CN101665882B - Aluminum preliminary alloy refiner containing titanium and vanadium, aluminum alloy containing titanium and vanadium and preparation method - Google Patents
Aluminum preliminary alloy refiner containing titanium and vanadium, aluminum alloy containing titanium and vanadium and preparation method Download PDFInfo
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- CN101665882B CN101665882B CN 200910167820 CN200910167820A CN101665882B CN 101665882 B CN101665882 B CN 101665882B CN 200910167820 CN200910167820 CN 200910167820 CN 200910167820 A CN200910167820 A CN 200910167820A CN 101665882 B CN101665882 B CN 101665882B
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Abstract
The invention discloses an aluminum preliminary alloy refiner containing titanium and vanadium, comprising the following components by weight percent: 1 to 99% of aluminum, 0.01 to 77% of vanadium, 0.01 to 77% of titanium, 0 to 20% of carbon and 0 to 23% of nitrogen, wherein at least one of carbon and nitrogen exists in preliminary alloy refiner. Aluminum alloy which contains titanium and vanadium comprises the following chemical components by weight percent: 0.001 to 1% of vanadium and 0.001 to 1% of titanium. The aluminum preliminary alloy refiner containing titanium and vanadium has five preparation methods, and aluminum alloy which contains titanium and vanadium have two preparation methods.
Description
Technical field
The invention belongs to aluminium and field of aluminum alloys, relate to master alloy fining agent and the aluminium alloy that contains the vanadium titanium and their preparation method containing vanadium titanium aluminium.
Background technology
Aluminium alloy, because of characteristics such as lightweight, aboundresources, good combination properties, is used widely in the fields such as machinery, communications and transportation, space flight and war industry, and its demand increases year by year.Along with hi-tech development, to the higher requirement of comprehensive mechanical performance proposition of aluminium and aluminium alloy.According to the Hall-Petch formula, crystal grain thinning is the effective means that improves the intensity of aluminium and aluminium alloy and improve its plasticity and toughness.Therefore, aluminium and the aluminium alloy that can use different crystal fining methods to obtain to there is tiny equiaxed grain structure, and be the most simple and effective method to adding grain-refining agent in melt.During aluminium and aluminium alloy are produced, traditional fining agent is main mainly with carbide, the boride of titaniferous, but, in the industrial application of nearly more than ten years, finds in use to come with some shortcomings, as the Al-Ti-B master alloy as its grain-refining agent, but the TiB produced because adding this type of fining agent
2particle can be assembled, precipitate in aluminium liquid, not only causes the decline to the thinning effect of aluminium and aluminium alloy crystal grain, particularly, to the aluminium alloy containing Zr, Cr, easily causes TiB
2particle " poisoning ", even lose the thinning effect to aluminium and aluminium alloy, and due to TiB
2the particle cluster size is larger, is unfavorable for the following process of the goods such as aluminium foil; While using the Al-Ti-C master alloy as fining agent, although it is less to add the TiC size of particles of fining agent generation, and unlike TiB
2particle is easy to assemble like that, thereby more potential when producing aluminium foil, but the wettability of liquid aluminium and carbon is poor, and the TiC particle easily reacts generation Al with molten aluminium
4c
3, cause equally the quick decline to the thinning effect of aluminium and alloy thereof.In a word, some defects due to traditional grain-refining agent itself, restricted the raising of aluminium and aluminium alloy over-all properties too.Therefore, be necessary fining agent and the aluminum-system that further exploitation is new with research.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, the master alloy fining agent containing vanadium titanium aluminium, the aluminium alloy that contains the vanadium titanium and their preparation method are provided, to improve the over-all properties of aluminium alloy.
One, containing master alloy fining agent of vanadium titanium aluminium and preparation method thereof
Master alloy fining agent containing vanadium titanium aluminium of the present invention, its component comprises aluminium, vanadium, titanium, carbon or/and nitrogen, and the weight percentage of each component is: aluminium 1～99%, vanadium 0.01～77%, titanium 0.01～77%, carbon 0～20%, nitrogen 0～23%; Wherein, carbon, nitrogen have a kind of existence at least in described master alloy fining agent.
Master alloy fining agent containing vanadium titanium aluminium of the present invention, its preparation method has following five kinds.
