CN106399788A - Tungsten alloy and preparation method thereof - Google Patents

Tungsten alloy and preparation method thereof Download PDF

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Publication number
CN106399788A
CN106399788A CN201610938274.4A CN201610938274A CN106399788A CN 106399788 A CN106399788 A CN 106399788A CN 201610938274 A CN201610938274 A CN 201610938274A CN 106399788 A CN106399788 A CN 106399788A
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parts
oxide
tungsten
tungsten alloy
manganese
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林海英
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/04—Alloys based on tungsten or molybdenum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/10—Alloys containing non-metals
    • C22C1/1036—Alloys containing non-metals starting from a melt
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/10—Alloys containing non-metals
    • C22C1/1036—Alloys containing non-metals starting from a melt
    • C22C1/1047—Alloys containing non-metals starting from a melt by mixing and casting liquid metal matrix composites
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/0005—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with at least one oxide and at least one of carbides, nitrides, borides or silicides as the main non-metallic constituents
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/0084—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ carbon or graphite as the main non-metallic constituent

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Composite Materials (AREA)
  • Powder Metallurgy (AREA)

Abstract

The invention discloses a tungsten alloy. The tungsten alloy comprises, by weight, 100-102 parts of tungsten, 10-12 parts of aluminum, 8-10 parts of copper, 1-3 parts of molybdenum oxide, 4-6 parts of manganese, 1-3 parts of vanadium boride, 2-4 parts of neodymium oxide, 1-3 parts of tin, 1-3 parts of dysprosium oxide, 2-4 parts of praseodymium oxide, 5-7 parts of yttrium oxide, 2-4 parts of chromic oxide, 1-3 parts of boron carbide, 6-8 parts of titanium dioxide, 1-3 parts of silicon carbide and 1-3 parts of graphite powder. The tungsten alloy is high in strength.

