CN107761021B - Manganese-doped orthorhombic tin oxide reinforced silver-based electrical contact material and preparation method thereof - Google Patents
Manganese-doped orthorhombic tin oxide reinforced silver-based electrical contact material and preparation method thereof Download PDFInfo
- Publication number
- CN107761021B CN107761021B CN201710813021.9A CN201710813021A CN107761021B CN 107761021 B CN107761021 B CN 107761021B CN 201710813021 A CN201710813021 A CN 201710813021A CN 107761021 B CN107761021 B CN 107761021B
- Authority
- CN
- China
- Prior art keywords
- electrical contact
- contact material
- tin
- silver
- manganese
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C49/00—Alloys containing metallic or non-metallic fibres or filaments
- C22C49/02—Alloys containing metallic or non-metallic fibres or filaments characterised by the matrix material
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C47/00—Making alloys containing metallic or non-metallic fibres or filaments
- C22C47/14—Making alloys containing metallic or non-metallic fibres or filaments by powder metallurgy, i.e. by processing mixtures of metal powder and fibres or filaments
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C49/00—Alloys containing metallic or non-metallic fibres or filaments
- C22C49/14—Alloys containing metallic or non-metallic fibres or filaments characterised by the fibres or filaments
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
- H01H1/00—Contacts
- H01H1/02—Contacts characterised by the material thereof
- H01H1/021—Composite material
- H01H1/023—Composite material having a noble metal as the basic material
- H01H1/0237—Composite material having a noble metal as the basic material and containing oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
- H01H11/00—Apparatus or processes specially adapted for the manufacture of electric switches
- H01H11/04—Apparatus or processes specially adapted for the manufacture of electric switches of switch contacts
- H01H11/048—Apparatus or processes specially adapted for the manufacture of electric switches of switch contacts by powder-metallurgical processes
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Powder Metallurgy (AREA)
- Contacts (AREA)
Abstract
本发明涉及一种掺锰正交相氧化锡增强银基电触头材料及其制备方法，属于电触头材料技术领域。主要技术方案如下银基电触头材料，包括如下质量百分比的材料：银：80wt％‑98wt％；第二相：2wt％‑20wt％；所述的第二相为含有锰的氧化锡。所述第二相的纤维长度为0.1微米～1000微米，直径为0.0010.01微米～100微米，长径比为(2：1)～(200：1)；第二相中锡和锰元素的摩尔比为(4：1)～(100：1)；该方法制备的银‑氧化锡触头材料中氧化锡增强相为纤维形貌，并有部分为正交相锡，在电弧作用过程中，正交相可发生相变，二次增强触头材料，从而提高触头的工作寿命。The invention relates to a manganese-doped orthorhombic tin oxide reinforced silver-based electrical contact material and a preparation method thereof, belonging to the technical field of electrical contact materials. The main technical solution is the following silver-based electrical contact material, including the following mass percentage materials: silver: 80wt%-98wt%; second phase: 2wt%-20wt%; the second phase is tin oxide containing manganese. The fiber length of the second phase is 0.1 micrometers to 1000 micrometers, the diameter is 0.0010.01 micrometers to 100 micrometers, and the aspect ratio is (2:1) to (200:1); The molar ratio is (4:1)～(100:1); the tin oxide reinforced phase in the silver-tin oxide contact material prepared by this method is in the form of fibers, and part of it is orthorhombic tin, and in the process of arc action , the orthorhombic phase can undergo a phase change, and the contact material is strengthened twice, thereby improving the working life of the contact.
Description
Technical field
The present invention relates to one kind to mix manganese orthorhombic phase stannic oxide reinforced Ag-based electrical contact material and preparation method thereof, belongs to electric touching
Head material technical field.
Background technique
Electrical contact carries the effect of connection, carrying and breaking current in electronic circuit, is all kinds of device for switching, instrument
The core element of instrument.Ag-MeO (silver-metallic oxide) is utilized using conductivity in metal and the highest Ag of thermal conductivity as matrix
MeO (metal oxide) is the molten bath under the stable electric arc of the second phase, makes up the defect of Ag matrix easy splash, melting welding under electric arc,
Have become research and most widely used, function admirable electrical contact material.Wherein, Ag-CdO (silver-cadmium oxide) has stable low
Resistance and good arc resistance energy, are assigned always the appellation of " omnipotent contact ", are widely used in various mesolow electric appliances.
However, Ag-CdO all suffers from the harm of " cadmium poison " in the overall process for producing, using recycling, to human health and natural environment
It threatens, has caused the great attention of national governments.European Union, which once released, " to be limited in electrical, electronic equipment and uses certain nocuousness
Substances Directive " (RoHS instruction), application of the Ag-CdO in electric appliance is limited, but due to production technology, Ag-CdO contact
Limitation was exempted in July, 2021.But in recent years, the environmental consciousness of global human is increasingly enhanced, and national governments make laws to destruction
The behavior of environment is harsh year by year, and international high-end electric appliance business men such as Schneider, Chinese mugwort Bobbi group company (AG) etc. are by environmentally friendly parameter
It is added in supplier's evaluation criteria, after 4 years at the end of the exemption phase, Ag-CdO most probably formally steps down from the stage of history.It faces
Such severe challenge, China's Electrical Contact Industry research and develop the environment-friendly type electrical contact product of high quality, seize the first market opportunities, have become and compel
The task of the eyebrows and eyelashes.
Ag-SnO2(silver-tin) is with its good arc resistant ability and the anti-material transfer ability under DC load
Show one's talent, becomes most potential Ag-CdO alternative materials.For Ag-SnO2Performance Optimization Work there are many report,
And many achievements are obtained.But the SnO in the contact material reported at present2Mostly rutile structure, and orthorhombic phase structure oxygen
Change application of the tin in contact and has not yet to see report.