1, the first preparation method's processing step:
(1) batching
Raw material is aluminium and containing vanadium titanium base-material, according to the above-mentioned described aluminium of master alloy fining agent containing vanadium titanium aluminium, vanadium, titanium, carbon or/and the weight percentage of nitrogen calculate and the described raw material of weighing;
(2) mixing and moulding
The aluminium that step (1) is prepared and carry out ball milling containing vanadium titanium base-material, Ball-milling Time mixes and is limited with above-mentioned raw materials, then by the raw material compression moulding that mixes or compression moulding after drying, forms pressed compact;
(3) sintering
Pressed compact prepared by step (2) is placed in heat treatment furnace, sintering under the atmosphere that passes into nitrogen or argon gas or hydrogen, 300～750 ℃ of sintering temperatures, soaking time 0.5～4 hour, insulation cools to the furnace below 100 ℃ and comes out of the stove after finishing, and obtains the master alloy fining agent containing vanadium titanium aluminium;
In aforesaid method, described is (V containing vanadium titanium base-material
1-xti
x) C
y, (V
1-xti
x) N
y, (V
1-xti
x) (C
1-y, N
y) at least one, or be VC
y, VN
y, V (C
1-y, N
y) at least one and TiC
y, TiN
y, Ti (C
1-y, N
y) at least one, described VC
y, VN
y, TiC
y, TiN
y,(V
1-xti
x) C
y(V
1-xti
x) N
yin, 0<x<1,0<y≤1, described (V
1-xti
x) (C
1-y, N
y), V (C
1-y, N
y), Ti (C
1-y, N
y) in, 0<x<1,0<y<1.
2, the second preparation method's processing step:
(1) batching
Raw material is aluminum or aluminum alloy and containing vanadium titanium base-material, according to the above-mentioned described aluminium of master alloy fining agent containing vanadium titanium aluminium, vanadium, titanium, carbon or/and the weight percentage of nitrogen calculate and the described raw material of weighing;
(2) fusing
The aluminum or aluminum alloy that step (1) is prepared is placed in process furnace, logical rare gas element forms protective atmosphere or adds insulating covering agent, then heating makes it form molten aluminum liquid or the aluminum alloy melt of 650 ℃～1200 ℃, add in aluminium liquid or aluminum alloy melt and, after stirring, at 650 ℃～1200 ℃, be incubated 0.1～2 hour containing vanadium titanium base-material load weighted in step (1) again;
(3) casting is solidified
Aluminium alloy prepared by step (2) is cast into ingot casting, is cooled to after room temperature the oxide skin of removing the ingot casting surface, obtains the master alloy fining agent containing vanadium titanium aluminium;
In aforesaid method, described is (V containing vanadium titanium base-material
1-xti
x) C
y, (V
1-xti
x) N
y, (V
1-xti
x) (C
1-y, N
y) at least one, or be VC
y, VN
y, V (C
1-y, N
y) at least one and TiC
y, TiN
y, Ti (C
1-y, N
y) at least one, described VC
y, VN
y, TiC
y, TiN
y, (V
1-xti
x) C
y(V
1-xti
x) N
yin, 0<x<1,0<y≤1, described (V
1-xti
x) (C
1-y, N
y), V (C
1-y, N
y), Ti (C
1-y, N
y) in, 0<x<1,0<y<1;
In aforesaid method, described insulating covering agent is at least one in Repone K, sodium-chlor, lithium chloride, Potassium monofluoride, sodium pyrosulfate.
3, the third preparation method's processing step:
(1) batching
Raw material is aluminium, contains vanadium base-material, titaniferous base-material and carbonaceous reducing agent, calculates and the described raw material of weighing according to the weight percentage of the above-mentioned described aluminium of master alloy fining agent containing vanadium titanium aluminium, vanadium, titanium, carbon;
(2) mixing and moulding
The aluminium powder that step (1) is prepared, containing vanadium base-material, titaniferous base-material and carbonaceous reducing agent, carry out ball milling, Ball-milling Time mixes and is limited with above-mentioned raw materials, then by the raw material compression moulding that mixes or compression moulding after drying, forms pressed compact;
(3) sintering
Pressed compact prepared by step (2) is placed in reduction reaction furnace, or pressed compact prepared by step (2) is placed in reduction reaction furnace and passes into nitrogen or ammonia or its mixed gas, furnace air to be got rid of is warming up to 500 ℃～650 ℃ insulations 0.5 hour～2 hours later, then be heated to 900 ℃～1300 ℃ insulations 1～4 hour, insulation cools to the furnace below 100 ℃ and comes out of the stove after finishing, and obtains the master alloy fining agent containing vanadium titanium aluminium;
Or pressed compact prepared by step (2) is placed in reduction reaction furnace, be warming up to 500 ℃～650 ℃ insulations 0.1～2 hour under vacuum condition, or add nitrogen or ammonia or its mixed gas while being warming up to 500 ℃～650 ℃ under vacuum condition and in 500 ℃～650 ℃ insulations 0.1～2 hour, then be heated to 900 ℃～1300 ℃ insulations 1～4 hour, insulation cools to the furnace below 100 ℃ and comes out of the stove after finishing, and obtains the master alloy fining agent containing vanadium titanium aluminium;
In aforesaid method, described is V containing the vanadium base-material
2o
5, V
2o
3, at least one in ammonium meta-vanadate, described titaniferous base-material is TiO
2, at least one in metatitanic acid, described carbonaceous reducing agent is at least one in carbon black, gac, graphite, charcoal.