Description

A kind of tungsten alloy and preparation method thereof
Technical field
The present invention relates to a kind of tungsten alloy and preparation method thereof.
Background technology
Tungsten alloy is the alloy adding other elements composition with tungsten for base.In a metal, the fusing point highest of tungsten, elevated temperature strength All good with creep-resistant property and heat conduction, conductive and electron emission capability, ratio is great, except being largely used to manufacture hard alloy and work Outside alloy addition, tungsten and its alloy are widely used in electronics, electric light source industry, are also used in the departments such as space flight, casting, weapon Make rocket nozzle, die casting, armor-piercing bullet core, contact, heater and heat screen etc..
1907, a kind of tungsten alloy of low nickel-content came out, and it is prepared by machining process, but seriously Fragility hamper its application.Until 1909, the Martha Coolidge (w.D.Coolidge) of General Electric Apparatus Co.(U.S.A.) passed through powder Last metallurgy method is obtained tungsten strip, recycles machining to produce the tungsten filament at room temperature with ductility, thus having established tungsten filament The basis of processing industry, has also established the basis of powder metallurgy.
But this " ductility " tungsten alloy shows obvious fragility after bulb is lighted.1913, put down strange (Pintsch) Invent thoriatde-tungsten wire (content of ThO2 is 1%～2%), so that the fragility of incandescent filament substantially reduces.Originally, under filament Vertical (see the sink-resistance performance of tungsten filament) is not a problem, because filament now is raw silk rings, but after 1913, blue rice Raw silk rings is changed to taenidium by your (Langmuir), and so, when bulb uses, the effect of high operating temperature and deadweight makes filament Sagging, thus pure tungsten and thorium tungsten are all difficult to meet use requirement.
In order to solve that tungsten filament is sagging and the problems such as short life, 1917, Bai Si (A.Pacz) invented " constant under high temperature The tungsten alloy of shape ".Originally, he adopts fire-clay crucible roasting WO3 when preparing pure tungsten it is not intended to this WO3 of middle discovery reduces institute Obtain the tungsten filament helix that tungsten powder is made, abnormal mystically no longer sagging after recrystallization.Subsequently, through 218 experimental verifications repeatedly, He finds to add the silicate of potassium and sodium in wolframic acid (WO3 H2O) finally, is obtained through reduction, compacting, sintering, processing etc. Tungsten filament, form quite thick grainiess after recrystallization, neither soft and sag resistance, this is earliest not sagging tungsten filament.Bai Si Discovery established not sagging tungsten filament production basis, up to now the U.S. still not sagging tungsten filament is called " 218 tungsten filament ", in honour of This great discovery of Bai Si.
The production process of doping tungsten alloy is tediously long, including Tungsten smelting, powder metallurgy base and the several main rank of plastic working Section.
It is raw material that ammonium paratungstate (APT) is generally selected in the production of doping tungsten alloy.From tungsten concentrate produce ammonium paratungstate except Outside traditional classical technique, the 1950's has carried out the research of extraction and ion exchange in the world, and China was in 70 years In generation, also uses these techniques, thus simplifying technological process, improves the response rate of tungsten.Since the sixties in 20th century, many Country all adopts blue tungsten oxide doping process to replace Tungstic anhydride. doping, thus improve doping effect in succession.The acid of tungsten powder Washing is to start the sixties in 20th century to be applied to produce, and its main purpose is to wash away unnecessary dopant in tungsten powder, micropowder With part objectionable impurities, thus improving processing characteristics, improve the high-temperature behavior of tungsten filament.From the sixties in 20th century, pass rolls Preparation method is continuously available application.Groove rolling is so that blank is passed through in the pass of the roll being rotating for a pair, in nip pressure Make section reduce under effect to extend with length.
Although only small part tungsten ore is finally made into lamp tungsten filament and similar product, tungsten and is held in technology in science The most important meaning of load is exactly the conversion to practical application for its achievement in research.The knowledge being obtained is in the new neck of powder metallurgy Domain, especially has immeasurable value in the manufacture of hard alloy.However, current tungsten alloy intensity on the market is not Foot.
Content of the invention
The technical problem to be solved in the present invention is to provide high tungsten alloy of a kind of intensity and preparation method thereof.
For solving the above problems, the present invention adopts the following technical scheme that：
A kind of tungsten alloy, including the raw material of following parts by weight proportioning：Tungsten 100-102 part, aluminum 10-12 part, copper 8-10 part, oxidation Molybdenum 1-3 part, manganese 4-6 part, vanadium boride 1-3 part, Dineodymium trioxide 2-4 part, stannum 1-3 part, dysprosia 1-3 part, praseodymium oxide 2-4 part, oxidation Yttrium 5-7 part, chromic oxide 2-4 part, boron carbide 1-3 part, titanium dioxide 6-8 part, carborundum 1-3 part and graphite powder 1-3 part.
Further, including the raw material of following parts by weight proportioning：102 parts of tungsten, 10 parts of aluminum, 8 parts of copper, 1 part of molybdenum oxide, manganese 4 parts, 1 part of vanadium boride, 2 parts of Dineodymium trioxide, 1 part of stannum, 1 part of dysprosia, 2 parts of praseodymium oxide, 5 parts of yittrium oxide, 2 parts of chromic oxide, carbon Change 1 part of boron, 6 parts of titanium dioxide, 1 part of carborundum and 1 part of graphite powder.
Further, including the raw material of following parts by weight proportioning：100 parts of tungsten, 12 parts of aluminum, 10 parts of copper, 3 parts of molybdenum oxide, 6 parts of manganese, 3 parts of vanadium boride, 4 parts of Dineodymium trioxide, 3 parts of stannum, 3 parts of dysprosia, 4 parts of praseodymium oxide, 7 parts of yittrium oxide, 4 parts of chromic oxide, 3 parts of boron carbide, 8 parts of titanium dioxide, 3 parts of carborundum and 3 parts of graphite powder.
Further, including the raw material of following parts by weight proportioning：101 parts of tungsten, 11 parts of aluminum, 9 parts of copper, 2 parts of molybdenum oxide, manganese 5 parts, 2 parts of vanadium boride, 3 parts of Dineodymium trioxide, 2 parts of stannum, 2 parts of dysprosia, 3 parts of praseodymium oxide, 6 parts of yittrium oxide, 3 parts of chromic oxide, carbon Change 2 parts of boron, 7 parts of titanium dioxide, 2 parts of carborundum and 2 parts of graphite powder.
