CN108441668A - A kind of silver tungsten contact material and preparation method thereof - Google Patents
A kind of silver tungsten contact material and preparation method thereof Download PDFInfo
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Abstract
The present invention discloses a kind of silver-colored tungsten contact material, and the material is used as basis material using silver, and tungsten is as the first reinforced phase, and graphene is as the second reinforced phase, and nickel is as third reinforced phase.The invention further relates to the preparation methods of silver-colored tungsten contact material：Silver/graphene oxide/nickel composite powder is prepared with chemical method；Metal tungsten powder is mixed with the silver/graphene oxide/nickel composite powder, obtains silver/tungsten/graphene oxide/nickle composite powder；Silver/tungsten/the graphene oxide/nickle composite powder is subjected to reduction treatment, silver/tungsten/graphene/nickel composite granule is obtained, contact material is being prepared by PM technique or precast body compression moulding, air pressure infiltration technique.The present invention improves the interface quality of silver-colored tungsten due to the introducing of nickel；Due to the introducing of graphene, material resistance fusion welding energy is improved, reduces the high-temperature oxydation situation of tungsten, reduces contact resistance, method is easy to operate, technique is easily-controllable, easily accomplishes scale production.
Description
Technical field
The present invention relates to a kind of preparation methods of the electric contact composite material of field of material technology, specifically, be related to
It is a kind of novel silver tungsten contact material and preparation method thereof.
Background technology
Silver-tungsten composite material is one of now widely used contact material.Mechanical property due to fine silver and electrical contact
Performance is insufficient, to meet the requirement of contact material, all can prepare silver-based electricity using other reinforcements of increase and silver are compound
Contact material.Tungsten is widely used by the best reinforcement as high current silver-based electric contact material.But silver-colored tungsten material is big
Tungstates can be generated during current switching, tungstates is the non-conductor of electricity, contact resistance can be caused to increase, in turn
Contact temperature is gone up, and ultimately causing contact generation melting welding leads to switch failure.Silver is bad to the wetability of tungsten, leads to material interface
In conjunction with bad, cause interface resistance to increase, material property is made to decline.
Graphene is as a kind of appearance of New Type of Carbon, to receive pass the features such as its excellent conduction, heat conduction, high intensity
Note.Although the research and development of graphene reinforced metal-matrix composite is slow, the excellent conduction of graphene, heat conduction and mechanicalness
Major transformation can will be brought to metal-base composites performance boost.The combination of graphene and traditional reinforcement, also will be graphite
Alkene obtains the key of important breakthrough, the defect of traditional material is made up with certain performances of graphene, to make traditional material obtain
Optimization improvement.
The Chinese invention patent of Publication No. CN 105798319A provides a kind of preparation side of silver-colored tungsten electrical contact material
Method and device, it is to prepare silver-colored tungsten electrical contact raw material powder using " in-situ synthesis ", and powder preparation engineering includes stock, sets
Change reaction, separation, drying, reduction process；Again through sintering circuit, silver-tungsten composite material is obtained.The invention obtains silver powder particles ruler
It is very little it is uniform, grain size is small, easy-regulating, and silver powder and tungsten particle film layer form the electrical contact material of fine and close combination.The patent of invention is simultaneously
The interface cohesion for not improving silver-colored tungsten inherently, is still silver and tungsten direct combination, only changes complex method, prepared to obtain
To silver-colored tungsten material still have low density the problem of.Meanwhile the patent does not promote silver-colored tungsten material resistance fusion welding energy.
The Chinese invention patent of Publication No. CN 104480335B provides a kind of preparation method of silver tungsten contact material.
This method is to mix silver powder and tungsten powder, and gained silver tungsten mixed-powder is placed in ball mill with high purity nickel ball and water and carries out ball milling,
Silver-colored tungsten mixed-powder after gained ball milling is through drying, annealing, molding, infiltration processing.The invention by silver-colored tungsten mixed-powder with it is high-purity
Nickel ball and water are placed in progress ball milling specific time in ball mill by specific proportioning, are both more uniformly distributed the mixing of silver powder and tungsten powder,
It realizes that ball milling is carried out at the same time with nickel element is introduced again, also allows to arrive tungsten because the nickel that ball milling is lost equably covers in high purity nickel ball
The surface of particle, to achieve the purpose that the wettability for being effectively improved silver to tungsten.The patent of invention considers the interface cohesion of silver-colored tungsten,
But there are still some problems.Ball-milling medium is water in the patent of invention, and high purity nickel ball is ground in mechanical milling process by hard particles tungsten
Damage obtains micro-nano nickel powder, and the high temperature that mechanical milling process generates at this time is enough that micro-nano nickel powder is made to aoxidize in water, generates nickel oxide, and
Nickel oxide can not be combined with tungsten, and then can not obtain the tungsten particle that nickel covers.In addition, introducing interface improvement by way of abrading-ball
Elemental nickel, obtained nickel particle are irregular pattern, and the extremely difficult control of nickel content, cannot be satisfied the requirement of electrical contact field,
Also it can not stablize and carry out large-scale production application.
