CN108103339A - A kind of preparation method of silver-based barium titanate composited contact material - Google Patents
A kind of preparation method of silver-based barium titanate composited contact material Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
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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
- B22F3/12—Both compacting and sintering
- B22F3/16—Both compacting and sintering in successive or repeated steps
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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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
- C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
- C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
- C04B35/468—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates
- C04B35/4682—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates based on BaTiO3 perovskite phase
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/624—Sol-gel processing
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—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
- 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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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C5/00—Alloys based on noble metals
- C22C5/06—Alloys based on silver
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
- H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
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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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
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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
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
Abstract
The present invention relates to the preparations of contact material, it is desirable to provide a kind of preparation method of silver-based barium titanate composited contact material.This method includes：(1) sol-gal process is prepared for Barium Titanate nano-powder；(2) silver powder and barium carbonate powder are mixed to get Ag/BaTiO through ball-milling technology3Composite granule；(3) by Ag/BaTiO3Ag/BaTiO is made through cold pressing+heat pressing process in composite granule3Composite material.In the present invention, Ag/BaTiO3The building-up process of composite granule is in mechanical milling process, by BaTiO3It is added gradually in Ag powder, compared to traditional blending processes of powders, effectively reduces enhancing phase agglomeration traits during powder mixing machine, obtained composite granule is evenly.Compared to Ag/SnO2For, manufactured Ag/BaTiO3Composite material has lower resistivity.
Description
Technical field
The invention belongs to metal-base composites technical fields, and in particular to a kind of compound electrical contact of novel silver-based barium titanate
The preparation of material, the material are applied to the equipment such as low-voltage electrical apparatus.
Background technology
Electrical contact element is the key element of the electric appliances such as switch, instrument, instrument, relay, is responsible for and is connected and disconnected from electricity
The task of stream, performance directly influence break-make capacity, service life and the operational reliability of whole set equipment.All the time, Ag/
CdO contact materials because its with the excellent performances such as low contact resistance, anti-melting welding, resistance to arc erosion obtained widely should
With.But Ag/CdO can discharge toxic Cd steam in use, endanger health of people.And with environmentally friendly Ag/
SnO2The appearance of contact material, Ag/CdO are gradually substituted.Ag/SnO2With high thermal stability, the features such as anti electric arc corrosion,
It is developed rapidly it.But Ag/SnO2Contact material still remains many shortcomings, horse light deliver " silver-based point connects
Touch material modification and preparation process "《Rare metal bulletin》2007 (10), document point out Ag/SnO2There are Wen Sheng during use
The phenomenon that excessively high, this is because Ag/SnO2Contact material contact resistance is excessively high to be caused；In addition, Ag/SnO2Machinability compared with
Difference constrains Ag/SnO2Development.
In order to eliminate Ag/SnO2Contact material there are the defects of, to AgSnO2Composite material has done relatively more improvement,
Such as to process optimization, to powder modified etc., although performance can be improved in a certain respect, cause comprehensive
It can decline.Therefore, it is badly in need of a kind of contact material that can eliminate drawbacks described above.
The BaTiO of Ca-Ti ore type3Ceramics because it has excellent ferroelectricity, piezoelectricity, dielectricity, capacitor, memory material,
Electric light display board etc. has a wide range of applications, and has the good reputation of " pillar of electronic ceramics industry ".
The content of the invention
The problem to be solved in the present invention is to overcome existing contact material Ag/SnO2This defect of high resistivity, provides one
The preparation method of kind novel silver-based barium titanate contact material.
