPam1/2。
Comparative example
Use Ti4O7Powder prepares electrode material, and processing step is as follows：By Ti4O7Powder is packed into graphite jig, Ti4O7Powder
The amount for being packed into mold is limited with the maximum capacity no more than mold, then Ti will be housed4O7The mold of powder is put into plasma discharging
In sintering furnace, and it is evacuated to discharge plasma sintering stove is closed after 1Pa to the Ti in mold4O7Powder applies continuous sintering
Pressure 50MPa, while with the heating rate of 80 DEG C/min to 1250 DEG C, keeping vacuumizing, it keeps keeping the temperature under sintering pressure and burn
15min is tied, cools to room temperature after sintering with the furnace, release is come out of the stove up to Ti4O7Conductive material.
It is tested through Archimedes's drainage, gained Ti4O7The consistency of conductive material is 93.7%, through four-point probe
Test, gained Ti4O7The conductivity of conductive material is 757S/cm, is tested through Vickers, hardness 1183HV, through meter
It calculates, toughness 4.80MPam1/2。
Ti is can be seen that from embodiment 1 and comparative example4O7- Ni composite conducting materials and Ti4O7Conductive material is compared, not only
Excellent conductivity and consistency are maintained, and toughness significantly improves, hardness reduces, thus processability improves.
Embodiment 2
The preparation method of sub- titanium oxide-metal composite conductive material described in the present embodiment is as follows：
(1) dispensing
Using TiO powders, copper powder as raw material, each raw material is measured according to the following mass percent of each raw material:
TiO powders:99.5%
Copper powder:0.5%
(2) batch mixing and granulation
The raw material measured is fitted into ball mill, abrading-ball is added and wet grinding media ball milling obtains mixed slurry in 72 hours,
The abrading-ball is 10 by ball material mass ratio:1 is added, and the wet grinding media is alcohol, and the addition of wet grinding media is described to submerge
Raw material and grinding sphere are limited.The polyethylene glycol that gained mixed slurry is dried at 50 DEG C to, added 10wt% successively is molding
Agent, and be uniformly mixed, be granulated, granular mixture is formed, pellet is obtained；
(3) it is molded
Pellet obtained by step (2) is packed into the cavity of mold, 5s is suppressed at 100MPa, is pressed into base sample；
(4) it is sintered
The base sample prepared in step (2) is placed in vacuum sintering furnace, the degumming 6 hours at vacuum degree 1Pa, 350 DEG C,
Degumming terminates to cool to room temperature with the furnace, and vacuum-sintering is then carried out in vacuum sintering furnace to the base sample after degumming：1 × 10- 11100 DEG C of heat preservation sintering 3h are warming up to the heating rate of 8 DEG C/min under the vacuum condition of Pa, are cooled to the furnace after sintering
Room temperature obtains TiO-Cu composite conducting materials.
It is tested through Archimedes's drainage, the consistency of gained composite conducting material is 95.3%, through four-point probe
The conductivity of test, gained composite conducting material is 1532S/cm.
Embodiment 3
The preparation method of sub- titanium oxide-metal composite conductive material described in the present embodiment is as follows：
(1) dispensing
With Ti3O5Powder, copper powder, manganese powder are raw material, and each raw material is measured according to the following mass percent of each raw material:
Ti3O5Powder：70%
Copper powder：15%
Manganese powder：15%
(2) batch mixing and granulation
The raw material measured is fitted into ball mill, abrading-ball is added and wet grinding media ball milling obtains mixed slurry in 12 hours,
The abrading-ball is 8 by ball material mass ratio:1 is added, and the wet grinding media is acetone, and the addition of wet grinding media is to submerge the original
Material and grinding sphere are limited.It is forming agent that gained mixed slurry is dried at 50 DEG C to dry, addition 5wt% paraffin successively,
And be uniformly mixed, be granulated, granular mixture is formed, pellet is obtained；
(3) it is molded
Pellet obtained by step (2) is packed into rubber die sleeve, is put into cold isostatic press by hanging basket, is pushed in 300MPa
System 3 seconds, is pressed into base sample；
(4) it is sintered
The base sample prepared in step (2) is placed in vacuum sintering furnace, degumming 4 is small at vacuum degree 0.1Pa, 600 DEG C
When, degumming terminates to cool to room temperature with the furnace, and low pressure sintering is then carried out in low-pressure sintering furnace to the base sample after degumming：In 1Pa
Vacuum condition under 980 DEG C of heat preservation sintering 1h are warming up to the heating rate of 5 DEG C/min, after soaking time expires, in the temperature
Under to be passed through argon gas to Ar Pressure be 2MPa, then continue to be sintered 1h under the temperature and the Ar Pressure, with furnace cooling after sintering
But to room temperature, release comes out of the stove to obtain Ti3O5- Mn-Cu composite conducting materials；
It is tested through Archimedes's drainage, the consistency of gained composite conducting material is 96.2%, through four-point probe
The conductivity of test, gained composite conducting material is 427S/cm.