4, the 4th kind of preparation method's processing step:
(1) batching
Raw material is aluminium, contains vanadium base-material, titaniferous base-material, carbonaceous reducing agent and certainly spread inducer, aluminium, containing vanadium base-material, titaniferous base-material and carbonaceous reducing agent, according to the weight percentage of the above-mentioned described aluminium of master alloy fining agent containing vanadium titanium aluminium, vanadium, titanium, carbon, calculate and weighing, certainly to spread inducer be aluminium, containing 0.1～5% of vanadium base-material, titaniferous base-material and carbonaceous reducing agent gross weight;
(2) mixing and moulding
The aluminium that step (1) is prepared, containing vanadium base-material, titaniferous base-material, carbonaceous reducing agent with certainly spread inducer and carry out ball milling, Ball-milling Time mixes and is limited with described raw material, then by the raw material compression moulding or the rear compression moulding of oven dry that mix, form pressed compact;
(3) certainly spread synthetic
Pressed compact prepared by step (2) is placed in process furnace, or pressed compact prepared by step (2) is placed in process furnace and passes into nitrogen, bring out self-propagating reaction at 800 ℃～1300 ℃, after having reacted, cool to the furnace below 100 ℃ and come out of the stove, obtain the master alloy fining agent containing vanadium titanium aluminium;
Described containing the vanadium base-material be vanadium, containing at least one in barium oxide, described titaniferous base-material is at least one in titanium, titanium-containing oxide, described carbonaceous reducing agent is at least one in carbon black, gac, graphite, wood charcoal powder, and described is a kind of in magnesium, calcium chloride, calcium from spreading inducer.
5, the 5th kind of preparation method's processing step:
(1) batching
Raw material is aluminium, contains vanadium base-material, titaniferous base-material, carbonaceous reducing agent and certainly spread inducer, aluminium, containing vanadium base-material, titaniferous base-material and carbonaceous reducing agent, according to the weight percentage of the above-mentioned described aluminium of master alloy fining agent containing vanadium titanium aluminium, vanadium, titanium, carbon, calculate and weighing, certainly to spread inducer be aluminium, containing 0.1～5% of vanadium base-material, titaniferous base-material and carbonaceous reducing agent gross weight;
(2) mixing and moulding
Ball milling is carried out in step (1) is prepared contain vanadium base-material, titaniferous base-material, carbonaceous reducing agent and certainly spread inducer, and Ball-milling Time mixes and is limited with described raw material, then, by the raw material compression moulding or the rear compression moulding of oven dry that mix, forms pressed compact;
(3) certainly spread synthetic
The aluminium of step (1) metering is placed in to the molten aluminum liquid that process furnace adds 800 ℃～1300 ℃ of thermosettings, or the aluminium of step (1) metering is placed in to process furnace and passes into nitrogen, then the molten aluminum liquid that adds 800 ℃～1300 ℃ of thermosettings, the pressed compact again prepared by step (2) is placed in the process furnace that above-mentioned molten aluminum liquid is housed, be cast into ingot casting 800 ℃～1300 ℃ insulations after 0.1 hour～2 hours, be cooled to after room temperature the oxide skin of removing the ingot casting surface, obtain the master alloy fining agent containing vanadium titanium aluminium;
Described containing the vanadium base-material be vanadium, containing at least one in barium oxide, described titaniferous base-material is at least one in titanium, titanium-containing oxide, described carbonaceous reducing agent is at least one in carbon black, gac, graphite, wood charcoal powder, and described is a kind of in magnesium, calcium chloride, calcium from spreading inducer.