To solve the above problems, the solution of the present invention is：
A kind of preparation method of novel silver-based barium titanate contact material is provided, is included the following steps：
(1) CH is compared according to the amount of substance3COOH:Ba(Ac)2=20~28:1、CH3CH2OH:Ti(OC4H9)4=5~7:1,
Be configured to acetic acid-barium acetate aqueous solution that barium acetate concentration is 0.1~1.0mol/L respectively, butyl titanate concentration be 0.1~
The ethyl alcohol of 1.0mol/L-butyl titanate aqueous solution；
(2) at room temperature, under continuous stirring, it is added dropwise and matches somebody with somebody dropwise into the prepared acetic acid of step (1)-barium acetate aqueous solution
The ethyl alcohol-butyl titanate the aqueous solution made, be sufficiently stirred titanium-barium mixed liquor A, the acetic acid-barium acetate water is made
The acetic acid of solution-barium acetate amount in terms of Ba, ethyl alcohol-butyl titanate amount in the ethyl alcohol-butyl titanate aqueous solution in terms of Ti,
Ba:The amount ratio of Ti substances is 1:1；Acetic acid is added in the titanium-barium mixed liquor A to adjust to pH=4~7, then adds in dispersant A
Fully dissolving obtains mixed liquid B, and the amount of the substance of the dispersant A is with acetic acid-barium acetate of acetic acid-barium acetate aqueous solution
The 1~5% of the amount of substance in terms of Ba；Wet gel is formed after mixed liquid B is aged 12~36h, by wet gel through 80~100 DEG C
Lower 6~10h drying；Product after drying is pulverized and is positioned in Muffle furnace, 1~5h is calcined at 700~1000 DEG C,
Up to BaTiO3Powder；
(3) BaTiO that will be prepared in step (2)3Powder is put into funnel, and dispersant B and ball milling are added in ball grinder
Medium simultaneously seals, the sealing cover of the ball grinder be reserved with just for the funnel let slip a remark through aperture, by the funnel
Let slip a remark through the aperture and funnel made to be located on ball milling tank level, the part that funnel is located above ball grinder is fixed,
Make BaTiO under 400-800r/min (preferably 500r/min) rotating speed3It is added gradually in Ag powder, 3~10h of ball milling is to get silver
Based composite powder A；The BaTiO3Mass ratio between powder and Ag powder is 12:88；
(4) the silver-based composite granule A obtained after ball milling is placed in drying box and dries and sieved to obtain composite granule
B；
(5) composite granule B is placed in cold pressing forming mould, using cold isostatic compaction, obtains biscuit A；
(6) biscuit A is positioned in Muffle furnace, 5~9h is sintered under the conditions of 800~920 DEG C, obtains biscuit B；
(7) obtained biscuit B is positioned in heat pressing and molding mold, it is hot-forming to obtain biscuit C；
(8) biscuit C is positioned in Muffle furnace, 3~6h is sintered under the conditions of 650~750 DEG C, obtain silver-based electric contact material
Material.
In the present invention, the grain size of silver powder used is 0.5~5 μm in step (3), and purity is more than 99.99%.
In the present invention, dispersant A described in step (2) is calgon, polyethylene pyrrole network alkanone, dodecyl bromination
One kind of ammonia.
In the present invention, ball-milling medium is alcohol in step (3), and alcohol quality dosage is BaTiO3Powder and Ag powder gross masses
5~10 times；Dispersant B is polyethylene pyrrole network alkanone, unrighted acid, one kind of citric acid, and quality dosage is BaTiO3
Powder and 0.1~0.5wt.% of Ag powder gross masses.
In the present invention, screening described in step (4) is crossed sieve using 200 mesh and is carried out.
In the present invention, isostatic cool pressing pressure used is 600~1000MPa in step (5), is carried out at 25 DEG C of room temperature.
In the present invention, described in step (6) it is hot-forming be in hot pressing temperature be 150~450 DEG C, pressure be 300~
Pressurize 3-10min (preferably 5min) under the conditions of 600MPa.
Chinese and English character A, B, C of the present invention etc. only to distinguish substance, have no other meanings.
The silver-based barium titanate electricity that the present invention also protection is prepared using the preparation method of above-mentioned silver-based barium titanate contact material
Contact material.
Compared with prior art, the beneficial effects of the present invention are：
The present invention takes in ball milling the Style of mixing powder that enhancing phase is added in into matrix, compared to will directly enhance phase habitually in the past
Ball mill is put into matrix and carries out ball milling, and the distribution of obtained composite granule enhancing mutually evenly is in the base.
The fabricating technology of the present invention will not generate harmful effect to environment.The technique of cold pressing+hot pressing of use, is compared
Toward for common cold pressing pressing process, prepared contact material improves the distributing homogeneity for enhancing phase particle, material
Consistency is closer to theoretical value, and density is evenly.
The present invention takes the lead in using Ca-Ti ore type BaTiO3Ceramics are accordingly used to prepare contact material as enhancing, the present invention
The Ag/BaTiO prepared3Contact material.Compared to Ag/SnO2For, Ag/BaTiO3Contact material has lower electricity
Resistance rate.