Embodiment 4
The preparation method of sub- titanium oxide-metal composite conductive material described in the present embodiment is as follows：
(1) dispensing
With Ti4O7Powder, niobium tantalum alloy powder are raw material, and each raw material is measured according to the following mass percent of each raw material:
Ti4O7Powder：40%
Niobium tantalum alloy powder：60%
(2) batch mixing and granulation
The raw material measured is fitted into ball mill, abrading-ball is added and wet grinding media ball milling obtains mixed slurry in 12 hours,
The abrading-ball is 6 by ball material mass ratio:1 is added, and the wet grinding media is deionized water, and the addition of wet grinding media is to submerge
It states raw material and grinding sphere is limited.The SD glue that gained mixed slurry is dried at 50 DEG C to, added 0.5wt% successively is forming agent
And be uniformly mixed, be granulated, granular mixture is formed, pellet is obtained；
(3) it is molded
Pellet prepared by step (2) after mixing, is sent into from the feed device of injector and is expected with 10wt% polyethylene
Cylinder in, be heated to 140 DEG C make its melt after, 50Mpa pressurize 5s are forced by plunger, pressurize demoulds after terminating cooling and shaping
Base sample；
(4) it is sintered
The base sample prepared in step (3) is first soaked into 4h in 70 DEG C of solvent naphtha, it is viscous to assist in removing polyethylene
Agent is tied, is then placed in vacuum sintering furnace, the degumming 8 hours at vacuum degree 0.5Pa, 400 DEG C, degumming terminates to cool to room with the furnace
Then temperature carries out vacuum-sintering to the base sample after degumming in vacuum sintering furnace：1 × 10-1Under the vacuum condition of Pa with 4 DEG C/
The heating rate of min is warming up to 1350 DEG C of heat preservation sintering 1h, cools to room temperature with the furnace after sintering, obtains Ti4O7- Nb-Ta is multiple
Close conductive material；
It is tested through Archimedes's drainage, the consistency of gained composite conducting material is 98.5%, is surveyed through being vortexed conductivity apparatus
The conductivity of examination, gained composite conducting material is 1385S/cm.
Embodiment 5
The preparation method of sub- titanium oxide-metal composite conductive material described in the present embodiment is as follows：
(1) dispensing
With Ti5O9Powder, silver powder are raw material, and each raw material is measured according to the following mass percent of each raw material:
Ti5O9Powder：90%
Silver powder：10%
(2) batch mixing and granulation
The raw material measured is fitted into ball mill, abrading-ball is added and wet grinding media ball milling obtains mixed slurry in 24 hours,
The abrading-ball is 8 by ball material mass ratio:1 is added, and the wet grinding media is acetone, and the addition of wet grinding media is to submerge the original
Material and grinding sphere are limited.The polyethylene glycol that gained mixed slurry is dried at 50 DEG C to, added 5wt% successively is forming agent,
And be uniformly mixed, be granulated, granular mixture is formed, pellet is obtained；
(3) it is molded
Pellet obtained by step (2) is packed into rubber die sleeve, is put into cold isostatic press by hanging basket, is pushed in 200MPa
System 3 seconds, is pressed into base sample；
(4) it is sintered
The base sample prepared in step (2) is placed in vacuum sintering furnace, degumming 6 is small at vacuum degree 0.1Pa, 550 DEG C
When, degumming terminates to cool to room temperature with the furnace, and low pressure sintering is then carried out in low-pressure sintering furnace to the base sample after degumming：In 1Pa
Vacuum condition under 950 DEG C of heat preservation sintering 2h are warming up to the heating rate of 6 DEG C/min, after soaking time expires, in the temperature
Under to be passed through argon gas to Ar Pressure be 6MPa, then continue to be sintered 2h under the temperature and the Ar Pressure, with furnace cooling after sintering
But to room temperature, release comes out of the stove to obtain Ti5O9- Ag composite conducting materials；
It is tested through Archimedes's drainage, the consistency of gained composite conducting material is 96.7%, through four-point probe
The conductivity of test, gained composite conducting material is 959S/cm.
