CN109306421B - A kind of anti-erosion molybdenum alloy electrode and its manufacturing method - Google Patents
A kind of anti-erosion molybdenum alloy electrode and its manufacturing method Download PDFInfo
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- CN109306421B CN109306421B CN201811091063.7A CN201811091063A CN109306421B CN 109306421 B CN109306421 B CN 109306421B CN 201811091063 A CN201811091063 A CN 201811091063A CN 109306421 B CN109306421 B CN 109306421B
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- 229910001182 Mo alloy Inorganic materials 0.000 title claims abstract description 54
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 27
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims abstract description 22
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000498 ball milling Methods 0.000 claims abstract description 20
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000956 alloy Substances 0.000 claims abstract description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 15
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 15
- 229910052796 boron Inorganic materials 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000013078 crystal Substances 0.000 claims abstract description 7
- 239000012535 impurity Substances 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 51
- 229910052750 molybdenum Inorganic materials 0.000 claims description 49
- 239000011733 molybdenum Substances 0.000 claims description 49
- 239000000843 powder Substances 0.000 claims description 45
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 34
- 238000005245 sintering Methods 0.000 claims description 24
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 230000009467 reduction Effects 0.000 claims description 15
- 238000000137 annealing Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 10
- 239000010935 stainless steel Substances 0.000 claims description 10
- 229910001220 stainless steel Inorganic materials 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 238000005242 forging Methods 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- 239000011863 silicon-based powder Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000003595 mist Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 4
- 238000004886 process control Methods 0.000 claims description 3
- 238000005056 compaction Methods 0.000 claims description 2
- 238000012369 In process control Methods 0.000 claims 1
- 239000003292 glue Substances 0.000 claims 1
- 238000010965 in-process control Methods 0.000 claims 1
- 230000007797 corrosion Effects 0.000 abstract description 29
- 238000005260 corrosion Methods 0.000 abstract description 29
- 239000011521 glass Substances 0.000 abstract description 29
- 238000001953 recrystallisation Methods 0.000 abstract description 9
- 229910045601 alloy Inorganic materials 0.000 abstract description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract description 2
- 229910008423 Si—B Inorganic materials 0.000 abstract description 2
- 229920001296 polysiloxane Polymers 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 18
- 239000000463 material Substances 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000005611 electricity Effects 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 229910006295 Si—Mo Inorganic materials 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000000156 glass melt Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
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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
-
- B22F1/0003—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/02—Compacting only
- B22F3/04—Compacting only by applying fluid pressure, e.g. by cold isostatic pressing [CIP]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/24—After-treatment of workpieces or articles
- B22F3/26—Impregnating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
- B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/02—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture in electric furnaces, e.g. by dielectric heating
- C03B5/027—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture in electric furnaces, e.g. by dielectric heating by passing an electric current between electrodes immersed in the glass bath, i.e. by direct resistance heating
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/045—Alloys based on refractory metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/24—After-treatment of workpieces or articles
- B22F2003/248—Thermal after-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
Abstract
The invention discloses a kind of anti-erosion molybdenum alloy electrode and its manufacturing methods, it is made up of solid-liquid doping and the doping of multielement ball milling, recrystallization temperature is higher than 1300 DEG C, and microstructure is uniformly having a size of 20~70 μm of crystal grain, and by forming following weight percentage components: ZrO23~5wt%, 0.8~1.2wt% of Si, 0.1~0.5wt% of B, GeO20.001~3wt%, SnO20.001~3wt%, Bi2O30.001~3wt%, W 0~5wt% and Al2O30~4wt%, surplus are Mo and the impurity that can not be rejected.The present invention can be good at guaranteeing that alloy has good corrosion resistance, high recrystallization temperature and high-temperature behavior by the reasonably content of control zirconium oxide and the proportion of the silicone content of Mo-Si-B alloy and boron content, while have good processing performance again.In addition, mixing other specific aim microelements in molybdenum alloy electrode of the present invention, also to improve it for the erosion-resisting characteristics of different glass liquid.