Specific embodiment
Below to technical scheme further instruction, it is described below and is only intended to understand the present invention, and do not have to
In restriction the scope of the present invention
Embodiment 1
(1) Ba is compared according to the amount of substance:Ti=1, CH3CH2OH:Ti(OC4H9)4=5:1, CH3COOH:Ba(Ac)2=20:
1, acetic acid-barium acetate aqueous solution, the ethyl alcohol-butyl titanate water of 100ml, 0.1mol/L of 100ml, 0.1mol/L are configured to respectively
Solution；
(2) at 25 DEG C of room temperature, under continuous stirring, dripped dropwise into the prepared acetic acid of step (1)-barium acetate aqueous solution
Add the prepared ethyl alcohol of step (1)-butyl titanate aqueous solution, carry out being sufficiently stirred 1h that titanium-barium mixed liquor A is made；To mixed liquor A
It adds in acetic acid and adjusts pH=4, then to 1% (Ba of addition in mixed liquor A2+The amount of substance) calgon fully dissolve to obtain
Mixed liquid B；Wet gel is formed after mixed liquid B is aged 12h, wet gel is dried through 80 DEG C, 10h；Product after drying is ground
Powder is positioned in Muffle furnace by grinds, and 5h is calcined at 700 DEG C to get BaTiO3Powder；
(3) BaTiO prepared in 0.24g steps (2) is weighed3Powder is put into stainless steel funnel, and stainless steel funnel is put
It is above the ball grinder equipped with 1.76g silver powder and fixed, leting slip a remark for stainless steel funnel and is made the aperture reserved through sealing cover
Funnel is located on ball milling tank level, then adds in alcohol 10g, polyethylene glycol 0.002g, makes under 500r/min rotating speeds
BaTiO3It is added gradually in Ag powder, ball milling 3h is to get silver-based composite granule A；
(4) the silver-based composite granule A after ball milling is placed in 80 DEG C of drying in drying box and is sieved with the sieve of crossing of 200 mesh
Get composite granule B；
(5) composite granule B is placed in cold pressing forming mould, at 25 DEG C of room temperature, using 600MPa cold isostatic compactions, obtained
To biscuit A；
(6) biscuit A is positioned in Muffle furnace, 9h is sintered under the conditions of 800 DEG C, obtain biscuit B；
(7) obtained biscuit B is positioned in heat pressing and molding mold, hot pressing temperature be 150 DEG C, pressure is 600MPa items
Pressurize 5min obtains biscuit C under part；
(8) biscuit C is positioned in Muffle furnace, 6h is sintered under the conditions of 650 DEG C, obtain silver-based electric contact material.
Resistivity, hardness, the consistency of the silver-based electric contact material of measured above-mentioned preparation, numerical value such as subordinate list 1.
Embodiment 2
(1) Ba is compared according to the amount of substance:Ti=1, CH3CH2OH:Ti(OC4H9)4=7:1, CH3COOH:Ba(Ac)2=28:
1, acetic acid-barium acetate aqueous solution, the ethyl alcohol-butyl titanate water of 100ml, 1.0mol/L of 100ml, 1.0mol/L are configured to respectively
Solution；
(2) at 25 DEG C of room temperature, under continuous stirring, dripped dropwise into the prepared acetic acid of step (1)-barium acetate aqueous solution
Add the prepared ethyl alcohol of step (1)-butyl titanate aqueous solution, carry out being sufficiently stirred 3h that titanium-barium mixed liquor A is made；To mixed liquor A
It adds in acetic acid and adjusts pH=7, then to 5% (Ba of addition in mixed liquor A2+The amount of substance) polyethylene pyrrole network alkanone fully dissolve
Obtain mixed liquid B；Wet gel is formed after mixed liquid B is aged 36h, wet gel is dried through 100 DEG C, 6h；By the production after drying
Object is pulverized, and powder is positioned in Muffle furnace, and 1h is calcined at 1000 DEG C to get BaTiO3Powder；
(3) BaTiO prepared in 0.24g steps (2) is weighed3Powder is put into stainless steel funnel, and stainless steel funnel is put
It is above the ball grinder equipped with 1.76g silver powder and fixed, leting slip a remark for stainless steel funnel and is made the aperture reserved through sealing cover
Funnel is located on ball milling tank level, then adds in alcohol 20g, unrighted acid 0.01g, makes under 500r/min rotating speeds
BaTiO3It is added gradually in Ag powder, ball milling 10h is to get silver-based composite granule A；
(4) the silver-based composite granule A after ball milling is placed in 80 DEG C of drying in drying box and is sieved with the sieve of crossing of 200 mesh
Get composite granule B；
(5) composite granule B is placed in cold pressing forming mould, at 25 DEG C of room temperature, using 1000MPa cold isostatic compactions,
Obtain biscuit A；
(6) biscuit A is positioned in Muffle furnace, 5h is sintered under the conditions of 920 DEG C, obtain biscuit B；
(7) obtained biscuit B is positioned in heat pressing and molding mold, hot pressing temperature be 450 DEG C, pressure is 300MPa items
Pressurize 5min obtains biscuit C under part；
(8) biscuit C is positioned in Muffle furnace, 3h is sintered under the conditions of 750 DEG C, obtain silver-based electric contact material.