Embodiment 6
The preparation method of sub- titanium oxide-metal composite conductive material described in the present embodiment is as follows：
(1) dispensing
With Ti6O11Powder, lead powder are raw material, and each raw material is measured according to the following mass percent of each raw material:
Ti6O11Powder：85%
Lead powder：15%
(2) batch mixing and granulation
The raw material measured is fitted into ball mill, abrading-ball is added and wet grinding media ball milling obtains mixed slurry in 72 hours,
The abrading-ball is 6 by ball material mass ratio:1 is added, and the wet grinding media is acetone, and the addition of wet grinding media is to submerge the original
Material and grinding sphere are limited.The polyethylene glycol that gained mixed slurry is dried at 50 DEG C to, added 3wt% successively is forming agent,
And be uniformly mixed, be granulated, granular mixture is formed, pellet is obtained；
(3) it is molded
Pellet obtained by step (2) is packed into the cavity of mold, 4s is suppressed at 80MPa, is pressed into base sample；
(4) it is sintered
By in the merging vacuum sintering furnace prepared in step (2), the degumming 4 at vacuum degree 0.1Pa, 350 DEG C of base sample is small
When, degumming terminates to cool to room temperature with the furnace, and low pressure sintering is then carried out in low-pressure sintering furnace to the base sample after degumming：In 1Pa
Vacuum condition under 500 DEG C of heat preservation sintering 1.5h are warming up to the heating rate of 6 DEG C/min, after soaking time expires, in the temperature
It is 4MPa that argon gas to Ar Pressure is passed through under degree, then continues to be sintered 1.5h under the temperature and the Ar Pressure, after sintering with
Stove is cooled to room temperature, and release comes out of the stove to obtain Ti6O11- Pb composite conducting materials；
The consistency that gained composite conducting material is tested through Archimedes's drainage is 95.9%, is surveyed through four-point probe
The conductivity of examination, gained composite conducting material is 700S/cm.
Embodiment 7
The preparation method of sub- titanium oxide-metal composite conductive material described in the present embodiment is as follows：
(1) dispensing
With Ti7O13Powder, molybdenum powder are raw material, and each raw material is measured according to the following mass percent of each raw material:
Ti7O13Powder：99%
Molybdenum powder：1%
(2) batch mixing and granulation
The raw material measured is fitted into ball mill, abrading-ball is added and wet grinding media ball milling obtains mixed slurry in 12 hours,
The abrading-ball is 8 by ball material mass ratio:1 is added, and the wet grinding media is alcohol, and the addition of wet grinding media is to submerge the original
Material and grinding sphere are limited.The polyethylene glycol that gained mixed slurry is dried at 50 DEG C to, added 10wt% successively is forming agent,
And be uniformly mixed, be granulated, granular mixture is formed, pellet is obtained；
(3) it is molded
Pellet obtained by step (2) is packed into the cavity of mold, 4s is suppressed at 100MPa, is pressed into base sample；
(4) it is sintered
The base sample prepared in step (2) is placed in vacuum sintering furnace, degumming 8 is small at vacuum degree 0.1Pa, 600 DEG C
When, degumming terminates to cool to room temperature with the furnace, and low pressure sintering is then carried out in low-pressure sintering furnace to the base sample after degumming：In 1Pa
Vacuum condition under 1400 DEG C of heat preservation sintering 1h are warming up to the heating rate of 6 DEG C/min, after soaking time expires, in the temperature
Under to be passed through argon gas to Ar Pressure be then 4MPa continues to be sintered 2h, furnace cooling after sintering under the temperature and the Ar Pressure
To room temperature, release comes out of the stove to obtain Ti7O13- Mo composite conducting materials；
The consistency that gained composite conducting material is tested through Archimedes's drainage is 92.6%, is surveyed through four-point probe
The conductivity of examination, gained composite conducting material is 421S/cm.
Embodiment 8
The preparation method of sub- titanium oxide-metal composite conductive material described in the present embodiment is as follows：
(1) dispensing
With Ti8O15Powder, zirconium powder are raw material, and each raw material is measured according to the following mass percent of each raw material:
Ti8O15Powder：92%
Zirconium powder：8%
(2) batch mixing and granulation
The raw material measured is fitted into ball mill, abrading-ball is added and wet grinding media ball milling obtains mixed slurry in 12 hours,
The abrading-ball is 8 by ball material mass ratio:1 is added, and the wet grinding media is deionized water, and the addition of wet grinding media is to submerge
It states raw material and grinding sphere is limited.The paraffin that gained mixed slurry is dried at 50 DEG C to, added 5wt% successively is forming agent,
And be uniformly mixed, be granulated, granular mixture is formed, pellet is obtained；
(3) it is molded
Pellet obtained by step (2) is packed into the cavity of mold, 4s is suppressed at 100MPa, is pressed into base sample；
(4) it is sintered
The base sample prepared in step (2) is placed in vacuum sintering furnace, degumming 8 is small at vacuum degree 0.1Pa, 600 DEG C
When, degumming terminates to cool to room temperature with the furnace, and low pressure sintering is then carried out in low-pressure sintering furnace to the base sample after degumming：In 1Pa
Vacuum condition under 1000 DEG C of heat preservation sintering 1h are warming up to the heating rate of 6 DEG C/min, after soaking time expires, in the temperature
Under to be passed through argon gas to Ar Pressure be 4MPa, then continue to be sintered 2h under the temperature and the Ar Pressure, with furnace cooling after sintering
But to room temperature, release comes out of the stove to obtain Ti8O15- Zr composite conducting materials；
It is tested through Archimedes's drainage, the consistency of gained composite conducting material is 97.6%；Through four-point probe
The conductivity of test, gained composite conducting material is 392S/cm.