Summary of the invention
To make up the deficiencies in the prior art, the present invention provides one kind and mixes manganese orthorhombic phase stannic oxide reinforced Ag-based electrical contact material
And preparation method thereof.This method can be used for preparing the Ag-based electrical contact material that reinforced phase is orthohormbic structure fiber morphology tin oxide,
Under arcing, orthorhombic phase tin oxide undergoes phase transition expansion and forms secondary hardening to matrix, and the hardness of contact can be improved and resist
Wearing character, to improve the electrical property of contact.Technical scheme is as follows: one kind mixing manganese orthorhombic phase tin oxide enhancing silver
Base electric contact material, the material including following mass percent:
Silver: 80wt%-98wt%；
Second phase: 2wt%-20wt%；Second phase is the tin oxide containing manganese.
The fibre length of second phase is 0.1 micron~1000 microns, and diameter is 0.01 micron~100 microns, major diameter
Than for (2:1)~(200:1)；The molar ratio of tin and manganese element is (4:1)~(100:1) in second phase；Tin oxide fibre 1~
50wt% is orthorhombic phase；
The material is prepared as follows:
Step 1: tin salt and manganous salt being weighed in proportion, and are added to the water to obtain mixed solution；
Step 2: mixed solution being carried out to be heated to reflux processing, obtains female salting liquid of colloidal suspension dispersion；
Step 3: configuration oxalic acid solution precipitating reagent；
Step 4: the titration of female salting liquid is added in oxalic acid solution and is co-precipitated, is reacted after uniform stirring, centrifugation point
From, and repeatedly washing obtains sediment；
Step 5: putting the precipitate in dry in baking oven；
Step 6: the sediment after drying being transferred to Muffle furnace and is calcined, the orthorhombic phase tin oxide for obtaining doping manganese is fine
Dimension；
Step 7: weighing orthorhombic phase tin oxide fibre and silver respectively according to the mass ratio in silver-tin electrical contact material
Powder, and by two kinds of powder ball milling mixings；
Step 8: gained silver-tin composite granule being injected into graphite jig, bulk is obtained by discharge plasma sintering
Silver-tin electrical contact material.
Further, tin salt described in step 1 includes one or more of stannous sulfate, nitric acid stannous, stannous chloride,
Manganous salt includes manganese sulfate, Mn nitrate, acetic acid Asia manganese, more than one in protochloride manganese, and stannous salinity is 0.001~
1mol/L。
Further, it is heated to reflux described in step 2 and carries out in an inert atmosphere, temperature is 20~150 DEG C, and the time is
1~48h.
Further, oxalic acid solution concentration described in step 3 is 0.001~1mol/L, and oxalic acid and metal ion rub
, than being (1:1)~(4:1), the metal ion includes stannous and sub- manganese ion for you.
Further, in coprecipitation reaction described in step 4, titration speed is 1~100ml/min, and reaction temperature is
20~80 DEG C, the reaction time is 0.5~4h.
Further, drying temperature described in step 5 is 40~200 DEG C, and the time is 4~48h.
Further, calcination temperature described in step 6 is 300~800 DEG C, and the time is 1~4h, and atmosphere is oxygenous
Atmosphere.
Further, in ball milling mixing described in step 7, ratio of grinding media to material be (1:6)~(6:1), Ball-milling Time be 4~
48h。
Further, in discharge plasma sintering described in step 8, sintering temperature is 400~800 DEG C, briquetting pressure
For 20~90MPa, soaking time is 5~60min.
A kind of preparation side for mixing manganese orthorhombic phase stannic oxide reinforced Ag-based electrical contact material is claimed in the present invention simultaneously
Method includes the following steps:
Step 1: tin salt and manganous salt being weighed in proportion, and are added to the water to obtain mixed solution；
Step 2: mixed solution being carried out to be heated to reflux processing, obtains female salting liquid of colloidal suspension dispersion；
Step 3: configuration oxalic acid solution precipitating reagent；
Step 4: the titration of female salting liquid is added in oxalic acid solution and is co-precipitated, is reacted after uniform stirring, centrifugation point
From, and repeatedly washing obtains sediment；
Step 5: putting the precipitate in dry in baking oven；
Step 6: the sediment after drying being transferred to Muffle furnace and is calcined, the orthogonal phase oxidation doped with a small amount of manganese is obtained
Tin fiber；
Step 7: weighing orthorhombic phase tin oxide fibre and silver respectively according to the mass ratio in silver-tin electrical contact material
Powder, and by two kinds of powder ball milling mixings；
Step 8: gained silver-tin composite granule being injected into graphite jig, bulk is obtained by discharge plasma sintering
Silver-tin electrical contact material.
Orthorhombic phase tin oxide is a kind of transitional face of amorphous oxide tin into rutile tin oxide transition process, and density is high
In the tin oxide of rutile structure, and rutile structure can be changed into when being acted on by electric arc hot-fluid, generate volume expansion, mention
The hardness of high composite material.This phase transformation strengthening under arcing can be to Ag-SnO2Contact performance generates secondary enhancing and makees
With improving the service life of contact.
Beneficial effects of the present invention are as follows: this method can be used for silver-oxidation of fiber morphology orthorhombic phase tin oxide enhancing
The stability of orthorhombic phase tin oxide can be improved in tin electrical contact material, the addition of manganese, to obtain in silver-tin after sintering
Certain orthorhombic phase tin oxide, this silver-tin electrical contact material at least have the advantages that following two: on the one hand, electric arc is made
Under, place is fixed fiber morphology tin oxide one end at molten bath with basal body interface by matrix, and the other end is through capillary action
Stabilised bath can reduce melt splash；On the other hand, orthorhombic phase tin oxide can be undergone phase transition in arcing, generate volume
Expansion, to play the role of secondary hardening contact.
Specific embodiment
The present invention is further described combined with specific embodiments below, if material of the present invention is without specified otherwise, equal city
Selling can obtain.