Description
Technical field
The invention belongs to technical field of alloy material, and in particular to a kind of anti-erosion molybdenum alloy electrode and its manufacturing method.
Background technique
Since application development of the Electric Melting Technology in glass furnace is swift and violent, to heating element-electrode of glass electric melting furnace
Demand it is also growing day by day.For molybdenum as electrode preferred material, importance is also self-evident.Although molybdenum has
There are many excellent performance, for example, high intensity, high rigidity, high temperature resistant, with the wellability of glass metal by force and to carry current density big.
But with the development of science and technology, the requirement to glass finished-product is also higher and higher, this also proposed more the high-temperature behavior of molybdenum
Carry out harsher requirement.It will be apparent that pure molybdenum can be increasingly difficult to fully meet the operating condition of such harshness.In practical electric smelting
In the application of kiln, the service life of domestic pure molybdenum electrode is very limited, and most short-lived can only survive 2-3 months, grows a bit
Also there was only 3 years or so time.Compared to some kilns for the furnace life of 8-10, the growing space of electrode life
It is also very big.
Summary of the invention
It is an object of the invention to overcome prior art defect, a kind of anti-erosion molybdenum alloy electrode is provided.
Another object of the present invention is to provide the preparation methods of above-mentioned anti-erosion molybdenum alloy electrode.
Technical scheme is as follows:
A kind of anti-erosion molybdenum alloy electrode is made up of solid-liquid doping and the doping of multielement ball milling, and recrystallization temperature is higher than
1300 DEG C, microstructure is uniformly having a size of 20~70 μm of crystal grain, and by forming following weight percentage components:
ZrO23~5wt%, 0.8~1.2wt% of Si, 0.1~0.5wt% of B, GeO20.001~3wt%, SnO20.001~3wt%,
Bi2O30.001~3wt%, W 0~5wt% and Al2O30~4wt%, surplus are Mo and the impurity that can not be rejected.
In a preferred embodiment of the invention, by forming following weight percentage components: ZrO23~5wt%,
0.8~1.2wt% of Si, 0.1~0.5wt% of B, GeO20.001~3wt%, SnO20.001~3wt%, Bi2O30.001~
3wt%, W 3~5wt% and Al2O31~4wt%, surplus are Mo and the impurity that can not be rejected.
In a preferred embodiment of the invention, by forming following weight percentage components: ZrO23~5wt%,
0.8~1.2wt% of Si, 0.1~0.5wt% of B, GeO20.001~3wt%, SnO20.001~3wt%, Bi2O30.001~
3wt% and Al2O31~4wt%, surplus are Mo and the impurity that can not be rejected.
The manufacturing method of above-mentioned anti-erosion molybdenum alloy electrode, includes the following steps:
(1) molybdenum raw material is weighed, which is high-purity molybdenum trioxide by the molybdenum dioxide of primary reduction preparation, by the dioxy
Change the weight that Mo weight contained by molybdenum calculates institute's zirconium oxide to be added, be converted into the quality of required zirconium nitrate, by the zirconium nitrate and
After deionized water mixing, heating stirring is made it completely dissolved, and obtains zirconium nitrate solution；
(2) by weighed molybdenum dioxide be placed in stainless steel bipyramid vacuum atomizing doping pot in, revolving speed be adjusted to 26~27HZ into
Row rotation；Nitrogen buffer gas is sprayed with the pressure of 0.25MPa~0.45MPa into stainless steel bipyramid vacuum atomizing doping pot
Above-mentioned 25~the 35min of zirconium nitrate solution for entering atomization, then opens steam valve, and steam pressure is adjusted to 0.12-0.2MPa, carries out
Vacuum drying continues 2.5~3.5h, obtains MoO2-ZrO2Powder；
(3) by above-mentioned MoO2-ZrO2Powder is sent into reduction furnace, in a hydrogen atmosphere, 950~1100 DEG C of Yu Wendu reduction 6
~9h, it is cooling, it is sieved containing ZrO2Doped molybdenum；
(4) by weighed W powder, Si powder, B powder, Al2O3Powder, GeO2Powder, SnO2Powder, Bi2O3Powder, step (3) resulting doping
Ball milling mixing is uniform in molybdenum powder and process control agent addition ball mill, is sieved after dry, obtains doping powder；
(5) above-mentioned doping powder is subjected to cold isostatic compaction, obtains blank；
(6) above-mentioned blank is sintered, sintering molybdenum alloy material is obtained after furnace cooling；
(7) it by after the heating of above-mentioned sintering molybdenum alloy material, first send to quick forging machine and forges, after being made annealing treatment, be then sent through
Finish forge is carried out in swager, is subsequently placed in vacuum sintering furnace and carries out Stress relieving annealing, obtains the anti-erosion molybdenum alloy electrode.
In a preferred embodiment of the invention, the step (5) are as follows: above-mentioned doping powder is added in gum cover and rams
Real, seal rubber sleeve after air, is then forced into 3~5min of pressure maintaining after 160~180MPa, is down to normal pressure later in abstraction gum cover,
Obtain blank；
In a preferred embodiment of the invention, the sintering temperature in the step (6) is 1950~2050 DEG C, is burnt
The knot time is 10~12h.
In a preferred embodiment of the invention, the temperature of the heating in the step (7) is 1500~1600 DEG C.
In a preferred embodiment of the invention, the temperature of the Stress relieving annealing in the step (7) be 1000~
1100 DEG C, the time is 1~3h.
It is further preferred that the process control agent is deionized water.
The beneficial effects of the present invention are:
1, contain ZrO in the material composition of anti-erosion molybdenum alloy electrode of the invention2, Si and B also contain W, Al2O3,
GeO2, SnO2And Bi2O3Therein several, remaining is molybdenum, the present invention by reasonably control zirconium oxide content and
The silicone content of Mo-Si-B alloy and the proportion of boron content can be good at guaranteeing that alloy has good corrosion resistance, high
Recrystallization temperature and high-temperature behavior, while having good processing performance again.In addition, also mixing other in molybdenum alloy electrode of the present invention
Specific aim microelement, to improve it for the erosion-resisting characteristics of different glass liquid.
2, the present invention is adulterated by solid-liquid doping and multielement ball milling, makes doping oxide (ZrO2, Al2O3, GeO2,
SnO2And Bi2O3It is one such or several) it is evenly distributed on the crystal grain and grain boundaries of molybdenum base material.Since electrode is in reality
Main failure mechanism in the electric melting furnace use process of border is grain-boundary attack, and subtle second in dipping molybdenum alloy electrode is mutually effective
Ground is gathered in grain boundaries, can achieve hinder low-melting compound grain boundaries generate, thus inhibit crystal boundary coarse and glass at
The infiltration divided, effectively delays erosion of the glass metal for crystal boundary.
3, the manufacturing method of the present invention is easily controllable, easy to operate, can prepare difference according to different glass liquid composition and match
Side, plays the performance of each element, this molybdenum alloy electrode is made to possess better high-temperature behavior, higher recrystallization temperature, more preferably
Corrosion-resistant property.
4, the present invention passes through the technique of controlled forge process and annealing, makes its tissue of anti-erosion molybdenum alloy material from core to surface
All highly uniform, compactness is good.
5, the present invention makes the uniform big crystal grain of the microstructure of electrode by the control of annealing process, crystallite dimension
Range about 20~70um can increase it in the creep-resistant property being melted in glass process, this dot characteristics can significantly extend
Service life of the horizontal intercalative electrode in electric melting process.
6, for anti-erosion molybdenum alloy electrode of the invention compared with pure molybdenum electrode, service life improves 50% than pure molybdenum electrode,
Possess higher crystallization temperature, better mechanical behavior under high temperature, more preferably anti-glass metal erosion performance.
Detailed description of the invention
Fig. 1 is 500 times of metallographic structure figures after the corrosion of pure molybdenum electrode in the comparison corrosion test of the embodiment of the present invention 1.
Fig. 2 is 500 times of metallographic groups after the corrosion of anti-erosion molybdenum alloy electrode in the comparison corrosion test of the embodiment of the present invention 1
Knit figure.
Fig. 3 is 500 times of metallographic structure figures after the corrosion of pure molybdenum electrode in the comparison corrosion test of the embodiment of the present invention 2.
Fig. 4 is 500 times of metallographic groups after the corrosion of anti-erosion molybdenum alloy electrode in the comparison corrosion test of the embodiment of the present invention 2
Knit figure.
Fig. 5 is 500 times of metallographic structure figures after the corrosion of pure molybdenum electrode in the comparison corrosion test of the embodiment of the present invention 3.
Fig. 6 is 500 times of metallographic groups after the corrosion of anti-erosion molybdenum alloy electrode in the comparison corrosion test of the embodiment of the present invention 3
Knit figure.
Specific embodiment
Technical solution of the present invention is further explained and described below by way of specific embodiment combination attached drawing.
Embodiment 1
(1) 80kg molybdenum raw material is weighed, which is high-purity molybdenum trioxide by the molybdenum dioxide of primary reduction preparation, is weighed
After 6kg zirconium nitrate is mixed with appropriate amount of deionized water, heating stirring is made it completely dissolved, then plus deionized water be diluted to 8L, obtain
Zirconium nitrate solution；
(2) weighed molybdenum dioxide is placed in stainless steel bipyramid vacuum atomizing doping pot, revolving speed is adjusted to 27HZ and is revolved
Turn；Nitrogen buffer gas sprays into mist into stainless steel bipyramid vacuum atomizing doping pot with the pressure of 0.25MPa~0.45MPa
The above-mentioned zirconium nitrate solution 30min changed, then opens steam valve, and steam pressure is adjusted to 0.12~0.2MPa, it is dry to carry out vacuum
It is dry, continue 3h, obtains MoO2-ZrO2Powder；
(3) by above-mentioned MoO2-ZrO2Powder is sent into reduction furnace, in a hydrogen atmosphere, 950 DEG C of 6~9h of reduction of Yu Wendu,
It is cooling, it is sieved containing ZrO2Doped molybdenum；
It (4) will be according to W 3wt%, Si 0.8wt%, B 0.1wt%, Al2O31wt%, GeO20.01wt%,
SnO20.01wt% and Bi2O3The weighed W powder of the ratio of 0.01wt%, Si powder, B powder, Al2O3Powder, GeO2Powder, SnO2Powder, Bi2O3
Ball milling mixing is uniform in powder, the resulting doped molybdenum of step (3) and deionized water addition ball mill, is sieved after 60 DEG C of dry 6h,
Obtaining average grain diameter is 2~10um doping powder；The additional amount of deionized water is the 4wt% of the total amount of rest materials, ball milling
It is 6h that time, which is the time of ball milling, and molybdenum ball material mass ratio is 4: 1, ball milling speed 300r/min, ball milling under nitrogen protection into
Row；
(5) above-mentioned doping powder is added in gum cover and is tamped, seal rubber sleeve after air, is then forced into abstraction gum cover
3~5min of pressure maintaining after 160~180MPa, is down to normal pressure later, obtains blank；
(6) above-mentioned blank being sintered, sintering molybdenum alloy material is obtained after furnace cooling, sintering temperature is 1950 DEG C,
Sintering time is 10h；
(7) it after above-mentioned sintering molybdenum alloy material being heated to 1500 DEG C under hydrogen protection, first send to quick forging machine and forges, always
Deflection is 50%, after being made annealing treatment, is then sent through in swager and carries out finish forge, total deformation 20%, is subsequently placed in true
Stress relieving annealing (temperature is 1000~1100 DEG C, and the time is 1~3h) is carried out in empty sintering furnace, obtains the anti-erosion molybdenum alloy
Electrode；The temperature of above-mentioned forging and finish forge is not less than 1450 DEG C.
Anti-erosion molybdenum alloy electrode manufactured in the present embodiment compares corrosion with pure molybdenum electrode in experimental glass kiln
Test, temperature are 1350 DEG C, and glass metal is high-boron-silicon glass, and the test period is heat preservation 2 weeks, current density 1.1A/cm2Root
According to ex-post analysis, molybdenum alloy electrode recrystallization temperature is higher than 1350 DEG C, and resistance to glass attack performance is good, and molybdenum closes under identical corrosive environment
The pure molybdenum of the volume ratio that gold is corroded few about 50%, therefore its service life improves 50% or more than pure molybdenum electrode, and will not be dirty
Contaminate glass metal.
The concrete outcome of above-mentioned comparison corrosion test is as depicted in figs. 1 and 2, anti-erosion molybdenum alloy electricity manufactured in the present embodiment
The length of pole is 78.71mm, density 9.92g/cm3, original volume 16.21cm3, volume is 14.58cm after corrosion3, volume subtracts
Few rate is 10.06%；And the length of pure molybdenum electrode as a comparison is 79.04mm, density 10.15g/cm3, original volume is
16.28cm3, volume is 12.71cm after corrosion3, volume slip is 21.93%.
Embodiment 2
(1) 80kg molybdenum raw material is weighed, which is high-purity molybdenum trioxide by the molybdenum dioxide of primary reduction preparation, is weighed
After 9kg zirconium nitrate is mixed with appropriate amount of deionized water, heating stirring is made it completely dissolved, then plus deionized water be diluted to 8L, obtain
Zirconium nitrate solution；
(2) weighed molybdenum dioxide is placed in stainless steel bipyramid vacuum atomizing doping pot, revolving speed is adjusted to 27HZ and is revolved
Turn；Nitrogen buffer gas sprays into mist into stainless steel bipyramid vacuum atomizing doping pot with the pressure of 0.25MPa~0.45MPa
The above-mentioned zirconium nitrate solution 30min changed, then opens steam valve, and steam pressure is adjusted to 0.12~0.2MPa, it is dry to carry out vacuum
It is dry, continue 3h, obtains MoO2-ZrO2Powder；
(3) by above-mentioned MoO2-ZrO2Powder is sent into reduction furnace, and in a hydrogen atmosphere, 1000 DEG C of Yu Wendu reduction 7h is cold
But, it is sieved containing ZrO2Doped molybdenum；
It (4) will be according to Si 1.0wt%, B 0.3wt%, Al2O30.5wt%, GeO20.05wt%, SnO20.05wt% and
Bi2O3The weighed Si powder of the ratio of 0.05wt%, B powder, Al2O3Powder, GeO2Powder, SnO2Powder, Bi2O3Powder, step (3) is resulting mixes
Miscellaneous molybdenum powder and deionized water are added in ball mill that ball milling mixing is uniform, are sieved after 60 DEG C of dry 6h, obtain average grain diameter be 2~
10um adulterates powder；The additional amount of deionized water is the 4wt% of the total amount of rest materials, and the time of ball milling is the time of ball milling to be
6h, molybdenum ball material mass ratio are 4: 1, and ball milling speed 300r/min, ball milling carries out under nitrogen protection；
(5) above-mentioned doping powder is added in gum cover and is tamped, seal rubber sleeve after air, is then forced into abstraction gum cover
3~5min of pressure maintaining after 160~180MPa, is down to normal pressure later, obtains blank；
(6) above-mentioned blank being sintered, sintering molybdenum alloy material is obtained after furnace cooling, sintering temperature is 2000 DEG C,
Sintering time is 11h；
(7) it after above-mentioned sintering molybdenum alloy material being heated to 1500 DEG C under hydrogen protection, first send to quick forging machine and forges, always
Deflection is 50%, after being made annealing treatment, is then sent through in swager and carries out finish forge, total deformation 20%, is subsequently placed in true
Stress relieving annealing (temperature is 1000~1100 DEG C, and the time is 1~3h) is carried out in empty sintering furnace, obtains the anti-erosion molybdenum alloy
Electrode；The temperature of above-mentioned forging and finish forge is not less than 1450 DEG C.
Anti-erosion molybdenum alloy electrode manufactured in the present embodiment compares corrosion with pure molybdenum electrode in experimental glass kiln
Test, temperature are 1400 DEG C, and glass metal is soda-lime glass, and the test period is heat preservation 2 weeks, current density 0.8A/cm2Basis
Ex-post analysis, molybdenum alloy electrode recrystallization temperature are higher than 1400 DEG C, and resistance to glass attack performance is good, molybdenum alloy under identical corrosive environment
The pure molybdenum of the volume ratio being corroded few about 30%, therefore its service life improves 30% or more than pure molybdenum electrode, and will not pollute
Glass metal.
The concrete outcome of above-mentioned comparison corrosion test is as shown in Figure 3 and Figure 4, anti-erosion molybdenum alloy electricity manufactured in the present embodiment
The length of pole is 78.27mm, density 9.91g/cm3, original volume 16.32cm3, volume is 14.68cm after corrosion3, volume subtracts
Few rate is 10.05%；And the length of pure molybdenum electrode as a comparison is 77.94mm, density 10.14g/cm3, original volume is
16.29cm3, volume is 14.01cm after corrosion3, volume slip is 14.00%.
Embodiment 3
(1) 80kg molybdenum raw material is weighed, which is high-purity molybdenum trioxide by the molybdenum dioxide of primary reduction preparation, is weighed
After 11kg zirconium nitrate is mixed with appropriate amount of deionized water, heating stirring is made it completely dissolved, then plus deionized water be diluted to 8L, obtain
Zirconium nitrate solution；
(2) weighed molybdenum dioxide is placed in stainless steel bipyramid vacuum atomizing doping pot, revolving speed is adjusted to 27HZ and is revolved
Turn；Nitrogen buffer gas sprays into mist into stainless steel bipyramid vacuum atomizing doping pot with the pressure of 0.25MPa~0.45MPa
The above-mentioned zirconium nitrate solution 30min changed, then opens steam valve, and steam pressure is adjusted to 0.12~0.2MPa, it is dry to carry out vacuum
It is dry, continue 3h, obtains MoO2-ZrO2Powder；
(3) by above-mentioned MoO2-ZrO2Powder is sent into reduction furnace, and in a hydrogen atmosphere, 1100 DEG C of Yu Wendu reduction 9h is cold
But, it is sieved containing ZrO2Doped molybdenum；
It (4) will be according to Si 1.2wt%, B 0.5wt%, GeO20.1wt%, SnO20.1wt% and Bi2O30.1wt%'s
The weighed Si powder of ratio, B powder, GeO2Powder, SnO2Powder, Bi2O3Ball is added in powder, the resulting doped molybdenum of step (3) and deionized water
Ball milling mixing is uniform in grinding machine, is sieved after 60 DEG C of dry 6h, and obtaining average grain diameter is 2~10um doping powder；Deionized water
Additional amount is the 4wt% of the total amount of rest materials, and it is 6h that the time of ball milling, which is the time of ball milling, and molybdenum ball material mass ratio is 4: 1, ball
Mill rate is 300r/min, and ball milling carries out under nitrogen protection；
(5) above-mentioned doping powder is added in gum cover and is tamped, seal rubber sleeve after air, is then forced into abstraction gum cover
3~5min of pressure maintaining after 160~180MPa, is down to normal pressure later, obtains blank；
(6) above-mentioned blank being sintered, sintering molybdenum alloy material is obtained after furnace cooling, sintering temperature is 2050 DEG C,
Sintering time is 12h；
(7) it after above-mentioned sintering molybdenum alloy material being heated to 1500 DEG C under hydrogen protection, first send to quick forging machine and forges, always
Deflection is 50%, after being made annealing treatment, is then sent through in swager and carries out finish forge, total deformation 20%, is subsequently placed in true
Stress relieving annealing (temperature is 1000~1100 DEG C, and the time is 1~3h) is carried out in empty sintering furnace, obtains the anti-erosion molybdenum alloy
Electrode；The temperature of above-mentioned forging and finish forge is not less than 1450 DEG C.
Anti-erosion molybdenum alloy electrode manufactured in the present embodiment compares corrosion with pure molybdenum electrode in experimental glass kiln
Test, temperature are 1300 DEG C, and glass metal is glass fibre raw material, and the test period is heat preservation 2 weeks, current density 0.5A/cm2.
According to ex-post analysis, molybdenum alloy electrode recrystallization temperature is higher than 1300 DEG C, and resistance to glass attack performance is good, molybdenum under identical corrosive environment
The pure molybdenum of the volume ratio that alloy is corroded few about 20%, therefore its service life improves 20% or more than pure molybdenum electrode, and will not
Pollute glass metal.
The concrete outcome of above-mentioned comparison corrosion test is as shown in Figure 5 and Figure 6, anti-erosion molybdenum alloy electricity manufactured in the present embodiment
The length of pole is 78.28mm, density 9.91g/cm3, original volume 16.46cm3, volume is 15.15cm after corrosion3, volume subtracts
Few rate is 9.30%；And the length of pure molybdenum electrode as a comparison is 78.34mm, density 9.95g/cm3, original volume is
16.51cm3, volume is 14.81cm after corrosion3, volume slip is 10.30%.
Physico-chemical analysis, the inspection of microcosmic metallographic have been carried out to finished product molybdenum alloy electrode prepared by the embodiment of the present invention 1 to embodiment 3
Survey, scanning electron microscope, the erosion-resisting characteristics in glass melts.By being tested above it is found that the made molybdenum of above-described embodiment 1 to 3 closes
99% or more, molybdenum alloy even grain size improves the recrystallization temperature of molybdenum alloy and makes the relative density of golden material
Use the service life.Comparison corrosion test has been carried out to pure molybdenum electrode and molybdenum alloy electrode of the invention, by same corrosive environment,
It is compared by corrosion condition, it is possible thereby to obtain the service life of molybdenum alloy electrode indirectly.Specifically: utilize small-sized reality
The electric smelting environment for testing glass furnace simulation Real Glass kiln is heated to the glass powder of 900 DEG C of fusing 50KG first with Si-Mo rod,
Horizontal four consistent molybdenum electrodes of size (wherein one is pure molybdenum electrode) of inserting carry out (the different vitrifying of electrified regulation glass metal again
Study point), it is continuously heating to 1300 DEG C~1400 DEG C and starts timing, heat preservation closed kiln, furnace cooling after 2 weeks.After cooling,
It breaks glass into pieces, takes out electrode, the glass dregs of electrode surface are removed, and measure its volume change.Testing result surface, molybdenum alloy
Few the 20~50% of the pure molybdenum electrode loss of the volume ratio that electrode is etched, therefore molybdenum alloy electrode of the invention is shown well
Erosion-resisting characteristics, the service life of purer molybdenum electrode improves 20~50% or more.
The foregoing is only a preferred embodiment of the present invention, the range that the present invention that therefore, it cannot be limited according to is implemented, i.e.,
Equivalent changes and modifications made in accordance with the scope of the invention and the contents of the specification should still be within the scope of the present invention.
Claims (9)
1. a kind of anti-erosion molybdenum alloy electrode, it is characterised in that: be made up, then tie of solid-liquid doping and the doping of multielement ball milling
Brilliant temperature is higher than 1300 DEG C, and microstructure is uniformly having a size of 20 ~ 70 μm of crystal grain, and by the group of following weight percent
It is grouped as: ZrO2 3~5wt%、Si 0.8~1.2wt%、B 0.1~0.5wt%、GeO2 0.001~3wt%、SnO2 0.001~3wt%、
Bi2O30.001 ~ 3wt%, W 0 ~ 5wt% and Al2O30 ~ 4wt%, surplus are Mo and the impurity that can not be rejected.
2. a kind of anti-erosion molybdenum alloy electrode as described in claim 1, it is characterised in that: by following weight percentage components
Composition: ZrO2 3~5wt%、Si 0.8~1.2wt%、B 0.1~0.5wt%、GeO2 0.001~3wt%、SnO2 0.001~3wt%、
Bi2O30.001 ~ 3wt%, W 3 ~ 5wt% and Al2O31 ~ 4wt%, surplus are Mo and the impurity that can not be rejected.
3. a kind of anti-erosion molybdenum alloy electrode as described in claim 1, it is characterised in that: by following weight percentage components
Composition: ZrO2 3~5wt%、Si 0.8~1.2wt%、B 0.1~0.5wt%、GeO2 0.001~3wt%、SnO2 0.001~3wt%、
Bi2O30.001 ~ 3wt% and Al2O31 ~ 4wt%, surplus are Mo and the impurity that can not be rejected.
4. the manufacturing method of anti-erosion molybdenum alloy electrode described in any claim, feature exist in a kind of claims 1 to 3
In: include the following steps:
(1) molybdenum raw material is weighed, which is high-purity molybdenum trioxide by the molybdenum dioxide of primary reduction preparation, by the molybdenum dioxide
Contained Mo weight calculates the weight of institute's zirconium oxide to be added, is converted into the quality of required zirconium nitrate, by the zirconium nitrate with go from
After sub- water mixing, heating stirring is made it completely dissolved, and obtains zirconium nitrate solution；
(2) weighed molybdenum dioxide is placed in stainless steel bipyramid vacuum atomizing doping pot, revolving speed is adjusted to 26 ~ 27 r/min progress
Rotation；Nitrogen buffer gas sprays into mist into stainless steel bipyramid vacuum atomizing doping pot with the pressure of 0.25MPa ~ 0.45MPa
Above-mentioned 25 ~ the 35min of zirconium nitrate solution changed, then opens steam valve, and steam pressure is adjusted to 0.12-0.2MPa, carries out vacuum
It is dry, continue 2.5 ~ 3.5h, obtains MoO2-ZrO2Powder；
(3) by above-mentioned MoO2-ZrO2Powder is sent into reduction furnace, in a hydrogen atmosphere, 950 ~ 1100 DEG C of 6 ~ 9h of reduction of Yu Wendu,
It is cooling, it is sieved containing ZrO2Doped molybdenum；
(4) by weighed W powder, Si powder, B powder, Al2O3Powder, GeO2Powder, SnO2Powder, Bi2O3Powder, step (3) resulting doped molybdenum
It is uniform with ball milling mixing in process control agent addition ball mill, it is sieved after dry, obtains doping powder；
(5) above-mentioned doping powder is subjected to cold isostatic compaction, obtains blank；
(6) above-mentioned blank is sintered, sintering molybdenum alloy material is obtained after furnace cooling；
(7) it by after the heating of above-mentioned sintering molybdenum alloy material, first send to quick forging machine and forges, after being made annealing treatment, be then sent through and swage
Finish forge is carried out in machine, is subsequently placed in vacuum sintering furnace and carries out Stress relieving annealing, obtains the anti-erosion molybdenum alloy electrode.
5. manufacturing method as claimed in claim 4, it is characterised in that: the step (5) are as follows: glue is added in above-mentioned doping powder
It is tamped in set, seal rubber sleeve after air, is then forced into 3 ~ 5min of pressure maintaining after 160 ~ 180MPa, is down to later often in abstraction gum cover
Pressure, obtains blank.
6. manufacturing method as claimed in claim 4, it is characterised in that: the sintering temperature in the step (6) is 1950 ~ 2050
DEG C, sintering time is 10 ~ 12h.
7. manufacturing method as claimed in claim 4, it is characterised in that: the temperature of the heating in the step (7) be 1500 ~
1600℃。
8. manufacturing method as claimed in claim 4, it is characterised in that: the temperature of the Stress relieving annealing in the step (7) is
1000 ~ 1100 DEG C, the time is 1 ~ 3h.
9. the manufacturing method as described in any claim in claim 4 to 8, it is characterised in that: the process control agent is
Deionized water.
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Effective date of registration: 20190813 Address after: 361000 Liansheng Road 339, Jimei North Road Industrial Zone, Xiamen City, Fujian Province Applicant after: Honglu Tungsten Molybdenum Industry Co., Ltd., Shiamen Applicant after: Xiamen University Address before: 361000 Liansheng Road 339, Jimei North Road Industrial Zone, Xiamen City, Fujian Province Applicant before: Honglu Tungsten Molybdenum Industry Co., Ltd., Shiamen |
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