Embodiment 9
The preparation method of sub- titanium oxide-metal composite conductive material described in the present embodiment is as follows：
(1) dispensing
With Ti9O17Powder, zirconium powder are raw material, and each raw material is measured according to the following mass percent of each raw material:
Ti9O17Powder：91%
Zirconium powder：9%
(2) batch mixing and granulation
The raw material measured is fitted into ball mill, abrading-ball is added and wet grinding media ball milling obtains mixed slurry in 36 hours,
The abrading-ball is 8 by ball material mass ratio:1 is added, and the wet grinding media is alcohol, and the addition of wet grinding media is to submerge the original
Material and grinding sphere are limited.The polyethylene glycol that gained mixed slurry is dried at 50 DEG C to, added 7wt% successively is forming agent,
And be uniformly mixed, be granulated, granular mixture is formed, pellet is obtained；
(3) it is molded
Pellet obtained by step (2) is packed into the cavity of mold, 3s is suppressed at 50MPa, 5s is suppressed under 100MPa, is pressed into
Base sample；
(4) it is sintered
The base sample prepared in step (2) is placed in vacuum sintering furnace, in vacuum degree 1 × 103Pa, degumming 8 at 600 DEG C
Hour, degumming terminates to cool to room temperature with the furnace, and vacuum-sintering is then carried out in vacuum sintering furnace to the base sample after degumming：
1350 DEG C of heat preservation sintering 4h are warming up to the heating rate of 6 DEG C/min under the vacuum condition of 1Pa, are cooled to the furnace after sintering
Room temperature obtains Ti9O17- Zr composite conducting materials；
It is tested through Archimedes's drainage, the consistency of gained composite conducting material is 93.9%；Through four-point probe
The conductivity of test, gained composite conducting material is 331S/cm.
Embodiment 10
The preparation method of sub- titanium oxide-metal composite conductive material described in the present embodiment is as follows：
(1) dispensing
With Ti9O17Powder, zirconium powder are raw material, and each raw material is measured according to the following mass percent of each raw material:
Ti9O17Powder：91%
Zirconium powder：9%
(2) batch mixing and granulation
The raw material measured is fitted into ball mill, abrading-ball is added and wet grinding media ball milling obtains mixed slurry in 36 hours,
The abrading-ball is 8 by ball material mass ratio:1 is added, and the wet grinding media is alcohol, and the addition of wet grinding media is to submerge the original
Material and grinding sphere are limited.The polyethylene glycol that gained mixed slurry is dried at 50 DEG C to, added 7wt% successively is forming agent,
And be uniformly mixed, be granulated, granular mixture is formed, pellet is obtained；
(3) it is molded
Pellet obtained by step (2) is packed into the cavity of mold, 3s is suppressed at 50MPa, 5s is suppressed under 100MPa, is pressed into
Base sample；
(4) it is sintered
The base sample prepared in step (2) is placed in vacuum sintering furnace, in vacuum degree 1 × 103Pa, degumming 8 at 600 DEG C
Hour, degumming terminates to cool to room temperature with the furnace, and vacuum-sintering is then carried out in vacuum sintering furnace to the base sample after degumming：
1350 DEG C of heat preservation sintering 1h are warming up to the heating rate of 6 DEG C/min under the vacuum condition of 1Pa, after soaking time expires, at this
At a temperature of be passed through argon gas to ar pressure be 2MPa, then continue at the temperature and ar pressure be sintered 2h, after sintering
Cool to room temperature with the furnace, release comes out of the stove to obtain Ti9O17- Zr composite conducting materials；
It is tested through Archimedes's drainage, the consistency of gained composite conducting material is 96.1%；Through four-point probe
The conductivity of test, gained composite conducting material is 352S/cm.
Embodiment 11
The preparation method of sub- titanium oxide-metal composite conductive material described in the present embodiment is as follows：
(1) dispensing
With TiO powders, zirconium powder is raw material, and each raw material is measured according to the following mass percent of each raw material:
TiO powders：99.5%
Zirconium powder：0.5%
(2) batch mixing
The raw material measured is fitted into ball mill, abrading-ball is added and wet grinding media ball milling obtains mixed slurry in 36 hours,
The abrading-ball is 8 by ball material mass ratio:1 is added, and the wet grinding media is alcohol, and the addition of wet grinding media is to submerge the original
Material and grinding sphere are limited, and drying obtains mixed powder at 50 DEG C after wet ball grinding；
(3) it is sintered
Mixed powder obtained by step (2) is packed into graphite jig, mixed powder is packed into the amount of mold with no more than mold
Maximum capacity is limited, and mold is put into discharge plasma sintering stove, and 1 × 10 is evacuated to sintering furnace-1To mold after Pa
In mixed powder apply continuous sintering pressure 30MPa, it is true keeping taking out while with the heating rate of 70 DEG C/min to 1200 DEG C
Sky keeps heat preservation sintering 5min under sintering pressure, cools to room temperature after sintering with the furnace, and release is come out of the stove compound up to TiO-Zr
Conductive material.