Embodiment 1
One kind mixing manganese orthorhombic phase stannic oxide reinforced Ag-based electrical contact material, each component mass percent are as follows: silver 88%, oxygen
Change tin (containing manganese) 12%；
The Ag-based electrical contact material is prepared as follows:
Step 1: by stannous sulfate and protochloride manganese, 8:1 is weighed in molar ratio, and is added in solution and is obtained mixed solution,
Middle stannous sulfate concentration is 0.1mol/L；
Step 2: mixed solution being heated to 40 DEG C of reflux 8h in argon atmosphere, the female salt for obtaining colloidal suspension dispersion is molten
Liquid；
Step 3: the molar ratio of configuration 0.1mol/L oxalic acid solution precipitating reagent, oxalic acid and stannous sulfate is 1:1；
Step 4: female salting liquid is added in oxalic acid solution with the rate titration of 10ml/min, it is anti-in 40 DEG C of uniform stirrings
1h is answered, is centrifugated, and repeatedly washing obtains sediment；
Step 5: putting the precipitate in baking oven in 80 DEG C of dry 12h；
Step 6: the sediment after drying being transferred to Muffle furnace in 300 DEG C of calcining 4h, obtains the oxidation doped with a small amount of manganese
Tin fiber；
Step 7: tin oxide fibre and silver powder are weighed respectively according to the mass ratio in silver-tin electrical contact material, and
By two kinds of powder ball milling mixings, ratio of grinding media to material 1:3, Ball-milling Time 12h；Step 8: gained silver-tin composite granule is infused
Enter graphite jig, blocky silver-tin electrical contact material is obtained by discharge plasma sintering, sintering temperature is 500 DEG C, molding
Pressure is 30MPa, soaking time 15min.
In the silver-tin electrical contact material of this example preparation: tin oxide fibre length is 10~20 microns, and diameter is
0.1~0.2 micron, draw ratio is (50:1)~(100:1), and has 10% orthorhombic phase in tin oxide.
Embodiment 2
One kind mixing manganese orthorhombic phase stannic oxide reinforced Ag-based electrical contact material, each component mass percent are as follows: silver 84%, oxygen
Change tin (containing manganese) 16%；
The Ag-based electrical contact material is prepared as follows:
Step 1: by stannous chloride and manganese sulfate, 10:1 is weighed in molar ratio, and is added in solution and is obtained mixed solution,
Wherein stannous chloride concentration is 0.001mol/L；
Step 2: mixed solution being heated to 80 DEG C of reflux 4h in argon atmosphere, the female salt for obtaining colloidal suspension dispersion is molten
Liquid；
Step 3: the molar ratio of configuration 0.001mol/L oxalic acid solution precipitating reagent, oxalic acid and stannous chloride is 4:1；
Step 4: female salting liquid being added in oxalic acid solution with the rate titration of 100ml/min, in 60 DEG C of uniform stirrings
3.5h, centrifuge separation are reacted, and repeatedly washing obtains sediment；
Step 5: putting the precipitate in baking oven in 200 DEG C of dry 4h；
Step 6: the sediment after drying being transferred to Muffle furnace in 500 DEG C of calcining 3.5h, obtains the oxygen doped with a small amount of manganese
Change tin fiber；
Step 7: tin oxide fibre and silver powder are weighed respectively according to the mass ratio in silver-tin electrical contact material, and
By two kinds of powder ball milling mixings, ratio of grinding media to material 2:1, Ball-milling Time 18h；
Step 8: gained silver-tin composite granule being injected into graphite jig, bulk is obtained by discharge plasma sintering
Silver-tin electrical contact material, sintering temperature are 600 DEG C, briquetting pressure 90MPa, soaking time 30min.
Tin oxide fibre length is 800~1000 microns in the silver-tin electrical contact material of this example preparation, and diameter is
50~100 microns, draw ratio is (10:1)~(20:1), and has 30% orthorhombic phase in tin oxide.
Embodiment 3
One kind mixing manganese orthorhombic phase stannic oxide reinforced Ag-based electrical contact material, each component mass percent are as follows: silver 98%, oxygen
Change tin (containing manganese) 2%；
The Ag-based electrical contact material is prepared as follows:
Step 1: by stannous chloride and Mn nitrate, 20:1 is weighed in molar ratio, and is added in solution and is obtained mixed solution,
Wherein stannous chloride concentration is 0.05mol/L；
Step 2: mixed solution being heated to 150 DEG C of reflux 1h in argon atmosphere, the female salt for obtaining colloidal suspension dispersion is molten
Liquid；
Step 3: the molar ratio of configuration 0.05mol/L oxalic acid solution precipitating reagent, oxalic acid and stannous chloride is 2:1；
Step 4: female salting liquid is added in oxalic acid solution with the rate titration of 1ml/min, it is anti-in 20 DEG C of uniform stirrings
4h is answered, is centrifugated, and repeatedly washing obtains sediment；
Step 5: putting the precipitate in baking oven in 40 DEG C of dry 48h；
Step 6: the sediment after drying being transferred to Muffle furnace in 550 DEG C of calcining 1h, obtains the oxidation doped with a small amount of manganese
Tin fiber；
Step 7: tin oxide fibre and silver powder are weighed respectively according to the mass ratio in silver-tin electrical contact material, and
By two kinds of powder ball milling mixings, ratio of grinding media to material 2:5, Ball-milling Time 8h.
Step 8: gained silver-tin composite granule being injected into graphite jig, bulk is obtained by discharge plasma sintering
Silver-tin electrical contact material, sintering temperature are 700 DEG C, briquetting pressure 40MPa, soaking time 5min.
Tin oxide fibre length is 200~500 microns in the silver-tin electrical contact material of this example preparation, and diameter is
10~30 microns, draw ratio is (15:1)~(30:1), and has 20% orthorhombic phase in tin oxide.