Two, containing vanadium-titanium-aluminum alloy and preparation method
Of the present invention containing vanadium-titanium-aluminum alloy, its chemical composition comprises vanadium and titanium, and the weight percentage of vanadium is 0.001～1%, and the weight percentage of titanium is 0.001～1%, and the existence form of vanadium, titanium is (V
1-xti
x) C
y, (V
1-xti
x) N
y, (V
1-xti
x) (C
1-y, N
y) at least one, or be VC
y, VN
y, V (C
1-y, N
y) at least one and TiC
y, TiN
y, Ti (C
1-y, N
y) at least one, described VC
y, VN
y, TiC
y, TiN
y,(V
1-xti
x) C
y(V
1-xti
x) N
yin, 0<x<1,0<y≤1, described (V
1-xti
x) (C
1-y, N
y), V (C
1-y, N
y), Ti (C
1-y, N
y) in, 0<x<1,0<y<1.
Of the present invention containing the preferred following component of vanadium-titanium-aluminum alloy and content thereof.
Containing the component of vanadium-titanium-aluminum alloy and the weight percentage of each component, be: 0.001～1%V, 0.001～1%Ti, 0～0.35%C, 0～0.35%N, surplus is Al, wherein, carbon, nitrogen have a kind of existence at least in aluminium;
Containing the component of vanadium titanium aluminum silicon alloy and the weight percentage of each component, be: 4～22%Si, 0～3.5%Cu, 0～1.3%Mg, 0～0.9%Mn, 0.001～1%Ti, 0.001～1%V, 0～0.35%C, 0～0.35%N, surplus is Al, wherein, carbon, nitrogen have a kind of existence at least in described aluminum silicon alloy;
Containing the component of vanadium titanium aluminum-copper alloy and the weight percentage of each component, be: 4.0～11%Cu, 0～2.0%Si, 0～0.25%Mg, 0～1.2%Mn, 0.001～1%Ti, 0.001～1%V, 0～0.35%C, 0～0.35%N, surplus is Al, wherein, carbon, nitrogen have a kind of existence at least in described aluminum-copper alloy;
Containing the component of vanadium titanium aluminum magnesium alloy and the weight percentage of each component, be: 4.5～11.0%Mg, 0～1.3%Si, 0～1.5%Zn, 0～1.4%Mn, 0.001～1%Ti, 0.001～1%V, 0～0.35%C, 0～0.35%N, surplus is Al, wherein, carbon, nitrogen have a kind of existence at least in described aluminum magnesium alloy.
Of the present invention containing vanadium-titanium-aluminum alloy, its preparation method has following two kinds.
1, the first preparation method's processing step:
(1) batching
Raw material is aluminum or aluminum alloy and ,Tai source, vanadium source, according to the above-mentioned chemical composition containing vanadium-titanium-aluminum alloy, calculates and the described raw material of weighing;
(2) fusing
The aluminum or aluminum alloy that step (1) is prepared is placed in process furnace and passes into rare gas element or add insulating covering agent, then heating makes its molten aluminum liquid or aluminum alloy melt that forms 650 ℃～1200 ℃, then by ,Tai source, load weighted vanadium source in step (1) add in aluminium liquid or aluminum alloy melt stir after in 650 ℃～1200 ℃ insulations 0.1～2 hour;
(3) casting is solidified
Aluminium alloy prepared by step (2) is cast into ingot casting, is cooled to after room temperature the oxide skin of removing the ingot casting surface, obtains the aluminium alloy containing the vanadium titanium;
,Tai source, described vanadium source is the above-mentioned master alloy fining agent containing vanadium titanium aluminium, or is (V
1-xti
x) C
y, (V
1-xti
x) N
y, (V
1-xti
x) (C
1-y, N
y) at least one, or be VC
y, VN
y, V (C
1-y, N
y) at least one and TiC
y, TiN
y, Ti (C
1-y, N
y) at least one, described VC
y, VN
y, TiC
y, TiN
y, (V
1-xti
x) C
y(V
1-xti
x) N
yin, 0<x<1,0<y≤1, described (V
1-xti
x) (C
1-y, N
y), V (C
1-y, N
y), Ti (C
1-y, N
y) in, 0<x<1,0<y<1;
Described insulating covering agent is at least one in Repone K, sodium-chlor, lithium chloride, Potassium monofluoride, sodium pyrosulfate.