The invention solves the problems that another technical problem be that a kind of preparation method of tungsten alloy is provided, comprise the following steps：
1）Tungsten 100-102 part, aluminum 10-12 part, copper 8-10 part, molybdenum oxide 1-3 part are poured into Metal Melting together with manganese 4-6 part In stove, it is then heated to 1100 DEG C, be stirred after all raw materials are completely melt, prepared liquid metals, standby；
2）By vanadium boride 1-3 part, Dineodymium trioxide 2-4 part, stannum 1-3 part, dysprosia 1-3 part, praseodymium oxide 2-4 part, yittrium oxide 5-7 part, Chromic oxide 2-4 part, boron carbide 1-3 part, titanium dioxide 6-8 part, carborundum 1-3 part are poured into step together with graphite powder 1-3 part Rapid 1）In prepared liquid mixing metal, and continue to heat 10 minutes, be sufficiently stirred for, prepared mixing liquid metal, standby；
3）By step 2）Prepared mixing liquid metal is poured in die casting machine and carries out die casting, obtains final product tungsten alloy.
The invention has the beneficial effects as follows：By being added with the material containing rare earth element such as dysprosia, praseodymium oxide, yittrium oxide Tungsten is modified so that the phase structure of tungsten and microstructure all change a lot, and with the addition of chromic oxide and Boron carbide is strengthened further so that finished product has outstanding intensity.
Specific embodiment
Embodiment 1：
A kind of tungsten alloy, including the raw material of following parts by weight proportioning：102 parts of tungsten, 10 parts of aluminum, 8 parts of copper, 1 part of molybdenum oxide, manganese 4 Part, 1 part of vanadium boride, 2 parts of Dineodymium trioxide, 1 part of stannum, 1 part of dysprosia, 2 parts of praseodymium oxide, 5 parts of yittrium oxide, 2 parts of chromic oxide, carbonization 1 part of boron, 6 parts of titanium dioxide, 1 part of carborundum and 1 part of graphite powder.
A kind of preparation method of tungsten alloy comprises the following steps：
1）To be poured in metal smelting-furnace together with 102 parts of tungsten, 10 parts of aluminum, 8 parts of copper, 4 parts of 1 part of molybdenum oxide and manganese, then heat To 1100 DEG C, it is stirred after all raw materials are completely melt, prepared liquid metals, standby；
2）By 1 part of vanadium boride, 2 parts of Dineodymium trioxide, 1 part of stannum, 1 part of dysprosia, 2 parts of praseodymium oxide, 5 parts of yittrium oxide, chromic oxide 2 It is poured into step 1 together with part, 1 part of boron carbide, 6 parts of titanium dioxide, 1 part of 1 part of carborundum and graphite powder）Prepared liquid mixing metal In, and continue to heat 10 minutes, it is sufficiently stirred for, prepared mixing liquid metal, standby；
3）By step 2）Prepared mixing liquid metal is poured in die casting machine and carries out die casting, obtains final product tungsten alloy.
Embodiment 2：
A kind of tungsten alloy, including the raw material of following parts by weight proportioning：100 parts of tungsten, 12 parts of aluminum, 10 parts of copper, 3 parts of molybdenum oxide, manganese 6 Part, 3 parts of vanadium boride, 4 parts of Dineodymium trioxide, 3 parts of stannum, 3 parts of dysprosia, 4 parts of praseodymium oxide, 7 parts of yittrium oxide, 4 parts of chromic oxide, carbonization 3 parts of boron, 8 parts of titanium dioxide, 3 parts of carborundum and 3 parts of graphite powder.
A kind of preparation method of tungsten alloy, comprises the following steps：
1）To be poured in metal smelting-furnace together with 100 parts of tungsten, 12 parts of aluminum, 10 parts of copper, 6 parts of 3 parts of molybdenum oxide and manganese, then heat To 1100 DEG C, it is stirred after all raw materials are completely melt, prepared liquid metals, standby；
2）By 3 parts of vanadium boride, 4 parts of Dineodymium trioxide, 3 parts of stannum, 3 parts of dysprosia, 4 parts of praseodymium oxide, 7 parts of yittrium oxide, chromic oxide 4 It is poured into step 1 together with part, 3 parts of boron carbide, 8 parts of titanium dioxide, 3 parts of 3 parts of carborundum and graphite powder）Prepared liquid mixing metal In, and continue to heat 10 minutes, it is sufficiently stirred for, prepared mixing liquid metal, standby；
3）By step 2）Prepared mixing liquid metal is poured in die casting machine and carries out die casting, obtains final product tungsten alloy.
Embodiment 3：
A kind of tungsten alloy, including the raw material of following parts by weight proportioning：101 parts of tungsten, 11 parts of aluminum, 9 parts of copper, 2 parts of molybdenum oxide, manganese 5 Part, 2 parts of vanadium boride, 3 parts of Dineodymium trioxide, 2 parts of stannum, 2 parts of dysprosia, 3 parts of praseodymium oxide, 6 parts of yittrium oxide, 3 parts of chromic oxide, carbonization 2 parts of boron, 7 parts of titanium dioxide, 2 parts of carborundum and 2 parts of graphite powder.
A kind of preparation method of tungsten alloy, comprises the following steps：
1）To be poured in metal smelting-furnace together with 101 parts of tungsten, 11 parts of aluminum, 9 parts of copper, 5 parts of 2 parts of molybdenum oxide and manganese, then heat To 1100 DEG C, it is stirred after all raw materials are completely melt, prepared liquid metals, standby；
2）By 2 parts of vanadium boride, 3 parts of Dineodymium trioxide, 2 parts of stannum, 2 parts of dysprosia, 3 parts of praseodymium oxide, 6 parts of yittrium oxide, chromic oxide 3 It is poured into step 1 together with part, 2 parts of boron carbide, 7 parts of titanium dioxide, 2 parts of 2 parts of carborundum and graphite powder）Prepared liquid mixing metal In, and continue to heat 10 minutes, it is sufficiently stirred for, prepared mixing liquid metal, standby；
3）By step 2）Prepared mixing liquid metal is poured in die casting machine and carries out die casting, obtains final product tungsten alloy.
Experimental example
Using the tungsten alloy of the present invention as experimental group, existing tungsten alloy carries out control experiment as a control group, and concrete outcome is such as Shown in following table：
By checking to 2 groups of experiments, the tungsten alloy of the present invention hardness and pressure resistance compared with existing common tungsten alloy Degree is high.
The invention has the beneficial effects as follows：By being added with the material containing rare earth element such as dysprosia, praseodymium oxide, yittrium oxide Tungsten is modified so that the phase structure of tungsten and microstructure all change a lot, and with the addition of chromic oxide and Boron carbide is strengthened further so that finished product has outstanding intensity.
The above, the only specific embodiment of the present invention, but protection scope of the present invention is not limited thereto, and any The change or replacement expected without creative work, all should cover within the scope of the present invention.