Embodiment 4
One kind mixing manganese orthorhombic phase stannic oxide reinforced Ag-based electrical contact material, each component mass percent are as follows: silver 94%, oxygen
Change tin (containing manganese) 6%；
Described Ag-based electrical contact material and preparation method thereof, the preparation method comprises the following steps:
Step 1: by stannous sulfate and acetic acid Asia manganese, 70:1 is weighed in molar ratio, and is added in solution and is obtained mixed solution,
Wherein stannous sulfate concentration is 0.001mol/L；
Step 2: mixed solution being heated to 130 DEG C of reflux 12h in argon atmosphere, the female salt for obtaining colloidal suspension dispersion is molten
Liquid；
Step 3: the molar ratio of configuration 0.01mol/L oxalic acid solution precipitating reagent, oxalic acid and stannous sulfate is 4:1；
Step 4: female salting liquid is added in oxalic acid solution with the rate titration of 90ml/min, it is anti-in 20 DEG C of uniform stirrings
4h is answered, is centrifugated, and repeatedly washing obtains sediment；
Step 5: putting the precipitate in baking oven in 60 DEG C of dry 32h；
Step 6: the sediment after drying being transferred to Muffle furnace in 400 DEG C of calcining 2.5h, obtains the oxygen doped with a small amount of manganese
Change tin fiber；
Step 7: tin oxide fibre and silver powder are weighed respectively according to the mass ratio in silver-tin electrical contact material, and
By two kinds of powder ball milling mixings, ratio of grinding media to material 3:1, Ball-milling Time is for 24 hours.
Step 8: gained silver-tin composite granule being injected into graphite jig, bulk is obtained by discharge plasma sintering
Silver-tin electrical contact material, sintering temperature are 500 DEG C, briquetting pressure 70MPa, soaking time 40min.
Tin oxide fibre length is 0.1~0.2 micron in the silver-tin electrical contact material of this example preparation, and diameter is
0.02~0.03 micron, draw ratio is (5:1)~(10:1), and it is orthorhombic phase that tin oxide, which has 23%,.
Embodiment 5
One kind mixing manganese orthorhombic phase stannic oxide reinforced Ag-based electrical contact material, each component mass percent are as follows: silver 80%, oxygen
Change tin (containing manganese) 20%；
The Ag-based electrical contact material is prepared as follows:
Step 1: by stannous chloride and acetic acid Asia manganese, 100:1 is weighed in molar ratio, and is added in solution and is obtained mixed solution,
Wherein stannous chloride concentration is 1mol/L；
Step 2: mixed solution being heated to 20 DEG C of reflux 48h in argon atmosphere, the female salt for obtaining colloidal suspension dispersion is molten
Liquid；
Step 3: the molar ratio of configuration 1mol/L oxalic acid solution precipitating reagent, oxalic acid and stannous chloride is 2:1；
Step 4: female salting liquid is added in oxalic acid solution with the rate titration of 1ml/min, it is anti-in 20 DEG C of uniform stirrings
0.5h is answered, is centrifugated, and repeatedly washing obtains sediment；
Step 5: putting the precipitate in baking oven in 120 DEG C of dry 16h；
Step 6: the sediment after drying is transferred in tube furnace, 600 DEG C of calcining 1h in oxygen atmosphere, obtain doped with
The tin oxide fibre of a small amount of manganese；
Step 7: tin oxide fibre and silver powder are weighed respectively according to the mass ratio in silver-tin electrical contact material, and
By two kinds of powder ball milling mixings, ratio of grinding media to material 2:1, Ball-milling Time 36h；
Step 8: gained silver-tin composite granule being injected into graphite jig, bulk is obtained by discharge plasma sintering
Silver-tin electrical contact material, sintering temperature are 600 DEG C, briquetting pressure 50MPa, soaking time 20min.
Tin oxide fibre length is 50~100 microns in the silver-tin electrical contact material of this example preparation, and diameter is
0.3~0.5 micron, draw ratio is (150:1)~(200:1), and having 1% in tin oxide is orthorhombic phase.
Embodiment 6
One kind mixing manganese orthorhombic phase stannic oxide reinforced Ag-based electrical contact material, each component mass percent are as follows: silver 82%, oxygen
Change tin (containing manganese) 18%；
Described Ag-based electrical contact material and preparation method thereof, the preparation method comprises the following steps:
Step 1: by stannous chloride and Mn nitrate, 8:1 is weighed in molar ratio, and is added in solution and is obtained mixed solution,
Middle stannous chloride concentration is 0.01mol/L；
Step 2: mixed solution being heated to 70 DEG C of reflux 36h in argon atmosphere, the female salt for obtaining colloidal suspension dispersion is molten
Liquid；
Step 3: the molar ratio of configuration 0.03mol/L oxalic acid solution precipitating reagent, oxalic acid and stannous chloride is 3:1；
Step 4: female salting liquid is added in oxalic acid solution with the rate titration of 30ml/min, it is anti-in 70 DEG C of uniform stirrings
3h is answered, is centrifugated, and repeatedly washing obtains sediment；
Step 5: putting the precipitate in baking oven and dried for 24 hours at 100 DEG C；
Step 6: the sediment after drying is transferred in tube furnace, 800 DEG C of calcining 2h in oxygen atmosphere, obtain doped with
The tin oxide fibre of a small amount of manganese；
Step 7: tin oxide fibre and silver powder are weighed respectively according to the mass ratio in silver-tin electrical contact material, and
By two kinds of powder ball milling mixings, ratio of grinding media to material 4:1, Ball-milling Time 28h.
Step 8: gained silver-tin composite granule being injected into graphite jig, bulk is obtained by discharge plasma sintering
Silver-tin electrical contact material, sintering temperature are 800 DEG C, briquetting pressure 20MPa, soaking time 45min.
Tin oxide fibre length is 200~300 microns in the silver-tin electrical contact material of this example preparation, and diameter is
10~15 microns, draw ratio is (20:1)~(30:1), and having 40% in tin oxide is orthorhombic phase.