Therefore, a kind of with good interface combination, the production technology that resistance fusion welding energy is good, environmentally friendly, inexpensive, controllability is good
Means realize that there is important industrial upgrading to be worth for the preparation of high-performance silver tungsten contact material.
Invention content
The present invention in view of the deficiency of the prior art and defect, provide it is a kind of based on chemical synthesis, powder metallurgy,
Novel silver tungsten contact material of liquid-phase infiltrating technology and preparation method thereof.
The present invention is used as basis material using silver, and tungsten is as the first reinforced phase, and graphene is as the second reinforced phase, nickel conduct
Third reinforced phase, prepares that consistency is high, conduct electricity very well, fusion welding resisting ability is strong, the low composite strengthening silver tungsten electricity of contact resistance
Contact material.Meanwhile this method is simple, process controllability is good, at low cost, easily accomplishes scale production, the silver tungsten electrical contact
Material structure is uniform, and performance is stablized.
According to the first aspect of the invention, a kind of silver-colored tungsten contact material is provided, the material is used as matrix material using silver
Material, tungsten as the first reinforced phase, graphene as the second reinforced phase, nickel as third reinforced phase, wherein：
The mass percentage of the tungsten is 12wt%-85wt%；
The mass percentage of the graphene is 0.1wt%-8wt%；
The mass percentage of the nickel is 0.5wt%-3wt%；
The silver is surplus.
According to the second aspect of the invention, a kind of preparation method of above-mentioned silver-colored tungsten contact material is provided, including：
Silver/graphene oxide/nickel composite powder is prepared with chemical method；
Metal tungsten powder is mixed with the silver/graphene oxide/nickel composite powder, it is multiple to obtain silver/tungsten/graphene oxide/nickel
Close powder；
Silver/tungsten/the graphene oxide/nickle composite powder is subjected to reduction treatment, it is compound to obtain silver/tungsten/graphene/nickel
Powder, the additive amount of wherein tungsten powder account for the 12wt%-85wt% of the silver/tungsten/graphene/nickel composite granule gross mass；
When the mass percentage of tungsten is 12wt%-25wt% in the silver/tungsten/graphene/nickel composite granule, pass through powder
Last metallurgical technology prepares silver/tungsten/graphene/nickel contact material；
In the silver/tungsten/graphene/nickel composite granule when mass percentage ＞ 25wt% and≤85wt% of tungsten, lead to
Cross precast body compression moulding, air pressure infiltration technique prepares the i.e. silver-colored tungsten contact material of silver/tungsten/graphene/nickel contact material.
Preferably, described that silver/graphene oxide/nickel composite powder is prepared with chemical method, refer to：
Silver nitrate solution is mixed with nickel nitrate solution, obtains silver nitrate-nickel nitrate mixed liquor；
Ascorbic acid solution is mixed with graphene oxide solution, obtains ascorbic acid-graphene oxide liquid mixture；
The silver nitrate-nickel nitrate mixed liquor is mixed with the ascorbic acid-graphene oxide liquid mixture, is obtained
Silver/graphene oxide/nickle composite powder.
It is highly preferred that described be prepared silver/graphene oxide/nickel composite powder with chemical method, have it is following a kind of or
Various features：
The concentration of the silver nitrate solution and the nickel nitrate solution is 0.05mol/L-2mol/L；
A concentration of 0.05mol/L-2mol/L of the ascorbic acid solution；
The mass concentration of the graphene oxide solution is 2%-2.5%；
The additive amount of the graphene oxide accounts for the 0.1wt%-8wt% of final silver-colored tungsten contact material gross mass.
It is highly preferred that the silver nitrate-nickel nitrate mixed liquor and the ascorbic acid-graphene oxide liquid mixture are carried out
Mixing, wherein：
Silver nitrate is restored with nickel nitrate by ascorbic acid, and nickel part coats or be coated on completely silver powder surface, while the packet
Whiting is deposited on graphene surface, obtains the suspension of silver/graphene oxide/nickle composite powder, is obtained through sedimentation, washing, drying
Obtain pure silver/graphene oxide/nickel composite powder.
It is highly preferred that the additive amount of wherein nickel accounts for the 0.5wt%-3wt% of final silver-colored tungsten contact material gross mass.
Preferably, described to mix metal tungsten powder with the silver/graphene oxide/nickel composite powder, wherein：
Silver/graphene oxide/nickle composite powder and tungsten powder are placed in ball milling in alcoholic media by planetary ball mill method and mix powder,
Through dry and sieving processing, silver/tungsten/graphene oxide/nickle composite powder is obtained.