The consistency that gained composite conducting material is tested through Archimedes's drainage is 93.7%；It is surveyed through four-point probe
The conductivity of examination, gained composite conducting material is 1443S/cm.
Embodiment 12
The preparation method of sub- titanium oxide-metal composite conductive material described in the present embodiment is as follows：
(1) dispensing
With Ti3O5Powder, chromium powder, tantalum powder are raw material, and each raw material is measured according to the following mass percent of each raw material:
Ti3O5Powder：73%
Chromium powder：12%
Tantalum powder：15%
(2) dispensing
The raw material measured is fitted into ball mill, abrading-ball is added and wet grinding media ball milling obtains mixed slurry in 72 hours,
The abrading-ball is 10 by ball material mass ratio:1 is added, and the wet grinding media is deionized water, and the addition of wet grinding media is to submerge
The raw material and grinding sphere are limited, and drying obtains mixed powder at 50 DEG C after wet ball grinding；
(3) it is sintered
Mixed powder obtained by step (2) is packed into graphite jig, mixed powder is packed into the amount of mold with no more than mold
Maximum capacity is limited, and mold is put into discharge plasma sintering stove, is evacuated to after 1Pa sintering furnace to mixed in mold
It closes powder and applies continuous sintering pressure 10MPa, while with the heating rate of 100 DEG C/min to 1150 DEG C, keeping vacuumizing, protect
Heat preservation sintering 25min under sintering pressure is held, cools to room temperature after sintering with the furnace, release is come out of the stove up to Ti3O5- Cr-Ta is compound
Conductive material.
It is tested through Archimedes's drainage, the consistency of gained composite conducting material is 96.9%；Through four-point probe
The conductivity of test, gained composite conducting material is 386S/cm.
Embodiment 13
The preparation method of sub- titanium oxide-metal composite conductive material described in the present embodiment is as follows：
(1) dispensing
With Ti5O9Powder, cobalt powder are raw material, and each raw material is measured according to the following mass percent of each raw material:
Ti5O9Powder：90%
Cobalt powder：10%
(2) dispensing
The raw material measured is fitted into ball mill, abrading-ball is added and wet grinding media ball milling obtains mixed slurry in 12 hours,
The abrading-ball is 6 by ball material mass ratio:1 is added, and the wet grinding media is deionized water, and the addition of wet grinding media is to submerge
It states raw material and grinding sphere is limited, drying obtains mixed powder at 50 DEG C after wet ball grinding；
(3) it is sintered
Mixed powder obtained by step (2) is packed into graphite jig, mixed powder is packed into the amount of mold with no more than mold
Maximum capacity is limited, and mold is put into hot-pressed sintering furnace, is evacuated to after 10Pa sintering furnace to the mixed powder in mold
Material applies continuous sintering pressure 50MPa, while with the heating rate of 70 DEG C/min to 1200 DEG C, is keeping vacuumizing, is keeping burning
Heat preservation sintering 15min under knot pressure power, cools to room temperature with the furnace after sintering, release is come out of the stove up to Ti5O9- Co composite conducting materials
Material.
The consistency that gained composite conducting material is tested through Archimedes's drainage is 95.7%, is surveyed through four-point probe
The conductivity of examination, gained composite conducting material is 812S/cm.
The SEM figures of gained composite conducting material section are shown in Fig. 3, and the fracture mode of material is grain boundary fracture as seen from the figure,
Ti after fracture5O9Crystal grain is high-visible, the fine particle in figure, and Momentum profiles analysis is it is found that it is metallic cobalt.
Embodiment 14
The preparation method of sub- titanium oxide-metal composite conductive material described in the present embodiment is as follows：
(1) dispensing
With Ti6O11Powder, silver powder are raw material, and each raw material is measured according to the following mass percent of each raw material:
Ti6O11Powder：99.5%
Silver powder：0.5%
(2) dispensing
The raw material measured is fitted into ball mill, abrading-ball is added and wet grinding media ball milling obtains mixed slurry in 72 hours,
The abrading-ball is 8 by ball material mass ratio:1 is added, and the wet grinding media is alcohol, and the addition of wet grinding media is to submerge the original
Material and grinding sphere are limited, and drying obtains mixed powder at 50 DEG C after wet ball grinding；
(3) it is sintered
Mixed powder obtained by step (2) is packed into graphite jig, mixed powder is packed into the amount of mold with no more than mold
Maximum capacity is limited, and mold is put into hot-pressed sintering furnace, is evacuated to after 40Pa sintering furnace to the mixed powder in mold
Material applies continuous sintering pressure 30MPa, while with the heating rate of 80 DEG C/min to 1000 DEG C, is keeping vacuumizing, is keeping burning
Heat preservation sintering 25min under knot pressure power, cools to room temperature with the furnace after sintering, release is come out of the stove up to Ti6O11- Ag composite conducting materials
Material.