Embodiment 7
One kind mixing manganese orthorhombic phase stannic oxide reinforced Ag-based electrical contact material, each component mass percent are as follows: silver 84%, oxygen
Change tin (containing manganese) 16%；
The Ag-based electrical contact material is prepared as follows:
Step 1: by stannous sulfate and Mn nitrate, 7:1 is weighed in molar ratio, and is added in solution and is obtained mixed solution,
Middle stannous sulfate concentration is 0.8mol/L；
Step 2: mixed solution being heated to 100 DEG C of reflux 42h in argon atmosphere, the female salt for obtaining colloidal suspension dispersion is molten
Liquid；
Step 3: the molar ratio of configuration 0.8mol/L oxalic acid solution precipitating reagent, oxalic acid and stannous sulfate is 1:1；
Step 4: female salting liquid is added in oxalic acid solution with the rate titration of 50ml/min, it is anti-in 40 DEG C of uniform stirrings
4h is answered, is centrifugated, and repeatedly washing obtains sediment；
Step 5: putting the precipitate in baking oven in 130 DEG C of dry 8h；
Step 6: the sediment after drying is transferred in tube furnace, 300 DEG C of calcining 4h in oxygen atmosphere, obtain doped with
The tin oxide fibre of a small amount of manganese；
Step 7: tin oxide fibre and silver powder are weighed respectively according to the mass ratio in silver-tin electrical contact material, and
By two kinds of powder ball milling mixings, ratio of grinding media to material 1:1, Ball-milling Time 4h；
Step 8: gained silver-tin composite granule being injected into graphite jig, bulk is obtained by discharge plasma sintering
Silver-tin electrical contact material, sintering temperature are 400 DEG C, briquetting pressure 50MPa, soaking time 60min.
Tin oxide fibre length is 500~800 microns in the silver-tin electrical contact material of this example preparation, and diameter is
10~15 microns, draw ratio is 50:1~70:1, and it is orthorhombic phase that tin oxide, which has 50%,.
Embodiment 8
One kind mixing manganese orthorhombic phase stannic oxide reinforced Ag-based electrical contact material, each component mass percent are as follows: silver 86%, oxygen
Change tin (containing manganese) 14%；
The Ag-based electrical contact material is prepared as follows:
Step 1: by nitric acid stannous and Mn nitrate, 50:1 is weighed in molar ratio, and is added in solution and is obtained mixed solution,
Wherein nitric acid stannous concentration is 0.2mol/L；
Step 2: mixed solution being heated to 80 DEG C of reflux 18h in argon atmosphere, the female salt for obtaining colloidal suspension dispersion is molten
Liquid；
Step 3: the molar ratio of configuration 0.3mol/L oxalic acid solution precipitating reagent, oxalic acid and nitric acid stannous is 3:2；
Step 4: female salting liquid is added in oxalic acid solution with the rate titration of 50ml/min, it is anti-in 70 DEG C of uniform stirrings
3h is answered, is centrifugated, and repeatedly washing obtains sediment；
Step 5: putting the precipitate in baking oven in 150 DEG C of dry 28h；
Step 6: the sediment after drying being transferred to 450 DEG C of calcining 1.5h in Muffle furnace, obtains the oxygen doped with a small amount of manganese
Change tin fiber；
Step 7: tin oxide fibre and silver powder are weighed respectively according to the mass ratio in silver-tin electrical contact material, and
By two kinds of powder ball milling mixings, ratio of grinding media to material 4:3, Ball-milling Time 30h；
Step 8: gained silver-tin composite granule being injected into graphite jig, bulk is obtained by discharge plasma sintering
Silver-tin electrical contact material, sintering temperature are 550 DEG C, briquetting pressure 60MPa, soaking time 50min.
Tin oxide fibre length is 6~10 microns in the silver-tin electrical contact material of this example preparation, and diameter is 3~4
Micron, draw ratio are (2:1)~(3:1), and having 24% in tin oxide is orthorhombic phase.
Embodiment 9
One kind mixing manganese orthorhombic phase stannic oxide reinforced Ag-based electrical contact material, each component mass percent are as follows: silver 86%, oxygen
Change tin (containing manganese) 14%；
The Ag-based electrical contact material is prepared as follows:
Step 1: by nitric acid stannous and acetic acid Asia manganese, 4:1 is weighed in molar ratio, and is added in solution and is obtained mixed solution,
Middle nitric acid stannous concentration is 0.5mol/L；
Step 2: mixed solution being heated to 50 DEG C of reflux 6h in argon atmosphere, the female salt for obtaining colloidal suspension dispersion is molten
Liquid；
Step 3: the molar ratio of configuration 0.5mol/L oxalic acid solution precipitating reagent, oxalic acid and nitric acid stannous is 3:2；
Step 4: female salting liquid is added in oxalic acid solution with the rate titration of 5ml/min, it is anti-in 30 DEG C of uniform stirrings
2.5h is answered, is centrifugated, and repeatedly washing obtains sediment；
Step 5: putting the precipitate in baking oven in 160 DEG C of dry 12h；
Step 6: the sediment after drying being transferred to 450 DEG C of calcining 1.5h in Muffle furnace, obtains the oxygen doped with a small amount of manganese
Change tin fiber；
Step 7: tin oxide fibre and silver powder are weighed respectively according to the mass ratio in silver-tin electrical contact material, and
By two kinds of powder ball milling mixings, ratio of grinding media to material 1:6, Ball-milling Time 40h；
Step 8: gained silver-tin composite granule being injected into graphite jig, bulk is obtained by discharge plasma sintering
Silver-tin electrical contact material, sintering temperature are 600 DEG C, briquetting pressure 60MPa, soaking time 50min.
This example preparation silver-tin electrical contact material in tin oxide fibre length be 1~3 micron, diameter be 0.1~
0.2 micron, draw ratio is (8:1)~(15:1), and it is orthorhombic phase that tin oxide, which has 42%,.