Preferably, the silver/tungsten/graphene oxide/nickle composite powder is subjected to reduction treatment, wherein：
Silver/tungsten/graphene oxide/the nickle composite powder is placed in hydrogen or hydrogen mixed gas atmosphere and carries out also original place
Reason, removes the oxygen-containing group of surface of graphene oxide, improves the electric conductivity of composite material.
It is highly preferred that the reduction treatment, wherein：Heating temperature is 350 DEG C -700 DEG C, heating time 2-6 hour.
Preferably, when the mass content of tungsten in the silver/tungsten/graphene/nickel composite granule is 12wt%-25wt%,
It by the silver/tungsten/graphene/nickel composite granule compression moulding, and is sintered, sintering temperature is 800 DEG C -900 DEG C, is burnt
It is 8-16 hours to tie the time, and sintering atmosphere is hydrogen, finally obtains silver/tungsten/graphene/nickel composite material.
It, will be described when the mass content of tungsten in the silver/tungsten/graphene/nickel composite granule is 26wt%-85wt%
Silver/tungsten/graphene/nickel composite granule carries out precast body compacting, obtains silver/tungsten/graphene/nickel skeleton structure, the skeleton structure
It is sintered 5-8 hours at 600 DEG C -800 DEG C, sintering atmosphere is hydrogen；Sintered skeleton is placed in silver-colored infiltration on piece, carries out air pressure
Infiltration, heating temperature are 900 DEG C -950 DEG C, and heating time is 4-8 hours, and sintering process is vacuum-sintering, air pressure infiltration stage
For argon gas or helium rare gas, infiltrating temperature is 980 DEG C -1100 DEG C, gas pressure 100MPa-1GPa, finally obtain silver/
Tungsten/graphene/nickel composite material.
First silver/graphene oxide/nickel composite powder is prepared with chemical method in the present invention, then by metal tungsten powder and silver/oxygen
The mixing of graphite alkene/nickel composite powder, when the mass fraction of tungsten is 12wt%-25wt% in composite powder, powder by reduction treatment,
PM technique prepares silver/tungsten/graphene/nickel contact material；In composite powder the mass fraction of tungsten be ＞ 25wt% and≤
When 85wt%, powder prepares silver/tungsten/graphene/nickel electricity by reduction treatment, precast body compression moulding, air pressure infiltration technique and connects
Touch material.Silver/tungsten/graphene/nickel material, due to the introducing of nickel, improves silver while holding conventional silver tungsten original performance
The interface quality of tungsten, simultaneously as the introducing of graphene, improves material resistance fusion welding energy, reduce the high-temperature oxydation of tungsten
Situation reduces contact resistance, and the preparation method is easy to operate, technique is easily-controllable, easily accomplishes scale production.
In the present invention, it may be convenient to control the pattern grain size of tungsten, graphene, the additive amount of nickel and silver matrix, it is preferred that
The additive amount of tungsten is 12wt%-85wt%, and graphene oxide additive amount is 0.1wt%-8wt%.The additive amount of nickel is
0.5wt%-3wt%, surplus are silver.Novel silver tungsten contact material prepared by the invention, hence it is evident that reduce and stabilize conventional silver
The contact resistance of tungsten material, and effectively improve the resistance fusion welding energy of conventional silver tungsten material.The present invention can be applied to big well
Electric current application demand.
Compared with prior art, the device have the advantages that：
(1) use chemical reduction method be added nickel, nickel content, that is, morphology controllable, meanwhile, nickel disperse in the base more
Even and tiny, part coats or is coated on Argent grain surface completely, and in the subsequent process, nickel plays preferably in silver-colored tungsten material
Good silver/tungsten/graphene/nickel the composite material of interface cohesion is prepared in interface improvement result.
(2) graphene is added, advantageously reduces the contact resistance of contact material, makes up conventional silver tungsten material resistance
Big and unstable disadvantage, meanwhile, the presence of graphene can inhibit the generation of tungsten oxide and wolframic acid silver, improve contact material
Reliability.
(3) when W content is in 26wt%-85wt%, the present invention uses air pressure infiltration method.It is soaked without pressure compared to traditional
Method is oozed, the higher contact material of consistency can be obtained, to promote finished material rate and material property indices.
Using above-mentioned technical proposal of the present invention, pass through the phase interworking of the technologies such as chemical synthesis, powder metallurgy, liquid-phase infiltrating
It closes, the novel silver tungsten contact material (silver/tungsten/graphene/nickel) haveing excellent performance that can be prepared.It is connect compared to conventional silver tungsten electricity
Material is touched, the electric life of silver/tungsten/graphene/nickel contact material improves 20%-30%, and contact resistance reduces 5%-
15%.