Claims (5)

1. a kind of tungsten alloy is it is characterised in that include the raw material of following parts by weight proportioning：Tungsten 100-102 part, aluminum 10-12 part, Copper 8-10 part, molybdenum oxide 1-3 part, manganese 4-6 part, vanadium boride 1-3 part, Dineodymium trioxide 2-4 part, stannum 1-3 part, dysprosia 1-3 part, oxidation Praseodymium 2-4 part, yittrium oxide 5-7 part, chromic oxide 2-4 part, boron carbide 1-3 part, titanium dioxide 6-8 part, carborundum 1-3 part and graphite Powder 1-3 part.
2. as claimed in claim 1 a kind of tungsten alloy it is characterised in that include following parts by weight proportioning raw material：Tungsten 102 Part, 10 parts of aluminum, 8 parts of copper, 1 part of molybdenum oxide, 4 parts of manganese, 1 part of vanadium boride, 2 parts of Dineodymium trioxide, 1 part of stannum, 1 part of dysprosia, praseodymium oxide 2 Part, 5 parts of yittrium oxide, 2 parts of chromic oxide, 1 part of boron carbide, 6 parts of titanium dioxide, 1 part of carborundum and 1 part of graphite powder.
3. as claimed in claim 1 a kind of tungsten alloy it is characterised in that include following parts by weight proportioning raw material：Tungsten 100 Part, 12 parts of aluminum, 10 parts of copper, 3 parts of molybdenum oxide, 6 parts of manganese, 3 parts of vanadium boride, 4 parts of Dineodymium trioxide, 3 parts of stannum, 3 parts of dysprosia, praseodymium oxide 4 Part, 7 parts of yittrium oxide, 4 parts of chromic oxide, 3 parts of boron carbide, 8 parts of titanium dioxide, 3 parts of carborundum and 3 parts of graphite powder.
4. as claimed in claim 1 a kind of tungsten alloy it is characterised in that include following parts by weight proportioning raw material：Tungsten 101 Part, 11 parts of aluminum, 9 parts of copper, 2 parts of molybdenum oxide, 5 parts of manganese, 2 parts of vanadium boride, 3 parts of Dineodymium trioxide, 2 parts of stannum, 2 parts of dysprosia, praseodymium oxide 3 Part, 6 parts of yittrium oxide, 3 parts of chromic oxide, 2 parts of boron carbide, 7 parts of titanium dioxide, 2 parts of carborundum and 2 parts of graphite powder.
5. a kind of preparation method of tungsten alloy is it is characterised in that comprise the following steps：
1）Tungsten 100-102 part, aluminum 10-12 part, copper 8-10 part, molybdenum oxide 1-3 part are poured into Metal Melting together with manganese 4-6 part In stove, it is then heated to 1100 DEG C, be stirred after all raw materials are completely melt, prepared liquid metals, standby；
2）By vanadium boride 1-3 part, Dineodymium trioxide 2-4 part, stannum 1-3 part, dysprosia 1-3 part, praseodymium oxide 2-4 part, yittrium oxide 5-7 part, Chromic oxide 2-4 part, boron carbide 1-3 part, titanium dioxide 6-8 part, carborundum 1-3 part are poured into step together with graphite powder 1-3 part Rapid 1）In prepared liquid mixing metal, and continue to heat 10 minutes, be sufficiently stirred for, prepared mixing liquid metal, standby；
3）By step 2）Prepared mixing liquid metal is poured in die casting machine and carries out die casting, obtains final product tungsten alloy.
CN201610938274.4A 2016-10-25 2016-10-25 Tungsten alloy and preparation method thereof Pending CN106399788A (en)

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