Embodiment 10
One kind mixing manganese orthorhombic phase stannic oxide reinforced Ag-based electrical contact material, each component mass percent are as follows: silver 94%, oxygen
Change tin (containing manganese) 6%；
The Ag-based electrical contact material is prepared as follows:
Step 1: by nitric acid stannous and manganese sulfate, 30:1 is weighed in molar ratio, and is added in solution and is obtained mixed solution,
Wherein nitric acid stannous concentration is 0.002mol/L；
Step 2: mixed solution being heated to 120 DEG C of reflux in argon atmosphere for 24 hours, the female salt for obtaining colloidal suspension dispersion is molten
Liquid；
Step 3: the molar ratio of configuration 0.005mol/L oxalic acid solution precipitating reagent, oxalic acid and nitric acid stannous is 5:2；
Step 4: female salting liquid is added in oxalic acid solution with the rate titration of 80ml/min, it is anti-in 50 DEG C of uniform stirrings
2h is answered, is centrifugated, and repeatedly washing obtains sediment；
Step 5: putting the precipitate in baking oven in 50 DEG C of dry 32h；
Step 6: the sediment after drying being transferred to 350 DEG C of calcining 3h in Muffle furnace, obtains the oxidation doped with a small amount of manganese
Tin fiber；
Step 7: tin oxide fibre and silver powder are weighed respectively according to the mass ratio in silver-tin electrical contact material, and
By two kinds of powder ball milling mixings, ratio of grinding media to material 5:3, Ball-milling Time 48h.
Step 8: gained silver-tin composite granule being injected into graphite jig, bulk is obtained by discharge plasma sintering
Silver-tin electrical contact material, sintering temperature are 450 DEG C, briquetting pressure 80MPa, soaking time 25min.
Tin oxide fibre length is 0.5~0.8 micron in the silver-tin electrical contact material of this example preparation, and diameter is
0.01~0.02 micron, draw ratio is (30:1)~(50:1), and having 15% in tin oxide is orthorhombic phase.
Embodiment 11
One kind mixing manganese orthorhombic phase stannic oxide reinforced Ag-based electrical contact material, each component mass percent are as follows: silver 96%, oxygen
Change tin (containing manganese) 4%；
The Ag-based electrical contact material is prepared as follows:
Step 1: by stannous sulfate and manganese sulfate, 80:1 is weighed in molar ratio, and is added in solution and is obtained mixed solution,
Wherein stannous sulfate concentration is 0.5mol/L；
Step 2: mixed solution being heated to 120 DEG C of reflux 30h in argon atmosphere, the female salt for obtaining colloidal suspension dispersion is molten
Liquid；
Step 3: the molar ratio of configuration 0.5mol/L oxalic acid solution precipitating reagent, oxalic acid and stannous sulfate is 4:1；
Step 4: female salting liquid is added in oxalic acid solution with the rate titration of 15ml/min, it is anti-in 80 DEG C of uniform stirrings
1h is answered, is centrifugated, and repeatedly washing obtains sediment；
Step 5: putting the precipitate in baking oven in 180 DEG C of dry 20h；
Step 6: the sediment after drying being transferred to 500 DEG C of calcining 2h in Muffle furnace, obtains the oxidation doped with a small amount of manganese
Tin fiber；
Step 7: tin oxide fibre and silver powder are weighed respectively according to the mass ratio in silver-tin electrical contact material, and
By two kinds of powder ball milling mixings, ratio of grinding media to material 7:3, Ball-milling Time 10h；
Step 8: gained silver-tin composite granule being injected into graphite jig, bulk is obtained by discharge plasma sintering
Silver-tin electrical contact material, sintering temperature are 650 DEG C, briquetting pressure 80MPa, soaking time 10min.
This example preparation silver-tin electrical contact material in tin oxide fibre length be 20~30 microns, diameter be 1~
2 microns, draw ratio is (15:1)~(20:1), and having 5% in tin oxide is orthorhombic phase.
Embodiment 12
One kind mixing manganese orthorhombic phase stannic oxide reinforced Ag-based electrical contact material, each component mass percent are as follows: silver 96%, oxygen
Change tin (containing manganese) 4%；
The Ag-based electrical contact material is prepared as follows:
Step 1: by nitric acid stannous and protochloride manganese, 6:1 is weighed in molar ratio, and is added in solution and is obtained mixed solution,
Middle nitric acid stannous concentration is 0.15mol/L；
Step 2: mixed solution being heated to 30 DEG C of reflux 46h in argon atmosphere, the female salt for obtaining colloidal suspension dispersion is molten
Liquid；
Step 3: the molar ratio of configuration 0.15mol/L oxalic acid solution precipitating reagent, oxalic acid and nitric acid stannous is 7:2；
Step 4: female salting liquid is added in oxalic acid solution with the rate titration of 70ml/min, it is anti-in 50 DEG C of uniform stirrings
2h is answered, is centrifugated, and repeatedly washing obtains sediment；
Step 5: putting the precipitate in baking oven in 140 DEG C of dry 42h；
Step 6: the sediment after drying being transferred to 700 DEG C of calcining 3h in Muffle furnace, obtains the oxidation doped with a small amount of manganese
Tin fiber；
Step 7: tin oxide fibre and silver powder are weighed respectively according to the mass ratio in silver-tin electrical contact material, and
By two kinds of powder ball milling mixings, ratio of grinding media to material 6:1, Ball-milling Time 44h.
Step 8: gained silver-tin composite granule being injected into graphite jig, bulk is obtained by discharge plasma sintering
Silver-tin electrical contact material, sintering temperature are 800 DEG C, briquetting pressure 90MPa, soaking time 5min.
Tin oxide fibre length is 60~80 microns in the silver-tin electrical contact material of this example preparation, diameter 0.5
~0.8 micron, draw ratio is (120:1)~(150:1), and it is orthorhombic phase that tin oxide, which has 36%,.