The present invention realizes that high-performance novel silver tungsten electricity connects with the good production technology means of a kind of environmental protection, low cost, controllability
The preparation of material is touched, not only there is important industrial value, but also there is extensive high-end applications foreground.
Description of the drawings
Fig. 1 be W content of the present invention be 12wt%-25wt% when a preferred embodiment preparation flow figure；
Fig. 2 is the preparation stream for the preferred embodiment that W content of the present invention is more than 25wt% and when being less than or equal to 85wt%
Cheng Tu.
Specific implementation mode
Technical scheme of the present invention is further described below, the following description is only to understand technical solution of the present invention
It is used, is not used in restriction the scope of the present invention, protection scope of the present invention is subject to claims.
As shown in Figure 1, the figure be W content of the present invention be 12wt%-25wt% when silver-colored tungsten contact material preparation stream
The preparation process of Cheng Tu, silver-colored tungsten contact material can successively be carried out according to the flow, also can according to practical application request, select into
Row separate step therein.
As shown in Fig. 2, the figure be W content of the present invention be more than 25wt% and less than or equal to 85wt% when silver-colored tungsten electricity connect
The preparation flow figure of material is touched, the preparation process of silver-colored tungsten contact material can successively be carried out according to the flow, also can be according to reality
Application demand, selection carry out separate step therein.
In the present invention, described silver tungsten contact material, that is, silver/tungsten/graphene/nickel contact material, wherein W content can be with
Preferably 25wt%-65wt%；The graphene content can be preferably 1wt%-5wt%, further preferably 3wt%-
5wt%；The content of the nickel can be preferably 1.2wt%-3wt%, further preferably 1.2wt%-1.5wt%.
Embodiment 1
The present embodiment provides a kind of preparation of silver/tungsten/graphene/nickel contact material, operating procedure is as follows：
I) material composition of silver/tungsten/graphene/nickel contact material
The material composition of silver/tungsten/graphene/nickel contact material is mainly metallic silver, tungsten, graphene, metallic nickel,
Wherein W content is 12wt%, and graphene content is 0.1wt%, and nickel content 0.5wt%, surplus is silver.
II) prepare the basic step of silver/tungsten/graphene/nickel contact material (flow is shown in attached drawing 1)
1) 0.1mol/L silver nitrate solutions, 0.1mol/L nickel nitrate solutions, 0.1mol/L ascorbic acid solutions (or Portugal are prepared
Grape sugar or citric acid or oxalic acid are one or more of).
2) it is formed according to material composition, takes the graphene oxide solution that quantitative ascorbic acid solution is 2% with mass concentration
Mixing, and stir evenly.
3) by above-mentioned steps 1) it is mixed with the mixed liquor in step 2), while being stirred with mechanical agitation or magneton.Nitre
Sour silver is restored with nickel nitrate by ascorbic acid, and is grown and deposited in surface of graphene oxide, and it is outstanding to generate silver/graphene oxide/nickel
Turbid is settled, centrifuge washing and drying, obtains silver/graphene oxide/nickel composite powder.
4) use planetary ball mill (or high energy ball mill/V-type batch mixer), abrading-ball that agate ball, grinding jar is used to use agate
Tank, ratio of grinding media to material 5：1, gained silver/graphene oxide/nickel composite powder is mixed with quantitative tungsten powder, it is 8 hours to mix the powder time, is obtained
To silver/tungsten/graphene oxide/nickel composite powder.
5) in a hydrogen atmosphere by silver/tungsten/graphene oxide/nickel composite powder, 400 DEG C heating reductase 12 hour, obtain silver/
Tungsten/graphene/nickel composite powder, wherein W content are 12wt%, and graphene content is 0.1wt%, nickel content 0.5wt%, remaining
Amount is silver.
6) it utilizes compression molding technology by silver/tungsten/graphene/nickel composite powder compression moulding, obtains silver/tungsten/graphene/nickel
The green body is positioned over sintering furnace by green body, and lower 870 DEG C of hydrogen atmosphere is sintered 13 hours, obtains silver/tungsten/graphite of high compaction
Alkene/nickel composite material.
Embodiment 2
With embodiment 1 main difference is that：Product W content in the present embodiment 2 is 25wt%, and graphene contains
Amount is 3wt%, and nickel content 1.5wt%, surplus is silver.
The preparation of the present embodiment silver/tungsten/graphene/nickel contact material, operating procedure are as follows：
I) material composition of silver/tungsten/graphene/nickel contact material
The material composition of silver/tungsten/graphene/nickel contact material is mainly metallic silver, tungsten, graphene, metallic nickel,
Wherein W content is 25wt%, and graphene content is 3wt%, and nickel content 1.5wt%, surplus is silver.
II) prepare the basic step of silver/tungsten/graphene/nickel contact material (attached drawing 1 is shown in technological process)
1) 0.2mol/L silver nitrate solutions, 0.2mol/L nickel nitrate solutions, 0.2mol/L citric acid solutions are prepared.
2) it is formed according to material composition, takes the graphene oxide solution that quantitative citric acid solution is 1.8% with mass concentration
Mixing, and stir evenly.
3) by above-mentioned steps 1) it is mixed with the mixed liquor in step 2), while being stirred with mechanical agitation or magneton.Nitre
Sour silver is restored with nickel nitrate by citric acid, and is grown and deposited in surface of graphene oxide, and it is suspended to generate silver/graphene oxide/nickel
Liquid is settled, centrifuge washing and drying, obtains silver/graphene oxide/nickel composite powder.
4) V-type batch mixer (or high energy ball mill/planetary ball mill) is used, by gained silver/graphene oxide/nickel composite powder
It is mixed with quantitative tungsten powder, it is 10 hours to mix the powder time, obtains silver/tungsten/graphene oxide/nickel composite powder.
5) it in a hydrogen atmosphere by silver/tungsten/graphene oxide/nickel composite powder, heats reductase 12 .5 hours for 420 DEG C, obtains
Silver/tungsten/graphene/nickel composite powder, wherein W content are 25wt%, and graphene content is 3wt%, nickel content 1.5wt%, remaining
Amount is silver.
6) it utilizes compression molding technology by silver/tungsten/graphene/nickel composite powder compression moulding, obtains silver/tungsten/graphene/nickel
The green body is positioned over sintering furnace by green body, and lower 900 DEG C of hydrogen atmosphere is sintered 16 hours, obtains silver/tungsten/graphite of high compaction
Alkene/nickel composite material.
Embodiment 3
The present embodiment 3 provides a kind of preparation of silver/tungsten/graphene/nickel contact material, and operating procedure is as follows：
I) material composition of silver/tungsten/graphene/nickel contact material
The material composition of silver/tungsten/graphene/nickel contact material is mainly metallic silver, tungsten, graphene, metallic nickel,
Wherein W content is 26wt%, and graphene content is 1wt%, and nickel content 1.2wt%, surplus is silver.
II) prepare the basic step of silver/tungsten/graphene/nickel contact material (attached drawing 2 is shown in technological process)
1) 1mol/L silver nitrate solutions, 1mol/L nickel nitrate solutions, 1mol/L ascorbic acid solutions are prepared.
2) it is formed according to material composition, takes the graphene oxide solution that quantitative ascorbic acid solution is 2% with mass concentration
Mixing, and stir evenly.
3) by above-mentioned steps 1) it is mixed with the mixed liquor in step 2), while with mechanical agitation.Silver nitrate and nickel nitrate
It is restored by ascorbic acid, and grows and deposit in surface of graphene oxide, generated silver/graphene oxide/nickel suspension, sunk
Drop, centrifuge washing and drying, obtain silver/graphene oxide/nickel composite powder.
4) use planetary ball mill, abrading-ball that agate ball, grinding jar is used to use agate pot, ratio of grinding media to material 4：1, by gained silver/
Graphene oxide/nickel composite powder is mixed with quantitative tungsten powder, and it is 7 hours to mix the powder time, and it is compound to obtain silver/tungsten/graphene oxide/nickel
Powder.
5) in a hydrogen atmosphere by silver/tungsten/graphene oxide/nickel composite powder, 400 DEG C heating reductase 12 hour, obtain silver/
Tungsten/graphene/nickel composite powder.
6) silver/tungsten/graphene/nickel composite powder is compressed to precast body skeleton using compression molding technology, obtain silver/tungsten/
The precast body is positioned over sintering furnace by graphene/nickel precast body, and lower 700 DEG C of hydrogen atmosphere is sintered 5 hours, obtains with hole
Silver/tungsten/graphene/nickel answer precast body.
7) precast body in the 6) step is positioned over graphite jig, the mold and preform shape size strict conformance, together
When silver-colored infiltration piece is placed in precast body bottom.Mold is placed in infiltration stove, lower 900 DEG C of vacuum state heats 6 hours, 6 hours
1050 DEG C are warming up to after heat preservation, to the backward stove of temperature in applying argon gas, air pressure 100MPa, air pressure infiltration process 0.5 hour, most
Silver/tungsten/graphene/nickel composite material is obtained eventually.
Embodiment 4
With embodiment 3 main difference is that：Product W content in the present embodiment is 65wt%, graphene content
For 5wt%, nickel content 3wt%, surplus is silver.
The preparation of silver/tungsten/graphene/nickel contact material, operating procedure are as follows in the present embodiment：
I) material composition of silver/tungsten/graphene/nickel contact material
The material composition of silver/tungsten/graphene/nickel contact material is mainly metallic silver, tungsten, graphene, metallic nickel,
Wherein W content is 65wt%, and graphene content is 5wt%, and nickel content 3wt%, surplus is silver.
II) prepare the basic step of silver/tungsten/graphene/nickel contact material (attached drawing 2 is shown in technological process)
1) 2mol/L silver nitrate solutions, 2mol/L nickel nitrate solutions, 2mol/L ascorbic acid solutions are prepared.
2) it is formed according to material composition, the graphene oxide for taking quantitative ascorbic acid solution to be 2.5% with mass concentration is molten
Liquid mixes, and stirs evenly.
3) by above-mentioned steps 1) it is mixed with the mixed liquor in step 2), while with mechanical agitation.Silver nitrate and nickel nitrate
It is restored by ascorbic acid, and grows and deposit in surface of graphene oxide, generated silver/graphene oxide/nickel suspension, sunk
Drop, centrifuge washing and drying, obtain silver/graphene oxide/nickel composite powder.
4) use planetary ball mill, abrading-ball that agate ball, grinding jar is used to use agate pot, ratio of grinding media to material 6：1, by gained silver/
Graphene oxide/nickel composite powder is mixed with quantitative tungsten powder, and it is 9 hours to mix the powder time, and it is compound to obtain silver/tungsten/graphene oxide/nickel
Powder.
5) it in a hydrogen atmosphere by silver/tungsten/graphene oxide/nickel composite powder, heats reductase 12 .5 hours for 450 DEG C, obtains
Silver/tungsten/graphene/nickel composite powder.
6) silver/tungsten/graphene/nickel composite powder is compressed to precast body skeleton using compression molding technology, obtain silver/tungsten/
The precast body is positioned over sintering furnace by graphene/nickel precast body, and lower 800 DEG C of hydrogen atmosphere is sintered 6 hours, obtains with hole
Silver/tungsten/graphene/nickel answer precast body.
7) precast body in the 6) step is positioned over graphite jig, the mold and preform shape size strict conformance, together
When silver-colored infiltration piece is placed in precast body bottom.Mold is placed in infiltration stove, lower 950 DEG C of vacuum state heats 7 hours, 7 hours
1100 DEG C are warming up to after heat preservation, to the backward stove of temperature in applying argon gas, air pressure 0.5GPa, air pressure infiltration process 0.5 hour, most
Silver/tungsten/graphene/nickel composite material is obtained eventually.
It should be understood that above-described embodiment is only some embodiments of the present invention, silver tungsten electricity of the present invention connects
Tactile material includes all systems suitable for the product, such as changes the content of matrix silver and other elements, or uses other
The combination of silver salt solution and reducing agent, graphene, nickel reinforcement and tungsten reinforcement can also be a kind of any other feed postition,
The formula of final composite material can be designed according to practical application request.
Although present disclosure is discussed in detail by above preferred embodiment, but it should be appreciated that above-mentioned
Description should not be regarded as limitation of the present invention.After those skilled in the art have read the above, for the present invention's
A variety of modifications and substitutions all will be apparent.Therefore, protection scope of the present invention should be limited to the appended claims.
Claims (10)
1. a kind of silver tungsten contact material, it is characterised in that：The material is used as basis material using silver, and tungsten is as the first enhancing
Phase, graphene as the second reinforced phase, nickel as third reinforced phase, wherein：
The mass percentage of the tungsten is 12wt%-85wt%；
The mass percentage of the graphene is 0.1wt%-8wt%；
The mass percentage of the nickel is 0.5wt%-3wt%；
The silver is surplus.
2. a kind of preparation method of silver-colored tungsten contact material described in claim 1, it is characterised in that：Including：
Silver/graphene oxide/nickel composite powder is prepared with chemical method；
Metal tungsten powder is mixed with the silver/graphene oxide/nickel composite powder, obtains silver/tungsten/graphene oxide/nickel composite powder
Body；
Silver/tungsten/the graphene oxide/nickle composite powder is subjected to reduction treatment, obtains silver/tungsten/graphene/nickel composite powder
Body, the additive amount of wherein tungsten powder account for the 12wt%-85wt% of the silver/tungsten/graphene/nickel composite granule gross mass；
When the mass percentage of tungsten is 12wt%-25wt% in the silver/tungsten/graphene/nickel composite granule, pass through powder smelting
Technology for gold prepares silver/tungsten/graphene/nickel contact material；
In the silver/tungsten/graphene/nickel composite granule when mass percentage ＞ 25wt% and≤85wt% of tungsten, by pre-
Body compression moulding processed, air pressure infiltration technique prepare the i.e. silver-colored tungsten contact material of silver/tungsten/graphene/nickel contact material.