2, the second preparation method's processing step:
(1) batching
Raw material comprises aluminum or aluminum alloy, vanadic salts, titanium salt and carbonaceous reducing agent, and aluminum or aluminum alloy, vanadic salts, titanium salt and carbonaceous reducing agent calculate and weighing according to the above-mentioned chemical composition in addition of denitrogenating containing vanadium-titanium-aluminum alloy;
(2) mixing and moulding
Vanadic salts, titanium salt and carbonaceous reducing agent that step (1) is prepared carry out ball milling, and Ball-milling Time mixes and is limited with described raw material, then by the raw material compression moulding that mixes or be wrapped to form blank with aluminium foil;
(3) fusing and casting
The aluminum or aluminum alloy of step (1) metering is placed in to process furnace, or the aluminum or aluminum alloy of step (1) metering is placed in to process furnace and passes into nitrogen, then be heated to 700 ℃～1200 ℃ and form aluminium liquid or aluminum alloy melt, the blank again prepared by step (2) is placed in the process furnace that above-mentioned molten aluminum liquid or aluminum alloy melt are housed, be cast into ingot casting in 700 ℃～1200 ℃ insulations after 0.4 hour～2 hours, be cooled to after room temperature the oxide skin of removing the ingot casting surface, obtain the aluminium alloy containing vanadium;
Described vanadic salts is at least one in vanadate, metavanadate, polyoxovanadate, described titanium salt is at least one in titanate, metatitanate, titanyl sulfate, and described carbonaceous reducing agent is at least one in carbon black, gac, graphite, wood charcoal powder, glucose, sucrose.
The present invention has following beneficial effect:
1, due to of the present invention, contain in the master alloy fining agent of vanadium titanium aluminium, the carbide that the existence form of vanadium titanium is the vanadium titanium or/and the nitride of vanadium, titanium or/and the carbonitride of vanadium, titanium, its characteristics are vanadium, compound fashionable showed state and the character of adding of titanium, be not that they add separately fashionable simple linear superposition, but show very complicated interaction, thereby refining aluminum alloy crystal grain more effectively, and can not cause the thinning effect decline.Experiment shows, the fining agent containing vanadium titanium aluminium of the present invention is better than the Al-Ti-B fining agent to the grain refining effect of aluminium alloy.
2, owing to having introduced nitrogen, can not only improve the grain refining effect of fining agent, and greatly improve the wettability of carbon and aluminium in the alloy, be conducive to the preparation containing the fining agent of vanadium titanium aluminium, promote containing the suitability for industrialized production of vanadium titanium aluminium fining agent and apply.
4, the vanadium-titanium-aluminum alloy that contains of the present invention is compared with existing aluminium alloy, and its crystal grain is more tiny, and mechanical property improves, and Application Areas is more extensive.
5, the method for the invention technique is simple, and raw material is easy to obtain, and is conducive to equilibrium and utilizes vanadium, titanium resource, reduces production costs, thereby is convenient to suitability for industrialized production.
The accompanying drawing explanation
Fig. 1 is the apparent pattern photo of aluminium ingot that adds the Al-Ti-B fining agent;
Fig. 2 is the apparent pattern photo of aluminium ingot that adds the master alloy fining agent containing vanadium titanium aluminium of the present invention.
Embodiment
Below by embodiment to master alloy fining agent containing vanadium titanium aluminium of the present invention, be described further containing vanadium-titanium-aluminum alloy and their preparation method.
Embodiment 1
The present embodiment is raw materials used and processing step is as follows:
Raw material is aluminium powder 1g, (V
0.95ti
0.05) C powder 99g.By aluminium powder and the (V measured
0.95ti
0.05) the C powder carries out rolling ball milling, ball material mass ratio is 6: 1, Ball-milling Time mixes be limited (approximately 10 hours) with raw material, then by the raw material compression moulding mixed, pressed compact is of a size of Φ 1.6cm * 2.5cm, continue after pressed compact is put into to process furnace, and pass into argon gas or hydrogen, flow 1.5L/min, after passing into argon gas or hydrogen to get rid of furnace air, (about 3min) is heated to 300 ℃ and in 300 ℃ of insulation 4h, after finishing, insulation comes out of the stove below furnace cooling to 100 ℃, obtain containing vanadium titanium aluminium intermediate alloy fining agent 76.30%V-3.78%Ti-18.92%C-1%Al.