Resistivity, hardness, the consistency of the silver-based electric contact material of measured above-mentioned preparation, numerical value such as subordinate list 1.
Embodiment 3
(1) Ba is compared according to the amount of substance:Ti=1, CH3CH2OH:Ti(OC4H9)4=5.5:1, CH3COOH:Ba(Ac)2=
24:1, acetic acid-barium acetate aqueous solution, the ethyl alcohol-metatitanic acid fourth of 100ml, 0.5mol/L of 100ml, 0.5mol/L are configured to respectively
Aqueous solution of ester；
(2) at 25 DEG C of room temperature, under continuous stirring, dripped dropwise into the prepared acetic acid of step (1)-barium acetate aqueous solution
Add the prepared ethyl alcohol of step (1)-butyl titanate aqueous solution, carry out being sufficiently stirred 2h that titanium-barium mixed liquor A is made；To mixed liquor A
It adds in acetic acid and adjusts pH=5, then to 3% (Ba of addition in mixed liquor A2+The amount of substance) dodecyl bromination ammonia fully dissolve
Obtain mixed liquid B；Mixed liquid B ageing is formed into wet gel afterwards for 24 hours, wet gel is dried through 90 DEG C, 8h；By the product after drying
It pulverizes, powder is positioned in Muffle furnace, 3h is calcined at 850 DEG C to get BaTiO3Powder；
(3) BaTiO prepared in 0.24g steps (2) is weighed3Powder is put into stainless steel funnel, and stainless steel funnel is put
It is above the ball grinder equipped with 1.76g silver powder and fixed, leting slip a remark for stainless steel funnel and is made the aperture reserved through sealing cover
Funnel is located on ball milling tank level, then adds in alcohol 15g, citric acid 0.006g, makes under 500r/min rotating speeds
BaTiO3It is added gradually in Ag powder, ball milling 6.5h is to get silver-based composite granule A；
(4) the silver-based composite granule A after ball milling is placed in 80 DEG C of drying in drying box and is sieved with the sieve of crossing of 200 mesh
Get composite granule B；
(5) composite granule B is placed in cold pressing forming mould, at 25 DEG C of room temperature, using 800MPa cold isostatic compactions, obtained
To biscuit A；
(6) biscuit A is positioned in Muffle furnace, 7h is sintered under the conditions of 860 DEG C, obtain biscuit B；
(7) obtained biscuit B is positioned in heat pressing and molding mold, hot pressing temperature be 300 DEG C, pressure is 450MPa items
Pressurize 5min obtains biscuit C under part；
(8) biscuit C is positioned in Muffle furnace, 4.5h is sintered under the conditions of 700 DEG C, obtain silver-based electric contact material.
Resistivity, hardness, the consistency of the silver-based electric contact material of measured above-mentioned preparation, numerical value such as subordinate list 1.