3. the preparation method of silver tungsten contact material according to claim 2, it is characterised in that：It is described to use chemical legal system
It is standby to obtain silver/graphene oxide/nickel composite powder, refer to：
Silver nitrate solution is mixed with nickel nitrate solution, obtains silver nitrate-nickel nitrate mixed liquor；
Ascorbic acid solution is mixed with graphene oxide solution, obtains ascorbic acid-graphene oxide liquid mixture；
The silver nitrate-nickel nitrate mixed liquor is mixed with the ascorbic acid-graphene oxide liquid mixture, obtain silver/
Graphene oxide/nickle composite powder.
4. the preparation method of silver tungsten contact material according to claim 3, it is characterised in that：With following a kind of or more
Kind feature：
The concentration of the silver nitrate solution and the nickel nitrate solution is 0.05mol/L-2mol/L；
A concentration of 0.05mol/L-2mol/L of the ascorbic acid solution；
The mass concentration of the graphene oxide solution is 2%-2.5%；
The additive amount of the graphene oxide accounts for the 0.1wt%-8wt% of final silver-colored tungsten contact material gross mass.
5. the preparation method of silver tungsten contact material according to claim 3, it is characterised in that：By the silver nitrate-nitre
Sour nickel mixed liquor is mixed with the ascorbic acid-graphene oxide liquid mixture, wherein：
Silver nitrate is restored with nickel nitrate by ascorbic acid, and nickel part coats or be coated on completely silver powder surface, while the coated composite powder
It is deposited on graphene surface, obtains the suspension of silver/graphene oxide/nickle composite powder, it is pure through sedimentation, washing, dry acquisition
Net silver/graphene oxide/nickel composite powder.
6. the preparation method of silver tungsten contact material according to claim 5, it is characterised in that：The additive amount of wherein nickel accounts for
The 0.5wt%-3wt% of final silver tungsten contact material gross mass.
7. the preparation method of silver tungsten contact material according to claim 2, it is characterised in that：It is described by metal tungsten powder with
Silver/the graphene oxide/nickel composite powder mixing, wherein：
Silver/graphene oxide/nickle composite powder and tungsten powder are placed in ball milling in alcoholic media by planetary ball mill method and mix powder, through dry
Dry and sieving processing, obtains silver/tungsten/graphene oxide/nickle composite powder.
8. the preparation method of silver tungsten contact material according to claim 2, it is characterised in that：By the silver/tungsten/oxidation
Graphene/nickel composite granule carries out reduction treatment, wherein：
Silver/tungsten/graphene oxide/the nickle composite powder is placed in hydrogen or hydrogen mixed gas atmosphere and carries out reduction treatment,
The oxygen-containing group for removing surface of graphene oxide, improves the electric conductivity of composite material.
9. the preparation method of silver tungsten contact material according to claim 8, it is characterised in that：The reduction treatment,
In：Heating temperature is 350 DEG C -700 DEG C, heating time 2-6 hour.
10. according to the preparation method of claim 2-9 any one of them silver tungsten contact materials, it is characterised in that：When described
When the mass content of tungsten is 12wt%-25wt% in silver/tungsten/graphene/nickel composite granule, by the silver/tungsten/graphene/nickel
Composite granule compression moulding, and be sintered, sintering temperature is 800 DEG C -900 DEG C, and sintering time is 8-16 hours, sintering
Atmosphere is hydrogen, finally obtains silver/tungsten/graphene/nickel composite material；
When the mass content of tungsten in the silver/tungsten/graphene/nickel composite granule be 26wt%-85wt% when, by the silver/tungsten/
Graphene/nickel composite granule carries out precast body compacting, obtains silver/tungsten/graphene/nickel skeleton structure, the skeleton structure is 600
DEG C -800 DEG C are sintered 5-8 hours, and sintering atmosphere is hydrogen；Sintered skeleton is placed in silver-colored infiltration on piece, carries out air pressure infiltration,
Heating temperature is 900 DEG C -950 DEG C, and heating time is 4-8 hours, and sintering process is vacuum-sintering, and the air pressure infiltration stage is argon gas
Or helium rare gas, infiltrating temperature are 980 DEG C -1100 DEG C, gas pressure 100MPa-1GPa, finally obtain silver/tungsten/stone
Black alkene/nickel composite material.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110614381A (en) * | 2019-08-06 | 2019-12-27 | 温州聚星电接触科技有限公司 | Preparation method of silver-based graphene electrical contact material and electrical contact material thereof |