Embodiment 2
The present embodiment is raw materials used and processing step is as follows:
Raw material is aluminium powder 1g, VC powder 5.25g, TiC powder 93.75g.By aluminium powder and the VC powder measured, the TiC powder carries out rolling ball milling, ball material mass ratio is 6: 1, Ball-milling Time mixes be limited (approximately 10 hours) with raw material, then by the raw material compression moulding mixed, pressed compact is of a size of Φ 1.6cm * 2.5cm, continue after pressed compact is put into to process furnace, and pass into argon gas or hydrogen, flow 1.5L/min, after passing into argon gas or hydrogen to get rid of furnace air, (3min) is heated to 700 ℃ and in 700 ℃ of insulation 1h, after finishing, insulation comes out of the stove below furnace cooling to 100 ℃, obtain containing vanadium titanium aluminium intermediate alloy fining agent 4.25%V-74.97%Ti-19.78%C-1%Al.
Embodiment 3
The present embodiment is raw materials used and processing step is as follows:
Raw material is aluminium powder 1g, (V
0.05ti
0.95) N powder 99g.By aluminium powder and the (V measured
0.05ti
0.95) the N powder carries out rolling ball milling, ball material mass ratio is 10: 1, Ball-milling Time mixes be limited (approximately 24 hours) with raw material, then by the raw material compression moulding mixed, pressed compact is of a size of Φ 1.6cm * 2.5cm, continue after pressed compact is put into to process furnace and is passed into nitrogen, flow is 5L/min, after passing into nitrogen to get rid of furnace air, (about 3min) is heated to 750 ℃ and in 750 ℃ of insulation 0.5h, come out of the stove below furnace cooling to 100 ℃ after insulation finishes, obtain containing vanadium titanium aluminium intermediate alloy fining agent 4.06%V-72.60%Ti-22.34%N-1%Al.
Embodiment 4
The present embodiment is raw materials used and processing step is as follows:
Raw material is aluminium powder 99g, VN powder 0.95g, TiN powder 0.05g.The aluminium powder measured is placed in to box type heater and passes into nitrogen or argon gas, then the molten aluminum liquid that adds 650 ℃ of thermosettings, by load weighted VN powder, TiN powder, add in aluminium liquid again and after stirring, in 650 ℃ of insulation 2h, insulation is cast into ingot casting after finishing, be cooled to after room temperature the oxide skin of removing the ingot casting surface, obtain containing vanadium titanium aluminium intermediate alloy fining agent 0.74%V-0.039%Ti-0.221%N-99%Al.
Embodiment 5
The present embodiment is raw materials used and processing step is as follows:
Raw material is ZAlCu4 aluminium alloy 99g, V
0.05ti
0.95c powder 1g.The aluminium alloy measured is placed in to the molten aluminum liquid that process furnace adds 1200 ℃ of thermosettings, and then by load weighted V
0.05ti
0.95the C powder adds in aluminium liquid and stirs, and add insulating covering agent NaCl and each 0.5g of KCl or lithium chloride 1g or Potassium monofluoride 1g or sodium pyrosulfate 1g, be incubated again 0.1h, insulation is cast into ingot casting after finishing, be cooled to after room temperature the oxide skin of removing the ingot casting surface, obtain containing vanadium titanium aluminium intermediate alloy fining agent 0.04%V-0.76%Ti-0.2%C-95.04%Al-3.96%Cu.
Embodiment 6
The present embodiment is raw materials used and processing step is as follows:
Raw material is aluminium powder 0.6g, V
2o
5powder 5g, TiO
2powder 50g, wood charcoal powder or gac 17.2g.By aluminium powder, the V measured
2o
5powder, TiO
2powder and wood charcoal powder or gac carry out rolling ball milling, ball material mass ratio is 5: 1, Ball-milling Time mixes be limited (approximately 10 hours) with raw material, then by the raw material compression moulding mixed, pressed compact is of a size of Φ 1.6cm * 2.5cm, continue after pressed compact is put into to process furnace, and pass into nitrogen or ammonia simultaneously, flow remains on 3L/min, after furnace air to be got rid of (about 3min) be heated to 650 ℃ and in 650 ℃ the insulation 0.5h, soaking time is warming up to 1300 ℃ and in 1300 ℃ of insulation 1h again at the expiration, insulation cools to the furnace below 100 ℃ and comes out of the stove after finishing, obtain containing vanadium titanium aluminium intermediate alloy fining agent 3.4%V-72.9%Ti-10.8%C-11.44%N-1.46%Al.