Comparative example 1
(1) Ba is compared according to the amount of substance:Ti=1, CH3CH2OH:Ti(OC4H9)4=6.5:1, CH3COOH:Ba(Ac)2=
24:1, acetic acid-barium acetate aqueous solution, the ethyl alcohol-metatitanic acid fourth of 100ml, 0.5mol/L of 100ml, 0.5mol/L are configured to respectively
Aqueous solution of ester；
(2) at 25 DEG C of room temperature, under continuous stirring, dripped dropwise into the prepared acetic acid of step (1)-barium acetate aqueous solution
Add the prepared ethyl alcohol of step (1)-butyl titanate aqueous solution, carry out being sufficiently stirred 1.5h that titanium-barium mixed liquor A is made；To mixing
Liquid A adds in acetic acid and adjusts pH=6, then to 2% (Ba of addition in mixed liquor A2+The amount of substance) dodecyl bromination ammonia it is abundant
Dissolving obtains mixed liquid B；Wet gel is formed after mixed liquid B is aged 20h, wet gel is dried through 85 DEG C, 9h；After drying
Product is pulverized, and powder is positioned in Muffle furnace, and 3h is calcined at 900 DEG C to get BaTiO3Powder；
(3) BaTiO prepared in 0.24g steps (2) is weighed3Powder is put into stainless steel funnel, and stainless steel funnel is put
It is above the ball grinder equipped with 1.76g silver powder and fixed, leting slip a remark for stainless steel funnel and is made the aperture reserved through sealing cover
Funnel is located on ball milling tank level, then adds in alcohol 15g, unrighted acid 0.01g, makes under 500r/min rotating speeds
BaTiO3It is added gradually in Ag powder, ball milling 10h is to get silver-based composite granule A；
(4) the silver-based composite granule A after ball milling is placed in 80 DEG C of drying in drying box and is sieved with the sieve of crossing of 200 mesh
Get composite granule B；
(5) composite granule B is placed in cold pressing forming mould, at 25 DEG C of room temperature, using 1000MPa cold isostatic compactions,
Obtain biscuit A；
(6) biscuit A is positioned in Muffle furnace, 6h is sintered under the conditions of 900 DEG C, obtain silver-based electric contact material.
Resistivity, hardness, the consistency of the silver-based electric contact material of measured above-mentioned preparation, numerical value such as subordinate list 1.
Comparative example 2
(1) Ba is compared according to the amount of substance:Ti=1, CH3CH2OH:Ti(OC4H9)4=6:1, CH3COOH:Ba(Ac)2=26:
1, acetic acid-barium acetate aqueous solution, the ethyl alcohol-butyl titanate water of 100ml, 0.6mol/L of 100ml, 0.6mol/L are configured to respectively
Solution；
(2) at 25 DEG C of room temperature, under continuous stirring, dripped dropwise into the prepared acetic acid of step (1)-barium acetate aqueous solution
Add the prepared ethyl alcohol of step (1)-butyl titanate aqueous solution, carry out being sufficiently stirred 2h that titanium-barium mixed liquor A is made；To mixed liquor A
It adds in acetic acid and adjusts pH=5, then to 4% (Ba of addition in mixed liquor A2+The amount of substance) polyethylene pyrrole network alkanone fully dissolve
Obtain mixed liquid B；Wet gel is formed after mixed liquid B is aged 18h, wet gel is dried through 100 DEG C, 7h；By the production after drying
Object is pulverized, and powder is positioned in Muffle furnace, and 4h is calcined at 850 DEG C to get BaTiO3Powder；
(3) BaTiO prepared in 0.24g steps (2) is weighed3Powder is directly placed into the ball grinder equipped with 1.76g silver powder,
Alcohol 16g, citric acid 0.012g are then added in, ball milling 6h is to get silver-based composite granule A under 500r/min rotating speeds；
(4) the silver-based composite granule A after ball milling is placed in 80 DEG C of drying in drying box and is sieved with the sieve of crossing of 200 mesh
Get composite granule B；
(5) composite granule B is placed in cold pressing forming mould, at 25 DEG C of room temperature, using 900MPa cold isostatic compactions, obtained
To biscuit A；
(6) biscuit A is positioned in Muffle furnace, 6h is sintered under the conditions of 900 DEG C, obtain biscuit B；
(7) obtained biscuit B is positioned in heat pressing and molding mold, hot pressing temperature be 200 DEG C, pressure is 500MPa items
Pressurize 5min obtains biscuit C under part；
(8) biscuit C is positioned in Muffle furnace, 4h is sintered under the conditions of 680 DEG C, obtain silver-based electric contact material.
Resistivity, hardness, the consistency of the silver-based electric contact material of measured above-mentioned preparation, numerical value such as subordinate list 1.
In the present invention, the Ag/BaTiO that is prepared by the way of the ball milling in Hun Fen3Contact material ratio directly will
Powder mixing carries out the Ag/BaTiO that ball milling is prepared3Contact material has lower resistivity；Under identical preparation process,
Ag/BaTiO prepared by embodiment 1, embodiment 2 and embodiment 33Contact material is than traditional Ag/SnO2Contact material electricity
Resistance rate is low；Independent cold-press process is compared, using the Ag/BaTiO prepared by cold pressing+heat pressing process3Contact material has lower
Resistivity, higher consistency, higher hardness.
Ag/BaTiO in 1 present invention of table3Material and Ag/SnO2Material compares
Claims (9)
1. a kind of preparation method of silver-based barium titanate contact material, it is characterised in that described method includes following steps：
(1) CH is compared according to the amount of substance3COOH:Ba(Ac)2=20~28:1、CH3CH2OH:Ti(OC4H9)4=5~7:1, respectively
It is configured to acetic acid-barium acetate aqueous solution that barium acetate concentration is 0.1~1.0mol/L, butyl titanate concentration is 0.1~1.0mol/
The ethyl alcohol of L-butyl titanate aqueous solution；
(2) at room temperature, under continuous stirring, it is added dropwise and prepares dropwise into the prepared acetic acid of step (1)-barium acetate aqueous solution
The ethyl alcohol-butyl titanate aqueous solution, be sufficiently stirred titanium-barium mixed liquor A, the acetic acid-barium acetate aqueous solution be made
Acetic acid-barium acetate amount in terms of Ba, ethyl alcohol-butyl titanate amount in the ethyl alcohol-butyl titanate aqueous solution is in terms of Ti, Ba:Ti
The amount ratio of substance is 1:1；Acetic acid is added in the titanium-barium mixed liquor A to adjust to pH=4~7, and it is abundant then to add in dispersant A
Dissolving obtains mixed liquid B, and the amount of the substance of the dispersant A is with Ba with acetic acid-barium acetate of acetic acid-barium acetate aqueous solution
The 1~5% of the amount of the substance of meter；Wet gel is formed after mixed liquid B is aged 12~36h, by wet gel through at 80~100 DEG C 6
~10h is dried；Product after drying is pulverized and is positioned in Muffle furnace, 1~5h is calcined at 700~1000 DEG C, i.e.,
Obtain BaTiO3Powder；
(3) BaTiO that will be prepared in step (2)3Powder is put into funnel, and dispersant B and ball-milling medium are added in simultaneously in ball grinder
Sealing, the sealing cover of the ball grinder be reserved with just for the funnel let slip a remark through aperture, by leting slip a remark for the funnel
Through the aperture and funnel is made to be located on ball milling tank level, the part that the funnel is located above ball grinder is fixed,
Make BaTiO under 400-800r/min rotating speeds3It is added gradually in Ag powder, 3~10h of ball milling is to get silver-based composite granule A；It is described
BaTiO3Mass ratio between powder and Ag powder is 12:88；
(4) the silver-based composite granule A obtained after ball milling is placed in drying box and dries and sieved to obtain composite granule B；
(5) composite granule B is placed in cold pressing forming mould, using cold isostatic compaction, obtains biscuit A；
(6) biscuit A is positioned in Muffle furnace, 5~9h is sintered under the conditions of 800~920 DEG C, obtains biscuit B；
(7) obtained biscuit B is positioned in heat pressing and molding mold, it is hot-forming to obtain biscuit C；
(8) biscuit C is positioned in Muffle furnace, 3~6h is sintered under the conditions of 650~750 DEG C, obtain silver-based electric contact material.
2. the method as described in claim 1, it is characterised in that：The grain size of silver powder used is 0.5~5 μm in step (3), purity
For more than 99.99%.
3. the method as described in claim 1, it is characterised in that：Dispersant A described in step (2) is calgon, poly- second
Alkene pyrrole network alkanone, one kind of dodecyl bromination ammonia.
4. the method as described in claim 1, it is characterised in that：Ball-milling medium described in step (3) is alcohol, and alcohol quality is used
It measures as BaTiO35~10 times of powder and Ag powder gross masses.
5. the method as described in claim 1, it is characterised in that：Dispersant B described in step (3) for polyethylene pyrrole network alkanone,
One kind of unrighted acid, citric acid, the dispersant B quality dosage are BaTiO3The 0.1 of powder and Ag powder gross masses~
0.5wt%.
6. the method as described in claim 1, it is characterised in that：Screening described in step (4) is crossed sieve using 200 mesh and is carried out.
7. the method as described in claim 1, it is characterised in that：In step (5) isostatic cool pressing pressure used for 600~
1000MPa is carried out at 25 DEG C of room temperature.
8. the method as described in claim 1, it is characterised in that：Hot-forming described in step (6) is to be in hot pressing temperature
150~450 DEG C, pressure obtain biscuit C for pressurize 3-10min under the conditions of 300~600MPa.
9. the silver-based barium titanate contact material that the method according to one of claim 1~8 is prepared.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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