Claims (10)
1. one kind mixes manganese orthorhombic phase stannic oxide reinforced Ag-based electrical contact material, which is characterized in that including following mass percent
Material:
Silver: 80wt%-98wt%；
Second phase: 2wt%-20wt%；Second phase is the tin oxide containing manganese；
The fibre length of second phase is 0.1 micron~1000 microns, and diameter is 0.01 micron~100 microns, and draw ratio is
(2:1)~(200:1)；The molar ratio of tin and manganese element is (4:1)~(100:1) in second phase；1~50wt% of tin oxide fibre
For orthorhombic phase；
The material is prepared as follows:
Step 1: tin salt and manganous salt being weighed in proportion, and are added to the water to obtain mixed solution；
Step 2: mixed solution being carried out to be heated to reflux processing, obtains female salting liquid of colloidal suspension dispersion；
Step 3: configuration oxalic acid solution precipitating reagent；
Step 4: the titration of female salting liquid is added in oxalic acid solution and is co-precipitated, is reacted after uniform stirring, is centrifugated, and
Repeatedly washing obtains sediment；
Step 5: putting the precipitate in dry in baking oven；
Step 6: the sediment after drying being transferred to Muffle furnace and is calcined, the orthorhombic phase tin oxide fibre of doping manganese is obtained；
Step 7: orthorhombic phase tin oxide fibre and silver powder are weighed respectively according to the mass ratio in silver-tin electrical contact material,
And by two kinds of ingredient ball milling mixings of tin oxide fibre and silver powder；
Step 8: gained silver-tin composite granule being injected into graphite jig, blocky silver-oxygen is obtained by discharge plasma sintering
Change tin electrical contact material.
2. Ag-based electrical contact material as described in claim 1, which is characterized in that tin salt described in step 1 includes sulfuric acid Asia
One or more of tin, nitric acid stannous, stannous chloride, manganous salt include manganese sulfate, Mn nitrate, acetic acid Asia manganese, protochloride
More than one in manganese, stannous salinity are 0.001~1mol/L.
3. Ag-based electrical contact material as described in claim 1, which is characterized in that be heated to reflux described in step 2 in inertia
It is carried out in atmosphere, temperature is 20~150 DEG C, and the time is 1~48h.
4. Ag-based electrical contact material as described in claim 1, which is characterized in that oxalic acid solution concentration described in step 3 is
The molar ratio of 0.001~1mol/L, oxalic acid and metal ion is (1:1)~(4:1), and the metal ion includes stannous and Asia
Manganese ion.
5. Ag-based electrical contact material as described in claim 1, which is characterized in that in coprecipitation reaction described in step 4, drop
Constant speed rate is 1~100ml/min, and reaction temperature is 20~80 DEG C, and the reaction time is 0.5~4h.
6. Ag-based electrical contact material as described in claim 1, which is characterized in that drying temperature described in step 5 be 40~
200 DEG C, the time is 4~48h.
7. Ag-based electrical contact material as described in claim 1, which is characterized in that calcination temperature described in step 6 be 300~
800 DEG C, the time is 1~4h, and atmosphere is oxygen-containing atmosphere.
8. Ag-based electrical contact material as described in claim 1, which is characterized in that in ball milling mixing described in step 7, ball material
Than for (1:6)~(6:1), Ball-milling Time is 4~48h.
9. Ag-based electrical contact material as described in claim 1, which is characterized in that discharge plasma sintering described in step 8
In, sintering temperature is 400~800 DEG C, and briquetting pressure is 20~90MPa, and soaking time is 5~60min.
10. a kind of preparation method for mixing manganese orthorhombic phase stannic oxide reinforced Ag-based electrical contact material as described in claim 1.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711358026.3A CN108085621B (en) | 2017-09-11 | 2017-09-11 | One kind mixing manganese orthorhombic phase stannic oxide reinforced Ag-based electrical contact material |
| CN201710813021.9A CN107761021B (en) | 2017-09-11 | 2017-09-11 | Manganese-doped orthorhombic tin oxide reinforced silver-based electrical contact material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710813021.9A CN107761021B (en) | 2017-09-11 | 2017-09-11 | Manganese-doped orthorhombic tin oxide reinforced silver-based electrical contact material and preparation method thereof |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711358026.3A Division CN108085621B (en) | 2017-09-11 | 2017-09-11 | One kind mixing manganese orthorhombic phase stannic oxide reinforced Ag-based electrical contact material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107761021A CN107761021A (en) | 2018-03-06 |
| CN107761021B true CN107761021B (en) | 2019-04-30 |
Family
ID=61265958
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711358026.3A Active CN108085621B (en) | 2017-09-11 | 2017-09-11 | One kind mixing manganese orthorhombic phase stannic oxide reinforced Ag-based electrical contact material |
| CN201710813021.9A Expired - Fee Related CN107761021B (en) | 2017-09-11 | 2017-09-11 | Manganese-doped orthorhombic tin oxide reinforced silver-based electrical contact material and preparation method thereof |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711358026.3A Active CN108085621B (en) | 2017-09-11 | 2017-09-11 | One kind mixing manganese orthorhombic phase stannic oxide reinforced Ag-based electrical contact material |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN108085621B (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5155990A (en) * | 1974-11-12 | 1976-05-17 | Sumitomo Electric Industries | |
| JPS51120927A (en) * | 1975-04-16 | 1976-10-22 | Sumitomo Electric Ind Ltd | Electric contact material |
| GB1507854A (en) * | 1974-04-01 | 1978-04-19 | Mallory & Co Inc P R | Electric contact materials |
| JPS55138046A (en) * | 1979-04-13 | 1980-10-28 | Matsushita Electric Works Ltd | Electric contact material |
| JPS55145140A (en) * | 1979-04-25 | 1980-11-12 | Nippon Tungsten Co Ltd | Electrical contact material |