The consistency that gained composite conducting material is tested through Archimedes's drainage is 95.9%, is surveyed through four-point probe
The conductivity of examination, gained composite conducting material is 612S/cm.
Embodiment 15
The preparation method of sub- titanium oxide-metal composite conductive material described in the present embodiment is as follows：
(1) dispensing
With Ti7O13Powder, aluminium powder are raw material, and each raw material is measured according to the following mass percent of each raw material:
Ti7O13Powder：40%
Aluminium powder：60%
(2) dispensing
The raw material measured is fitted into ball mill, abrading-ball is added and wet grinding media ball milling obtains mixed slurry in 36 hours,
The abrading-ball is 10 by ball material mass ratio:1 is added, and the wet grinding media is acetone, and the addition of wet grinding media is described to submerge
Raw material and grinding sphere are limited, and drying obtains mixed powder at 50 DEG C after wet ball grinding；
(3) it is sintered
Mixed powder obtained by step (2) is packed into stainless steel mould, mixed powder is packed into the amount of mold to be no more than mold
Maximum capacity be limited, and mold is put into hot-pressed sintering furnace, sintering furnace is evacuated to after 40Pa to the mixing in mold
Powder applies continuous sintering pressure 10MPa, while with the heating rate of 100 DEG C/min to 500 DEG C, is keeping vacuumizing, keep
Heat preservation sintering 5min under sintering pressure, cools to room temperature with the furnace after sintering, release is come out of the stove up to Ti7O13- Al composite conductings
Material.
The consistency that gained composite conducting material is tested through Archimedes's drainage is 98.9%, is surveyed through being vortexed conductivity apparatus
The conductivity of examination, gained composite conducting material is 25%IACS.
Embodiment 16
The preparation method of sub- titanium oxide-metal composite conductive material described in the present embodiment is as follows：
(1) dispensing
With Ti8O15Powder, copper powder, magnesium powder are raw material, and each raw material is measured according to the following mass percent of each raw material:
Ti8O15Powder：75%
Copper powder：15%
Magnesium powder：10%
(2) dispensing
The raw material measured is fitted into ball mill, abrading-ball is added and wet grinding media ball milling obtains mixed slurry in 36 hours,
The abrading-ball is 10 by ball material mass ratio:1 is added, and the wet grinding media is acetone, and the addition of wet grinding media is described to submerge
Raw material and grinding sphere are limited, and drying obtains mixed powder at 50 DEG C after wet ball grinding；
(3) it is sintered
Mixed powder obtained by step (2) is packed into sintered-carbide die, mixed powder is packed into the amount of mold to be no more than mould
The maximum capacity of tool is limited, and mold is put into hot-pressed sintering furnace, is evacuated to after 1Pa sintering furnace to the mixing in mold
Powder applies continuous sintering pressure 30MPa, while with the heating rate of 100 DEG C/min to 750 DEG C, is keeping vacuumizing, keep
Heat preservation sintering 5min under sintering pressure, cools to room temperature with the furnace after sintering, release is come out of the stove up to Ti8O15- Cu-Mg composite guides
Electric material.
The consistency that gained composite conducting material is tested through Archimedes's drainage is 96.5%, is surveyed through four-point probe
The conductivity of examination, gained composite conducting material is 427S/cm.
Embodiment 17
The preparation method of sub- titanium oxide-metal composite conductive material described in the present embodiment is as follows：
(1) dispensing
With Ti9O17Powder, titanium valve, vanadium powder are raw material, and each raw material is measured according to the following mass percent of each raw material:
Ti9O17Powder：97%
Titanium valve：2%
Vanadium powder：1%
(2) dispensing
The raw material measured is fitted into ball mill, abrading-ball is added and wet grinding media ball milling obtains mixed slurry in 24 hours,
The abrading-ball is 8 by ball material mass ratio:1 is added, and the wet grinding media is alcohol, and the addition of wet grinding media is to submerge the original
Material and grinding sphere are limited, and drying obtains mixed powder at 50 DEG C after wet ball grinding；
(3) it is sintered
Mixed powder obtained by step (2) is packed into graphite jig, and mixed powder is packed into the amount of mold with most no more than mold
Large capacity is limited, and mold is put into hot-pressed sintering furnace, is evacuated to after 1Pa to sintering furnace and is applied to the mixed powder in mold
Add continuous sintering pressure 40MPa, while with the heating rate of 100 DEG C/min to 950 DEG C, is keeping vacuumizing, keeping sintering pressure
Heat preservation sintering 5min under power, cools to room temperature with the furnace after sintering, release is come out of the stove up to Ti9O17- Ti-V composite conducting materials.
The consistency that gained composite conducting material is tested through Archimedes's drainage is 94.3%, is surveyed through four-point probe
The conductivity of examination, gained composite conducting material is 340S/cm.
Embodiment 18
The preparation method of sub- titanium oxide-metal composite conductive material described in the present embodiment is as follows：
(1) dispensing
With Ti9O17Powder, Nickel Aluminium Alloy Powder are raw material, and each raw material is measured according to the following mass percent of each raw material:
Ti9O17Powder：97%
Nickel Aluminium Alloy Powder：3%
(2) dispensing
The raw material measured is fitted into ball mill, abrading-ball is added and wet grinding media ball milling obtains mixed slurry in 24 hours,
The abrading-ball is 8 by ball material mass ratio:1 is added, and the wet grinding media is alcohol, and the addition of wet grinding media is to submerge the original
Material and grinding sphere are limited, and drying obtains mixed powder at 50 DEG C after wet ball grinding；
(3) it is sintered
Mixed powder obtained by step (2) is packed into graphite jig, and mixed powder is packed into the amount of mold with most no more than mold
Large capacity is limited, and mold is put into hot-pressed sintering furnace, is evacuated to after 1Pa to sintering furnace and is applied to the mixed powder in mold
Add continuous sintering pressure 40MPa, while with the heating rate of 100 DEG C/min to 680 DEG C, is keeping vacuumizing, keeping sintering pressure
Heat preservation sintering 5min under power, cools to room temperature with the furnace after sintering, release is come out of the stove up to Ti9O17- Ni-Al composite conducting materials
Material.
The consistency that gained composite conducting material is tested through Archimedes's drainage is 92.9%, is surveyed through four-point probe
The conductivity of examination, gained composite conducting material is 385S/cm.
Claims (9)
1. sub- titanium oxide-metal composite conductive material, it is characterised in that be made of sub- titanium oxide and metal M, form is non-powder
Shape, phase composition are metal and sub- titanium oxide, chemical formula TinO2n-1- M, in the chemical formula, n=1,3,4,5,6,7,8 or 9, M is
At least one of Co, Ni, Al, Cu, Pb, Ti, Fe, Zr, Mg, Ag, Zn, Cr, Mo, V, Mn, Nb, Ta, the Asia titanium oxide
Mass percent is 40%~85%, and the mass percent of metal M is 15%~60%.
2. the preparation method of sub- titanium oxide-metal composite conductive material described in a kind of claim 1, it is characterised in that processing step
It is as follows：
(1) dispensing
Using sub- titanium oxide powder and metal powder or sub- titanium oxide powder and alloyed powder as raw material, the Asia titanium oxide powder is TiO
Powder, Ti3O5Powder, Ti4O7Powder, Ti5O9Powder, Ti6O11Powder, Ti7O13Powder, Ti8O15Powder, Ti9O17In powder
One kind, the metal powder be Co powder, Ni powder, Al powder, Cu powder, Pb powder, Ti powder, Fe powder, Zr powder, Mg powder, Ag powder, Zn powder, Cr powder,
At least one of Mo powder, V powder, Mn powder, Nb powder, Ta powder, the alloyed powder be Co, Ni, Al, Cu, Pb, Ti, Fe, Zr, Mg,
The alloyed powder that at least two elements in Ag, Zn, Cr, Mo, V, Mn, Nb, Ta are formed, according to the quality hundred of following components and component
Score measures each raw material：
Sub- titanium oxide powder 40%~85%,
Metal powder or alloyed powder 15%~60%；
(2) batch mixing
The raw material that step (1) is measured carries out wet ball grinding, so that raw material is uniformly mixed, mixed powder is dried to obtain after wet ball grinding
Material；
(3) it is sintered
Mixed powder obtained by step (2) is packed into mold, the mold equipped with mixed powder is then put into discharge plasma sintering
In stove or hot-pressed sintering furnace, 1 × 10-1~1 × 103The mixed powder in mold is pressurizeed and is warming up under the vacuum condition of Pa
500~1200 DEG C of 5~25min of heat preservation sintering cool to room temperature with the furnace after sintering, come out of the stove after release up to sub- titanium oxide-
Metal composite conductive material, the amount that the mixed powder is packed into mold are limited with the maximum capacity no more than mold, the heating,
Pressing force is 10~50MPa during sintering and furnace cooling, and keeps same during heating, sintering and furnace cooling
Pressure.
3. the preparation method of sub- titanium oxide-metal composite conductive material according to claim 2, it is characterised in that the mold
For one kind in graphite jig, sintered-carbide die, steel die.