| CN111041546A (en) * | 2019-12-07 | 2020-04-21 | 福达合金材料股份有限公司 | Method for manufacturing silver-tungsten electrical contact with continuous silver layer on surface and product thereof |
| CN111961911A (en) * | 2020-07-24 | 2020-11-20 | 浙江耐迩合金科技有限公司 | Preparation method of silver-based electric contact material with high fusion welding resistance |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0554792A2 (en) * | 1992-02-05 | 1993-08-11 | BERU Ruprecht GmbH & Co. KG | Silver-nickel composite material for electrical contacts and electrodes |
| CN1858867A (en) * | 2006-05-22 | 2006-11-08 | 靖江市海源有色金属材料有限公司 | Silver-tungsten carbide base electric contact material of high anti-melting and welding property and its processing process |
| DE102006020988A1 (en) * | 2006-05-04 | 2007-11-08 | Nanogate Ag | Precious metal-containing nickel layer |
| CN101139663A (en) * | 2007-10-19 | 2008-03-12 | 厦门大学 | Preparation method of silver nickel composite material |
| CN104047038A (en) * | 2014-06-30 | 2014-09-17 | 句容市博远电子有限公司 | Nickel-chromium-copper-cobalt alloy electroplating solution and preparation method thereof |
| CN104480335A (en) * | 2014-11-28 | 2015-04-01 | 桂林电器科学研究院有限公司 | Preparation method of silver tungsten contact material |
| CN104700961A (en) * | 2015-03-18 | 2015-06-10 | 上海和伍新材料科技有限公司 | Graphene/silver composite material and preparation method thereof |
| US20150187983A1 (en) * | 2011-10-11 | 2015-07-02 | Korea Institute Of Science And Technology | Method for forming a transparent conductive film with metal nanowires having high linearity |
| CN105695788A (en) * | 2016-04-08 | 2016-06-22 | 上海和伍复合材料有限公司 | Graphene strengthening nickel base composite material and preparing method thereof |
| CN105779801A (en) * | 2016-04-08 | 2016-07-20 | 上海和伍复合材料有限公司 | Graphene enhanced silver nickel electric contact composite material and preparation method thereof |
| CN106711117A (en) * | 2017-01-24 | 2017-05-24 | 山东科大鼎新电子科技有限公司 | Graphene bonding silver wire and preparation method thereof |
-
2018
- 2018-04-13 CN CN201810328475.1A patent/CN108441668B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0554792A2 (en) * | 1992-02-05 | 1993-08-11 | BERU Ruprecht GmbH & Co. KG | Silver-nickel composite material for electrical contacts and electrodes |
| DE102006020988A1 (en) * | 2006-05-04 | 2007-11-08 | Nanogate Ag | Precious metal-containing nickel layer |
| CN1858867A (en) * | 2006-05-22 | 2006-11-08 | 靖江市海源有色金属材料有限公司 | Silver-tungsten carbide base electric contact material of high anti-melting and welding property and its processing process |
| CN101139663A (en) * | 2007-10-19 | 2008-03-12 | 厦门大学 | Preparation method of silver nickel composite material |
| US20150187983A1 (en) * | 2011-10-11 | 2015-07-02 | Korea Institute Of Science And Technology | Method for forming a transparent conductive film with metal nanowires having high linearity |
| CN104047038A (en) * | 2014-06-30 | 2014-09-17 | 句容市博远电子有限公司 | Nickel-chromium-copper-cobalt alloy electroplating solution and preparation method thereof |
| CN104480335A (en) * | 2014-11-28 | 2015-04-01 | 桂林电器科学研究院有限公司 | Preparation method of silver tungsten contact material |
| CN104700961A (en) * | 2015-03-18 | 2015-06-10 | 上海和伍新材料科技有限公司 | Graphene/silver composite material and preparation method thereof |
| CN105695788A (en) * | 2016-04-08 | 2016-06-22 | 上海和伍复合材料有限公司 | Graphene strengthening nickel base composite material and preparing method thereof |
| CN105779801A (en) * | 2016-04-08 | 2016-07-20 | 上海和伍复合材料有限公司 | Graphene enhanced silver nickel electric contact composite material and preparation method thereof |
| CN106711117A (en) * | 2017-01-24 | 2017-05-24 | 山东科大鼎新电子科技有限公司 | Graphene bonding silver wire and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110614381A (en) * | 2019-08-06 | 2019-12-27 | 温州聚星电接触科技有限公司 | Preparation method of silver-based graphene electrical contact material and electrical contact material thereof |
| CN111041546A (en) * | 2019-12-07 | 2020-04-21 | 福达合金材料股份有限公司 | Method for manufacturing silver-tungsten electrical contact with continuous silver layer on surface and product thereof |
| CN111041546B (en) * | 2019-12-07 | 2021-06-01 | 福达合金材料股份有限公司 | Method for manufacturing silver-tungsten electrical contact with continuous silver layer on surface and product thereof |
| CN111961911A (en) * | 2020-07-24 | 2020-11-20 | 浙江耐迩合金科技有限公司 | Preparation method of silver-based electric contact material with high fusion welding resistance |
| CN111961911B (en) * | 2020-07-24 | 2022-04-26 | 浙江耐迩合金科技有限公司 | Preparation method of silver-based electric contact material with high fusion welding resistance |
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