| JPS5618319A (en) * | 1979-07-21 | 1981-02-21 | Matsushita Electric Works Ltd | Method of manufacturing electric contact material |
| CN1234591A (en) * | 1999-05-10 | 1999-11-10 | 昆明理工大学 | Synthesis method for preparing silver-tin dioxide electric contact materials |
| CN1830599A (en) * | 2006-04-07 | 2006-09-13 | 桂林金格电工电子材料科技有限公司 | Silver composite tin oxide contact material and its preparation technology |
| CN104505287A (en) * | 2014-12-22 | 2015-04-08 | 东北大学 | Preparation method of rod-shaped tin oxide-reinforced silver-based electric contact material |
| CN105908108A (en) * | 2016-04-14 | 2016-08-31 | 西安工程大学 | Preparation method of tin oxide fiber reinforced silver-based electric contact alloy |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS523193A (en) * | 1975-06-24 | 1977-01-11 | Sumitomo Electric Ind Ltd | Electric contact material |
| US4680162A (en) * | 1984-12-11 | 1987-07-14 | Chugai Denki Kogyo K.K. | Method for preparing Ag-SnO system alloy electrical contact material |
| CA2033139A1 (en) * | 1989-12-26 | 1991-06-27 | Akira Shibata | Silver-metal oxide composite material and process for producing the same |
| CN106057526A (en) * | 2016-06-27 | 2016-10-26 | 温州中希电工合金有限公司 | Laminated silver-copper-brazing-filler-metal three-composite electrical contact material manufactured by coating and sleeving method and manufacturing method thereof |
| CN106298293A (en) * | 2016-08-22 | 2017-01-04 | 福达合金材料股份有限公司 | A kind of oxycompound additive silver nickel contact material and preparation method thereof |
-
2017
- 2017-09-11 CN CN201711358026.3A patent/CN108085621B/en active Active
- 2017-09-11 CN CN201710813021.9A patent/CN107761021B/en not_active Expired - Fee Related
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1507854A (en) * | 1974-04-01 | 1978-04-19 | Mallory & Co Inc P R | Electric contact materials |
| JPS5155990A (en) * | 1974-11-12 | 1976-05-17 | Sumitomo Electric Industries | |
| JPS51120927A (en) * | 1975-04-16 | 1976-10-22 | Sumitomo Electric Ind Ltd | Electric contact material |
| JPS55138046A (en) * | 1979-04-13 | 1980-10-28 | Matsushita Electric Works Ltd | Electric contact material |
| JPS55145140A (en) * | 1979-04-25 | 1980-11-12 | Nippon Tungsten Co Ltd | Electrical contact material |
| JPS5618319A (en) * | 1979-07-21 | 1981-02-21 | Matsushita Electric Works Ltd | Method of manufacturing electric contact material |
| CN1234591A (en) * | 1999-05-10 | 1999-11-10 | 昆明理工大学 | Synthesis method for preparing silver-tin dioxide electric contact materials |
| CN1830599A (en) * | 2006-04-07 | 2006-09-13 | 桂林金格电工电子材料科技有限公司 | Silver composite tin oxide contact material and its preparation technology |
| CN104505287A (en) * | 2014-12-22 | 2015-04-08 | 东北大学 | Preparation method of rod-shaped tin oxide-reinforced silver-based electric contact material |
| CN105908108A (en) * | 2016-04-14 | 2016-08-31 | 西安工程大学 | Preparation method of tin oxide fiber reinforced silver-based electric contact alloy |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108085621B (en) | 2019-05-31 |
| CN108085621A (en) | 2018-05-29 |
| CN107761021A (en) | 2018-03-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101425545B (en) | Environment protection type silicon solar cell back electric field aluminum pulp and producing method thereof | |
| CN101071687A (en) | Silver-nanotin oxide electric contact material and its preparing process | |
| CN103258584A (en) | Electric conductive silver paste and manufacturing method thereof | |
| CN106226365B (en) | A kind of preparation method of graphene/copper composite material | |
| CN105695791A (en) | Novel silver rare earth oxide alloy and preparing method thereof | |
| WO2021000451A1 (en) | "core-shell" structure functional conductive particle preparation method | |
| CN110549039A (en) | Carbon nano tube/nano silver soldering paste heat conduction material and preparation method thereof | |
| CN101468397A (en) | Method for preparing ATO conductive powder using nano antimony oxide and tin oxide powder | |
| CN101246759A (en) | A nano-homogeneous composite metal oxide conductive powder for transparent conductive materials | |
| CN107761021B (en) | Manganese-doped orthorhombic tin oxide reinforced silver-based electrical contact material and preparation method thereof | |
| CN113699402A (en) | Preparation method of silver tin oxide electrical contact material containing copper oxide nano additive | |
| CN106564937A (en) | Preparation method of antimony-doped nanometer tin oxide (ATO) powder | |
| CN106238749A (en) | A kind of trace salt auxiliary polyhydric alcohol method prepares ultra-long silver nanowire | |
| CN107910099A (en) | A kind of compound silver paste of graphene and preparation method thereof | |
| CN106732591A (en) | A kind of graphene-supported p N-shapeds Cu2O‑TiO2The preparation method of heterojunction nanometer material | |
| CN108439469B (en) | Preparation and application method of silver molybdate nano powder with nearly spherical structure | |
| CN107419125B (en) | A kind of preparation method of high stable type copper-based electric contact material | |
| CN106086503B (en) | A kind of highly conductive flexible silver-based composite material and preparation method thereof | |
| CN109065852A (en) | A kind of positive electrode and preparation method thereof | |
| CN115679110B (en) | Utilization method of titanium slag smelting dust | |
| CN107695360A (en) | Graphene is modified the preparation method of silver-colored stannic acid lanthanum electric contact composite material | |
| CN108408763B (en) | Preparation and application method of nano-tin oxide powder co-doped with niobium and indium | |
| CN106876199B (en) | A kind of preparation method of the siller tin oxide alloy as electric contact material of even tissue | |
| CN109659149A (en) | A kind of graphene absorbent charcoal composite material and its preparation method and application | |
| CN112259278B (en) | A kind of preparation method of particle composite fiber reinforced copper tin oxide contact material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190430 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |