CN105821272A - Grinding resistant molybdenum alloy material and preparation method thereof - Google Patents
Grinding resistant molybdenum alloy material and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- 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
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
- C22C32/0015—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
- C22C32/0031—Matrix based on refractory metals, W, Mo, Nb, Hf, Ta, Zr, Ti, V or alloys thereof
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Abstract
The invention provides a grinding resistant molybdenum alloy material. The grinding resistant molybdenum alloy material comprises Mo, Al2O3, Cr, Y2O3, Ti, Ni, Nb, Zr, C, Mn and B in parts by weight. The invention further provides a preparation method of the molybdenum alloy material; and the preparation method comprises the following steps: (1) ammonium tetramolybdate is prepared; (2) Al2O3/Mo mixed powder is prepared; (3) the Al2O3/Mo mixed powder, other components and a process control agent are uniformly mixed through ball milling, and are dried to obtain mixed powder; (4) a blank is obtained through cold isostatic pressing; and (5) the molybdenum alloy material is obtained through sintering under hydrogen atmosphere. Al2O3 particles and other alloy elements are uniformly distributed in a molybdenum base composite material through multielement doping and particle reinforcement, so that the molybdenum alloy brittleness is reduced, and the molybdenum base composite material is higher in wear resistance, higher in recrystallization temperature and excellent in comprehensive performance.
Description
Technical field
The invention belongs to rare metallic material processing technique field, be specifically related to a kind of wear-resistant molybdenum alloy material cut and preparation method thereof.
Background technology
Metal-base composites (MMCs) is with metal or alloy as matrix, the composite with fiber, whisker, granule etc. as reinforcement.MMCs has come out more than 40 year, and it has high specific strength, specific modulus, excellent physical property and the mechanical property such as wear-resistant, high temperature resistant so that it is become the key areas of various countries' research in new high-tech exploitation.
Molybdenum is a kind of metallic element, has fusing point high, the series of advantages such as thermal coefficient of expansion is low, but molybdenum and molybdenum alloy have black brittleness, recrystallization fragility and the shortcoming of high-temperature oxidation resistance difference, limit the use in terms of structural material of molybdenum and alloy thereof.
Aluminium oxide has high-melting-point, high rigidity and excellent chemical stability, is widely used in making various refractory brick, fire-clay crucible, high temperature resistant test apparatus and grinding agent, fire retardant, inserts etc.；But its poor toughness, it is impossible to stand the shortcomings such as bigger mechanical shock and also limit its range of application.
Utilize Mo and Al2O3Respective advantage, can make combination property and be better than pure Mo and pure Al2O3Composite, the research currently for this composite reported, but research is the most insufficient.
Summary of the invention
The technical problem to be solved is for above-mentioned the deficiencies in the prior art, it is provided that a kind of wear-resistant molybdenum alloy material cut.By multi-element doping and particle strengthening in this material, make Al2O3Granule is evenly distributed in molybdenum-base composite material, reduces molybdenum alloy fragility, makes molybdenum-base composite material obtain higher resistance to grinding performance, higher recrystallization temperature and excellent combination property.
For solving above-mentioned technical problem, the technical solution used in the present invention is: a kind of wear-resistant molybdenum alloy material cut, it is characterised in that comprise the composition of following weight portion: Mo70～72 parts, Al2O39～11 parts, Cr6～8 parts, Y2O35～8 parts, Ti3～5 parts, Ni3～4 parts, Nb2～4 parts, Zr1～3 parts, C1～2 parts, Mn1～2 parts, B0.1～0.15 part.
The above-mentioned a kind of wear-resistant molybdenum alloy material cut, it is characterised in that comprise the composition of following weight portion: Mo71 part, Al2O310 parts, Cr7 part, Y2O36 parts, Ti4 part, Ni3.5 part, Nb3 part, Zr2 part, C1.5 part, Mn1.5 part, B0.12 part.
It addition, present invention also offers a kind of method preparing the above-mentioned wear-resistant molybdenum alloy material cut, it is characterised in that the method comprises the following steps:
Step one, prepare ammonium molybdate solution according to the component requirements that need to prepare molybdenum alloy material, then ammonium molybdate solution is carried out the heavy crystallization of acid, sequentially passes through vacuum filtration, washing and dried afterwards, obtain ammonium tetramolybdate；
Step 2, according to need to prepare molybdenum alloy material component requirements prepare aluminum nitrate solution, again ammonium tetramolybdate described in step one is joined mix homogeneously in aluminum nitrate solution, and use citric acid that the pH value of mixed liquor is adjusted to 1.5～2.0, colloidal sol is obtained after standing, then after colloidal sol being dried and pulverizes, under conditions of temperature is 560 DEG C～570 DEG C, calcines 30min～60min, obtains Al2O3/ molybdenum oxide mixed-powder, afterwards by described Al2O3/ molybdenum oxide mixed-powder at hydrogen atmosphere, temperature be 650 DEG C～750 DEG C under conditions of reduce 8h～10h, obtain Al2O3/ Mo mixed-powder；
Step 3, weigh chromium powder, Y according to the component requirements that need to prepare molybdenum alloy material2O3Powder, titanium valve, nikel powder, niobium powder, zirconium powder, carbon dust, manganese powder and boron powder, then by the various powder weighed and Al described in step 22O3/ Mo mixed-powder and process control agent add ball milling mix homogeneously in planetary ball mill, obtain mixed-powder after drying；Described process control agent is stearic ethanol solution；
Step 4, mixed-powder described in step 3 is carried out cold isostatic compaction, obtain blank；The detailed process of described cold isostatic compaction is: first, part mixed-powder is added vibration tamp in gum cover, extract in gum cover seal rubber sleeve after air, then it is forced into pressurize 5min after 140MPa～150MPa with the compression rate of 15MPa/min～20MPa/min, is down to normal pressure with the rate of pressure reduction of 15MPa/min～20MPa/min afterwards；Then, residue mixed-powder is added vibration tamp in gum cover, extract in gum cover seal rubber sleeve after air, then it is forced into pressurize 1min～2min after 280MPa～300MPa with the compression rate of 25MPa/min～30MPa/min, it is depressurized to 100MPa with the rate of pressure reduction of 15MPa/min～20MPa/min afterwards, is finally down to normal pressure with the rate of pressure reduction of 10MPa/min～15MPa/min；
Step 5, in a hydrogen atmosphere, sinters blank described in step 4 19h～20h under conditions of temperature is 1920 DEG C～1950 DEG C, obtains the wear-resistant molybdenum alloy material cut after furnace cooling.
Above-mentioned method, it is characterised in that the temperature being dried described in step one is 100 DEG C～110 DEG C, and the described dry time is that the water content making solid matter is down to 0.5g/cm3～0.8g/cm3。
Above-mentioned method, it is characterised in that Al described in step 22O3In/Mo mixed-powder, the mean diameter of Mo powder is 5 μm～10 μm, Al2O3The mean diameter of powder is 350nm～450nm；Chromium powder described in step 3, Y2O3The mean diameter of powder, titanium valve, nikel powder, niobium powder, zirconium powder, carbon dust, manganese powder and boron powder is 15 μm～18 μm.
Above-mentioned method, it is characterised in that the time of ball milling described in step 3 is 4h～6h, the speed of ball milling is 280r/min～320r/min, and ball material mass ratio is (5～7): 1, and described ball milling is carried out under the protection of nitrogen or noble gas.
Above-mentioned method, it is characterised in that the addition of process control agent described in step 3 is Al2O3The 2%～3% of/Mo mixed-powder quality.
Above-mentioned method, it is characterised in that stearic ethanol solution described in step 3 is formed by stearic acid and dehydrated alcohol 2: 1 mix homogeneously by volume.
Above-mentioned method, it is characterised in that the temperature being dried described in step 3 is 50 DEG C～60 DEG C, and the described dry time is 5h～7h.
Above-mentioned method, it is characterised in that part mixed-powder described in step 4 accounts for the 40%～50% of mixed-powder total amount.
The present invention compared with prior art has the advantage that
1, the wear-resistant molybdenum alloy material hardness cut of the present invention is high, more than 500Hv；Anti-grinding performance is good, good toughness, and safe and reliable service life can improve 2～3 times than common molybdenum alloy material；
2, the wear-resistant molybdenum alloy material cut of the present invention, its crystal grain is the most tiny, and density and microhardness dramatically increase, it is possible to reach to improve the purpose of molybdenum alloy wear resistance at elevated temperature；
3, the present invention passes through multi-element doping and particle strengthening, makes Al2O3Granule is evenly distributed in molybdenum-base composite material, plays the corresponding function of each element, reduces molybdenum alloy fragility, makes molybdenum-base composite material obtain higher resistance to grinding performance, higher recrystallization temperature and excellent combination property.
4, preparation method of the present invention effectively reduces impurity content in ammonium molybdate, ammonium tetramolybdate purity is made to increase substantially, and the constant product quality of preparation, whole procedure technique is simple, easily controllable, it is tiny to strengthen granule, distribution ratio is more uniform, has the most wide application prospect.
Below in conjunction with embodiment, the present invention is described in further detail.
Detailed description of the invention
Embodiment 1
The wear-resistant molybdenum alloy material cut of the present embodiment includes the composition of following weight portion: Mo70 part, Al2O311 parts, Cr6 part, Y2O38 parts, Ti3 part, Ni4 part, Nb2 part, Zr3 part, C1 part, Mn2 part, B0.1 part.
The preparation method of the wear-resistant molybdenum alloy material cut of the present embodiment comprises the following steps:
Step one, according to need to prepare molybdenum alloy material component requirements prepare ammonium molybdate solution, then use nitric acid that ammonium molybdate solution carries out the heavy crystallization of acid, afterwards the solidliquid mixture containing crystalline solid is placed in vacuum suction filtration tank and carries out vacuum filtration, after pure water rinsing more than 3 times, it is placed in drying baker and is down to 0.8g/cm in 100 DEG C of water content being dried to solid matter3, obtain ammonium tetramolybdate；
Step 2, according to need to prepare molybdenum alloy material component requirements prepare aluminum nitrate solution, again ammonium tetramolybdate described in step one is joined mix homogeneously in aluminum nitrate solution, and use citric acid that the pH value of mixed liquor is adjusted to 1.5, colloidal sol is obtained after standing, then colloidal sol is formed dry state gel in 125 DEG C of vacuum drying again after heating evaporation under conditions of temperature is 90 DEG C, then, after dry state gel being pulverized, under conditions of temperature is 570 DEG C, calcines 30min, obtains Al2O3/ molybdenum oxide mixed-powder, afterwards by described Al2O3/ molybdenum oxide mixed-powder at hydrogen atmosphere, temperature be 650 DEG C under conditions of reduce 10h, obtain Al2O3/ Mo mixed-powder；Described Al2O3In/Mo mixed-powder, the mean diameter of Mo powder is 5 μm, Al2O3The mean diameter of powder is 450nm；
Step 3, weigh chromium powder, Y according to the component requirements that need to prepare molybdenum alloy material2O3Powder, titanium valve, nikel powder, niobium powder, zirconium powder, carbon dust, manganese powder and boron powder, then by the various powder weighed and Al described in step 22O3/ Mo mixed-powder and process control agent add ball milling mix homogeneously in planetary ball mill, obtain mixed-powder after drying；Described process control agent is stearic ethanol solution, and the addition of described process control agent is Al2O3The 2% of/Mo mixed-powder quality；The time of described ball milling is 5h, and ball material mass ratio is 5: 1, and ball milling speed is 320r/min, and described ball milling is carried out under nitrogen protection；Described stearic ethanol solution is formed by stearic acid and dehydrated alcohol 2:1 mixed preparing by volume；Described dry temperature is 60 DEG C, and the time being dried is 5h；Described chromium powder, Y2O3The mean diameter of powder, titanium valve, nikel powder, niobium powder, zirconium powder, carbon dust, manganese powder and boron powder is 15 μm；
Step 4, mixed-powder described in step 3 is carried out cold isostatic compaction, obtain blank；The detailed process of described cold isostatic compaction is: first, and part mixed-powder is added vibration tamp in gum cover, extracts in gum cover seal rubber sleeve after air, and the gum cover that will install powder body loads ferrum cage, immerses in hydraulic fluid；Then it is forced into pressurize 5min after 140MPa with the compression rate of 20MPa/min, is down to normal pressure with the rate of pressure reduction of 20MPa/min afterwards；Then, residue mixed-powder being added vibration tamp in gum cover, extract in gum cover seal rubber sleeve after air, the gum cover that will install powder body loads ferrum cage, immerses in hydraulic fluid；Then it is forced into pressurize 1min after 300MPa with the compression rate of 25MPa/min, is depressurized to 100MPa with the rate of pressure reduction of 20MPa/min afterwards, is finally down to normal pressure with the rate of pressure reduction of 10MPa/min；Described part mixed-powder accounts for the 50% of mixed-powder total amount；
Step 5, in a hydrogen atmosphere, sinters blank described in step 4 19h under conditions of temperature is 1950 DEG C, obtains the wear-resistant molybdenum alloy material cut after furnace cooling.
Molybdenum alloy material made to the present embodiment carries out following detection:
1, microcosmic detection:
Made for the present embodiment molybdenum alloy material is sequentially passed through polish, polish and caustic corrosion after, make metallographic observation sample, wherein caustic is by nitric acid, sulphuric acid and deionized water HNO by volume3∶H2SO4∶H2O=1: 1: 4 mixed preparing form.Described metallographic specimen is observed under scanning electron microscope and understands: pure molybdenum sintered body, average grain size about 30 μm, crystal boundary is the narrowest；And the most visible black alumina granule of the made molybdenum alloy material of the present embodiment, the crystal grain of matrix does not occur, i.e. the crystal boundary of matrix is not corroded out.
2, Vickers hardness detection:
By the Vickers hardness of made for the present embodiment molybdenum alloy material for pure Mo substrate, hardness is enhanced, and improves to 517Hv from the 230Hv of pure molybdenum.
3, the detection of the corrosive nature in different solutions:
Made for the present embodiment molybdenum alloy material and matrix molybdenum polarization curve in NaCl solution there are is bigger difference, the current potential corrigendum of matrix molybdenum, thus more resistant to corrosion；The made molybdenum alloy material of the present embodiment is very much like with matrix molybdenum polarization curve in NaOH solution, thus show that strengthening the addition of phase in NaOH solution the most substantially changes the polarization behavior of metal molybdenum.By the corrosion of more resistance to saline solution for alkali of made for the present embodiment molybdenum alloy material, its corrosion-susceptible performance in alkali liquor and saline solution is more or less the same.
By above detection, the hardness of the made molybdenum alloy material of the present embodiment is high, reaches 517Hv；Anti-grinding performance is good, and good toughness is safe and reliable, and service life can improve 2～3 times than common molybdenum alloy material；Molybdenum alloy crystal grain is the most tiny, and density and microhardness dramatically increase, thus reaches to improve the purpose of molybdenum alloy wear resistance at elevated temperature.
Embodiment 2
The wear-resistant molybdenum alloy material cut of the present embodiment includes the composition of following weight portion: Mo72 part, Al2O39 parts, Cr8 part, Y2O35 parts, Ti5 part, Ni3 part, Nb4 part, Zr1 part, C2 part, Mn1 part, B0.15 part.
The preparation method of the wear-resistant molybdenum alloy material cut of the present embodiment comprises the following steps:
Step one, according to need to prepare molybdenum alloy material component requirements prepare ammonium molybdate solution, then use nitric acid that ammonium molybdate solution carries out the heavy crystallization of acid, afterwards the solidliquid mixture containing crystalline solid is placed in vacuum suction filtration tank and carries out vacuum filtration, after pure water rinsing more than 3 times, it is placed in drying baker and is down to 0.5g/cm in 110 DEG C of water content being dried to solid matter3, obtain ammonium tetramolybdate；
Step 2, according to need to prepare molybdenum alloy material component requirements prepare aluminum nitrate solution, again ammonium tetramolybdate described in step one is joined mix homogeneously in aluminum nitrate solution, and use citric acid that the pH value of mixed liquor is adjusted to 2.0, colloidal sol is obtained after standing, then colloidal sol is formed dry state gel in 125 DEG C of vacuum drying again after heating evaporation under conditions of temperature is 90 DEG C, then, after dry state gel being pulverized, under conditions of temperature is 560 DEG C, calcines 60min, obtains Al2O3/ molybdenum oxide mixed-powder, afterwards by described Al2O3/ molybdenum oxide mixed-powder at hydrogen atmosphere, temperature be 750 DEG C under conditions of reduce 8h, obtain Al2O3/ Mo mixed-powder；Described Al2O3In/Mo mixed-powder, the mean diameter of Mo powder is 10 μm, Al2O3The mean diameter of powder is 350nm；
Step 3, weigh chromium powder, Y according to the component requirements that need to prepare molybdenum alloy material2O3Powder, titanium valve, nikel powder, niobium powder, zirconium powder, carbon dust, manganese powder and boron powder, then by the various powder weighed and Al described in step 22O3/ Mo mixed-powder and process control agent add ball milling mix homogeneously in planetary ball mill, obtain mixed-powder after drying；Described process control agent is stearic ethanol solution, and the addition of described process control agent is Al2O3The 3% of/Mo mixed-powder quality；The time of described ball milling is 6h, and ball material mass ratio is 7: 1, and ball milling speed is 280r/min, and described ball milling is carried out under argon shield；Described stearic ethanol solution is formed by stearic acid and dehydrated alcohol 2:1 mixed preparing by volume；Described dry temperature is 50 DEG C, and the time being dried is 7h；Described chromium powder, Y2O3The mean diameter of powder, titanium valve, nikel powder, niobium powder, zirconium powder, carbon dust, manganese powder and boron powder is 18 μm；
Step 4, mixed-powder described in step 3 is carried out cold isostatic compaction, obtain blank；The detailed process of described cold isostatic compaction is: first, and part mixed-powder is added vibration tamp in gum cover, extracts in gum cover seal rubber sleeve after air, and the gum cover that will install powder body loads ferrum cage, immerses in hydraulic fluid；Then it is forced into pressurize 5min after 150MPa with the compression rate of 15MPa/min, is down to normal pressure with the rate of pressure reduction of 15MPa/min afterwards；Then, residue mixed-powder being added vibration tamp in gum cover, extract in gum cover seal rubber sleeve after air, the gum cover that will install powder body loads ferrum cage, immerses in hydraulic fluid；Then it is forced into pressurize 1.5min after 280MPa with the compression rate of 30MPa/min, is depressurized to 100MPa with the rate of pressure reduction of 15MPa/min afterwards, is finally down to normal pressure with the rate of pressure reduction of 15MPa/min；Described part mixed-powder accounts for the 40% of mixed-powder total amount；
Step 5, in a hydrogen atmosphere, sinters blank described in step 4 20h under conditions of temperature is 1920 DEG C, obtains the wear-resistant molybdenum alloy material cut after furnace cooling.
Molybdenum alloy material made to the present embodiment carries out microcosmic detection, Vickers hardness detection and the detection of the corrosive nature in different solutions successively.By above detection, the hardness of the made molybdenum alloy material of the present embodiment is high, reaches 503Hv；Anti-grinding performance is good, and good toughness is safe and reliable, and service life can improve 2～3 times than common molybdenum alloy material；Molybdenum alloy crystal grain is the most tiny, and density and microhardness dramatically increase, thus reaches to improve the purpose of molybdenum alloy wear resistance at elevated temperature.
Embodiment 3
The wear-resistant molybdenum alloy material cut of the present embodiment includes the composition of following weight portion: Mo71 part, Al2O310 parts, Cr7 part, Y2O36 parts, Ti4 part, Ni3.5 part, Nb3 part, Zr2 part, C1.5 part, Mn1.5 part, B0.12 part.
The preparation method of the wear-resistant molybdenum alloy material cut of the present embodiment comprises the following steps:
Step one, according to need to prepare molybdenum alloy material component requirements prepare ammonium molybdate solution, then use nitric acid that ammonium molybdate solution carries out the heavy crystallization of acid, afterwards the solidliquid mixture containing crystalline solid is placed in vacuum suction filtration tank and carries out vacuum filtration, after pure water rinsing more than 3 times, it is placed in drying baker and is down to 0.7g/cm in 105 DEG C of water content being dried to solid matter3, obtain ammonium tetramolybdate；
Step 2, according to need to prepare molybdenum alloy material component requirements prepare aluminum nitrate solution, again ammonium tetramolybdate described in step one is joined mix homogeneously in aluminum nitrate solution, and use citric acid that the pH value of mixed liquor is adjusted to 1.8, colloidal sol is obtained after standing, then colloidal sol is formed dry state gel in 125 DEG C of vacuum drying again after heating evaporation under conditions of temperature is 90 DEG C, then, after dry state gel being pulverized, under conditions of temperature is 565 DEG C, calcines 45min, obtains Al2O3/ molybdenum oxide mixed-powder, afterwards by described Al2O3/ molybdenum oxide mixed-powder at hydrogen atmosphere, temperature be 700 DEG C under conditions of reduce 9h, obtain Al2O3/ Mo mixed-powder；Described Al2O3In/Mo mixed-powder, the mean diameter of Mo powder is 8 μm, Al2O3The mean diameter of powder is 400nm；
Step 3, weigh chromium powder, Y according to the component requirements that need to prepare molybdenum alloy material2O3Powder, titanium valve, nikel powder, niobium powder, zirconium powder, carbon dust, manganese powder and boron powder, then by the various powder weighed and Al described in step 22O3/ Mo mixed-powder and process control agent add ball milling mix homogeneously in planetary ball mill, obtain mixed-powder after drying；Described process control agent is stearic ethanol solution, and the addition of described process control agent is Al2O3The 2.5% of/Mo mixed-powder quality；The time of described ball milling is 4h, and ball material mass ratio is 6: 1, and ball milling speed is 300r/min, and described ball milling is carried out under argon shield；Described stearic ethanol solution is formed by stearic acid and dehydrated alcohol 2: 1 mixed preparing by volume；Described dry temperature is 55 DEG C, and the time being dried is 6h；Described chromium powder, Y2O3The mean diameter of powder, titanium valve, nikel powder, niobium powder, zirconium powder, carbon dust, manganese powder and boron powder is 17 μm；
Step 4, mixed-powder described in step 3 is carried out cold isostatic compaction, obtain blank；The detailed process of described cold isostatic compaction is: first, and part mixed-powder is added vibration tamp in gum cover, extracts in gum cover seal rubber sleeve after air, and the gum cover that will install powder body loads ferrum cage, immerses in hydraulic fluid；Then it is forced into pressurize 5min after 145MPa with the compression rate of 18MPa/min, is down to normal pressure with the rate of pressure reduction of 18MPa/min afterwards；Then, residue mixed-powder being added vibration tamp in gum cover, extract in gum cover seal rubber sleeve after air, the gum cover that will install powder body loads ferrum cage, immerses in hydraulic fluid；Then it is forced into pressurize 2min after 290MPa with the compression rate of 27MPa/min, is depressurized to 100MPa with the rate of pressure reduction of 18MPa/min afterwards, is finally down to normal pressure with the rate of pressure reduction of 12MPa/min；Described part mixed-powder accounts for the 45% of mixed-powder total amount；
Step 5, in a hydrogen atmosphere, sinters blank described in step 4 19.5h under conditions of temperature is 1930 DEG C, obtains the wear-resistant molybdenum alloy material cut after furnace cooling.
Molybdenum alloy material made to the present embodiment carries out microcosmic detection, Vickers hardness detection and the detection of the corrosive nature in different solutions successively.By above test, the hardness of the made molybdenum alloy material of the present embodiment is high, reaches 511Hv；Anti-grinding performance is good, and good toughness is safe and reliable, and service life can improve 2～3 times than common molybdenum alloy material；Molybdenum alloy crystal grain is the most tiny, and density and microhardness dramatically increase, thus reaches to improve the purpose of molybdenum alloy wear resistance at elevated temperature.
In above-described embodiment, the heavy crystallization of acid is prepared ammonium tetramolybdate and can be used existing technique, it is possible to use following selection process: preparation proportion is 1.14g/cm3～1.16g/cm3Ammonium molybdate solution, squeeze into after filtration in the heavy crystallization kettle of acid, stir and be passed through nitric acid, when solution ph reaches 4, stop acid adding；Solution temperature to keep temperature be 50 DEG C ± 5 DEG C in detection crystallization kettle, continues slow acid adding afterwards；When pH value reaches 2～2.5, stop acid adding；Open crystallization kettle valve, in making feed liquid inflow filter；After material is drained, carry out drip washing and dehydration；Afterwards the material in centrifuge is contained in plastic bag, and plastic bag mouth is tightened；The plastic bag that will be equipped with material is transferred in drying chamber, starts steam valve and heats up, and stops heating up when temperature is raised to 70 ± 5 DEG C, keeps this temperature 6h～7h；After drying time reaches, material is moved on in rustless steel charging tray, after continuing to dry 2h～4h under conditions of 70 ± 5 DEG C, i.e. crystallized.Described ammonium molybdate solution uses electric drive membrane separator to carry out filtering and impurity removing.
In above-described embodiment, the zinc powder of pore creating material can use existing zinc powder product, it is possible to uses following selection process to prepare: using natural gas as heating source, to preheat zinc-melting furnace, make furnace temperature raise；Putting into zinc ingot metal, continue to heat zinc-melting furnace, when furnace temperature is increased to 520～580 DEG C, zinc ingot metal is fused into zinc water；Being imported by zinc water in reverberatory furnace or kier, with natural gas as heating source, control bath temperature 470 DEG C～480 DEG C, stand 30h, to reach melt layering, upper strata is melt zinc concentrate；Remove the scum silica frost of weld pool surface；Melt zinc concentrate layering obtained is put in lead tower holding furnace and is preserved, and temperature controls at 590 DEG C～610 DEG C；Being imported by melt zinc concentrate in lead tower, control temperature is 900 DEG C～1000 DEG C makes zinc cadmium therein separate with high-boiling-point impurity lead and ferrum；The zinc cadmium vapor evaporated from lead tower is condensed into Zn-Cd alloy melt lead tower condenser, and be conducted in cadmium tower, control cadmium tower chamber temperature 850 DEG C～900 DEG C, make cadma matter separate with zinc, being imported in zinc powder condenser by pure zinc fume, zinc powder condenser is circulated by water lowers the temperature；Zinc fume is quenched to 90 DEG C～110 DEG C after entering zinc powder condenser, and zinc fume becomes zinc powder and falls into storage in powder-receiving hopper；Zinc powder in powder-receiving hopper is sequentially passed through mixer and grader, finally obtains finished product high-purity zinc powder, then send into finished product bin by conveyance conduit bottom grader, in described conveyance conduit, be passed through CO2Gas, and keep malleation.
In sum, the present invention passes through multi-element doping and particle strengthening, makes Al2O3Granule is evenly distributed in molybdenum-base composite material, plays the corresponding function of each element, reduces molybdenum alloy fragility, makes molybdenum-base composite material obtain higher resistance to grinding performance, higher recrystallization temperature and excellent combination property.In addition, preparation method of the present invention effectively reduces impurity content in ammonium molybdate, makes ammonium tetramolybdate purity increase substantially, and the constant product quality of preparation, whole procedure technique is simple, easily controllable, it is tiny to strengthen granule, distribution ratio is more uniform, has the most wide application prospect.
Embodiment described above, is only presently preferred embodiments of the present invention, not imposes any restrictions the present invention.Every any simple modification, change and equivalence change made above example according to the technology of the present invention essence, all still falls within the protection domain of technical solution of the present invention.
Claims (10)
1. the wear-resistant molybdenum alloy material cut, it is characterised in that comprise the composition of following weight portion: Mo70～72 parts, Al2O39～11 parts, Cr6～8 parts, Y2O35～8 parts, Ti3～5 parts, Ni3～4 parts, Nb2～4 parts, Zr1～3 parts, C1～2 parts, Mn1～2 parts, B0.1～0.15 part.
A kind of wear-resistant molybdenum alloy material cut the most according to claim 1, it is characterised in that comprise the composition of following weight portion: Mo71 part, Al2O310 parts, Cr7 part, Y2O36 parts, Ti4 part, Ni3.5 part, Nb3 part, Zr2 part, C1.5 part, Mn1.5 part, B0.12 part.
3. the method preparing the most wear-resistant molybdenum alloy material cut, it is characterised in that the method comprises the following steps:
Step one, prepare ammonium molybdate solution according to the component requirements that need to prepare molybdenum alloy material, then ammonium molybdate solution is carried out the heavy crystallization of acid, sequentially passes through vacuum filtration, washing and dried afterwards, obtain ammonium tetramolybdate；
Step 2, according to need to prepare molybdenum alloy material component requirements prepare aluminum nitrate solution, again ammonium tetramolybdate described in step one is joined mix homogeneously in aluminum nitrate solution, and use citric acid that the pH value of mixed liquor is adjusted to 1.5～2.0, colloidal sol is obtained after standing, then after colloidal sol being dried and pulverizes, under conditions of temperature is 560 DEG C～570 DEG C, calcines 30min～60min, obtains Al2O3/ molybdenum oxide mixed-powder, afterwards by described Al2O3/ molybdenum oxide mixed-powder at hydrogen atmosphere, temperature be 650 DEG C～750 DEG C under conditions of reduce 8h～10h, obtain Al2O3/ Mo mixed-powder；
Step 3, weigh chromium powder, Y according to the component requirements that need to prepare molybdenum alloy material2O3Powder, titanium valve, nikel powder, niobium powder, zirconium powder, carbon dust, manganese powder and boron powder, then by the various powder weighed and Al described in step 22O3/ Mo mixed-powder and process control agent add ball milling mix homogeneously in planetary ball mill, obtain mixed-powder after drying；Described process control agent is stearic ethanol solution；
Step 4, mixed-powder described in step 3 is carried out cold isostatic compaction, obtain blank；The detailed process of described cold isostatic compaction is: first, part mixed-powder is added vibration tamp in gum cover, extract in gum cover seal rubber sleeve after air, then it is forced into pressurize 5min after 140MPa～150MPa with the compression rate of 15MPa/min～20MPa/min, is down to normal pressure with the rate of pressure reduction of 15MPa/min～20MPa/min afterwards；Then, residue mixed-powder is added vibration tamp in gum cover, extract in gum cover seal rubber sleeve after air, then it is forced into pressurize 1min～2min after 280MPa～300MPa with the compression rate of 25MPa/min～30MPa/min, it is depressurized to 100MPa with the rate of pressure reduction of 15MPa/min～20MPa/min afterwards, is finally down to normal pressure with the rate of pressure reduction of 10MPa/min～15MPa/min；
Step 5, in a hydrogen atmosphere, sinters blank described in step 4 19h～20h under conditions of temperature is 1920 DEG C～1950 DEG C, obtains the wear-resistant molybdenum alloy material cut after furnace cooling.
Method the most according to claim 3, it is characterised in that the temperature being dried described in step one is 100 DEG C～110 DEG C, and the described dry time is that the water content making solid matter is down to 0.5g/cm3～0.8g/cm3。
Method the most according to claim 3, it is characterised in that Al described in step 22O3In/Mo mixed-powder, the mean diameter of Mo powder is 5 μm～10 μm, Al2O3The mean diameter of powder is 350nm～450nm；Chromium powder described in step 3, Y2O3The mean diameter of powder, titanium valve, nikel powder, niobium powder, zirconium powder, carbon dust, manganese powder and boron powder is 15 μm～18 μm.
Method the most according to claim 3; it is characterized in that, the time of ball milling described in step 3 is 4h～6h, and the speed of ball milling is 280r/min～320r/min; ball material mass ratio is (5～7): 1, and described ball milling is carried out under the protection of nitrogen or noble gas.
Method the most according to claim 3, it is characterised in that the addition of process control agent described in step 3 is Al2O3The 2%～3% of/Mo mixed-powder quality.
Method the most according to claim 3, it is characterised in that stearic ethanol solution described in step 3 is formed by stearic acid and dehydrated alcohol 2: 1 mix homogeneously by volume.
Method the most according to claim 3, it is characterised in that the temperature being dried described in step 3 is 50 DEG C～60 DEG C, and the described dry time is 5h～7h.
Method the most according to claim 3, it is characterised in that part mixed-powder described in step 4 accounts for the 40%～50% of mixed-powder total amount.
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