4. according to the preparation method of sub- titanium oxide-metal composite conductive material described in Claims 2 or 3, it is characterised in that step
(1) operation of wet method abrading-ball described in is：The raw material measured is fitted into ball mill, abrading-ball and wet grinding media ball milling 12 is added
Mixing wet feed is obtained within~72 hours, the abrading-ball presses ball material mass ratio (6~10):1 is added, and the wet grinding media is alcohol, third
The addition of ketone or deionized water, wet grinding media is limited with submerging raw material and grinding sphere.
5. according to the preparation method of sub- titanium oxide-metal composite conductive material described in Claims 2 or 3, it is characterised in that step
(3) heating rate of temperature-rise period is 70~100 DEG C/min when being sintered.
6. the preparation method of sub- titanium oxide-metal composite conductive material described in a kind of claim 1, it is characterised in that Asia oxidation
M in titanium-metal composite conductive material chemical formula is at least one of Cu, Pb, Zr, Ag, Mo, Mn, Nb, Ta, processing step
It is as follows：
(1) dispensing
Using sub- titanium oxide powder and metal powder or sub- titanium oxide powder and alloyed powder as raw material, the Asia titanium oxide powder is TiO
Powder, Ti3O5Powder, Ti4O7Powder, Ti5O9Powder, Ti6O11Powder, Ti7O13Powder, Ti8O15Powder, Ti9O17In powder
One kind, the metal powder are at least one of Cu powder, Pb powder, Zr powder, Ag powder, Mo powder, Mn powder, Nb powder, Ta powder, the alloy
Powder is the alloyed powder that at least two elements in Cu, Pb, Zr, Ag, Mo, Mn, Nb, Ta are formed, according to following components and component
Mass percent meter feedstock：
Sub- titanium oxide powder 40%~85%,
Metal powder or alloyed powder 15%~60%
(2) batch mixing and granulation
The raw material that step (1) is measured carries out wet ball grinding, so that raw material is sufficiently mixed uniformly, obtains mixed slurry, by gained
Mixed slurry is dried, adds forming agent and be uniformly mixed, be granulated successively, obtains pellet；
(3) it is molded
Pellet obtained by step (2) is pressed into base sample；
(4) it is sintered
By the base sample prepared in step (3) at 0.1~1Pa of vacuum degree, 350~600 DEG C degumming 4~8 hours, degumming terminates
Then postcooling carries out vacuum-sintering or low pressure sintering to room temperature to the base sample after degumming；
Vacuum-sintering：1 × 10-1~1 × 103It is warming up to 500~1400 DEG C of 1~4h of heat preservation sintering under the vacuum condition of Pa, burns
It cools to room temperature after knot with the furnace, obtains the multiple conductive condensation material of sub- titanium oxide-metal；
Low pressure sintering：1 × 10-1~1 × 103It is warming up to 500~1400 DEG C of 1~2h of heat preservation sintering under the vacuum condition of Pa, protects
After the warm time expires, it is 1~6MPa to be passed through argon gas to Ar Pressure at such a temperature, is then continued at the temperature and the Ar Pressure
It is sintered 1~2h, cools to room temperature after sintering with the furnace, release comes out of the stove to obtain sub- titanium oxide-metal composite conductive material；
The heating rate of temperature-rise period is 4~8 DEG C/min in the vacuum-sintering and low pressure sintering.
7. the preparation method of sub- titanium oxide-metal composite conductive material according to claim 6, it is characterised in that step (3)
Molding mode is one kind in compression molding, cold isostatic compaction, injection moulding.
8. the preparation method of sub- titanium oxide-metal composite conductive material described according to claim 6 or 7, it is characterised in that step
(2) forming agent is one kind in polyethylene glycol, paraffin, SD glue, and forming agent addition is gained mixed powder matter after drying
The 0.5%~10% of amount.
9. the preparation method of sub- titanium oxide-metal composite conductive material described according to claim 6 or 7, it is characterised in that step
(2) operation of wet method abrading-ball described in is：The raw material measured is fitted into ball mill, abrading-ball and wet grinding media ball milling 12 is added
Mixing wet feed is obtained within~72 hours, the abrading-ball presses ball material mass ratio (6~10):1 is added, and the wet grinding media is alcohol, third
The addition of ketone or deionized water, wet grinding media is limited with submerging the raw material and grinding sphere.
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| US5766789A (en) * | 1995-09-29 | 1998-06-16 | Energetics Systems Corporation | Electrical energy devices |
| FR2996222B1 (en) * | 2012-09-28 | 2015-10-09 | Saint Gobain Ct Recherches | FOLIED GRAINS OF TITANIUM OXIDES AND CERAMIC PRODUCTS COMPRISING SUCH GRAINS |
| CN103274456B (en) * | 2013-06-05 | 2016-01-20 | 四川大学 | Doped Ti 4o 7powder and preparation method thereof |
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