Embodiment 7
The present embodiment is raw materials used and processing step is as follows:
Raw material is aluminium powder 4.3g, ammonium meta-vanadate powder 58.47g, metatitanic acid powder 9.8g, carbon black or Graphite Powder 99 17.4g.Aluminium powder, ammonium meta-vanadate powder and the carbon black or the Graphite Powder 99 that measure are carried out to rolling ball milling, ball material mass ratio is 10: 1, Ball-milling Time mixes be limited (approximately 72 hours) with raw material, then by the raw material compression moulding mixed, pressed compact is of a size of Φ 1.6cm * 2.5cm, continue after pressed compact is put into to process furnace, be evacuated to 10
-2after Pa, pass into nitrogen 0.025MPa while being heated to 500 ℃, and in 500 ℃ of insulation 2h, soaking time is warming up to 900 ℃ and in 900 ℃ of insulation 4h again at the expiration, come out of the stove below furnace cooling to 100 ℃ after insulation finishes, obtain containing vanadium titanium aluminium intermediate alloy fining agent 59.29%V-11.15%Ti-10%C-9.55%N-10.01%Al.
The present embodiment is raw materials used and processing step is as follows:
Raw material is aluminium powder 40g, vanadium powder 10g, titanium valve 30g, carbon black or wood charcoal powder 5.96g, magnesium powder or MAG block 1g.By the aluminium powder measured, vanadium powder, carbon black or wood charcoal powder and magnesium powder or MAG block carry out rolling ball milling, ball material mass ratio is 10: 1, Ball-milling Time mixes be limited (approximately 12 hours) with raw material, then by the raw material compression moulding mixed, pressed compact is of a size of Φ 1.6cm * 2.5cm, continue after pressed compact is dried and to be placed in process furnace and to pass into nitrogen, flow velocity is 2.3L/min, be warming up to 1300 ℃ and bring out self-propagating reaction, cool to the furnace after having reacted below 100 ℃ and come out of the stove, obtain containing vanadium titanium aluminium intermediate alloy fining agent 10.22%V-30.65%Ti-10.09%C-8.17%N-40.87%Al.
Embodiment 9
The present embodiment is raw materials used and processing step is as follows:
Raw material is aluminium powder 100g, V
2o
3powder 28g, TiO
2powder 2g, gac 3.97g, Graphite Powder 99 3.73g, magnesium powder or MAG block 3g.By aluminium powder, the V measured
2o
3powder, TiO
2powder, gac, Graphite Powder 99 and magnesium powder or MAG block carry out rolling ball milling, ball material mass ratio is 8: 1, Ball-milling Time mixes be limited (approximately 20 hours) with raw material, then by the raw material compression moulding mixed, pressed compact is of a size of Φ 1.6cm * 2.5cm, continue after pressed compact is dried and to be placed in process furnace and to pass into nitrogen, flow velocity is 1L/min, be warming up to 800 ℃ and bring out self-propagating reaction, cool to the furnace after having reacted below 100 ℃ and come out of the stove, obtain containing vanadium titanium aluminium intermediate alloy fining agent 15.09%V-0.95%Ti-2.02%C-2.64%N-79.3%Al.
Embodiment 10
The present embodiment is raw materials used and processing step is as follows:
Raw material is aluminium powder 99g, V
2o
5powder 1.48g, TiO
2powder 1g, gac or Graphite Powder 99 1.3g, calcium chloride 2.5g.By the V measured
2o
5powder, TiO
2powder, gac or Graphite Powder 99 and calcium chloride carry out rolling ball milling, ball material mass ratio is 6: 1, Ball-milling Time mixes be limited (approximately 10 hours) with raw material, then, by the raw material compression moulding the oven dry that mix, pressed compact is of a size of Φ 1.0cm * 2.0cm.The aluminium powder measured is placed in to process furnace and adds 800 ℃ of molten aluminum liquids of thermosetting, then pressed compact is placed in to the process furnace (utilizing the temperature trigger self-propagating reaction of molten aluminum liquid) of the molten aluminum liquid that is equipped with 800 ℃, in 800 ℃ of insulation 2h, insulation is cast into ingot casting after finishing, be cooled to after room temperature the oxide skin of removing the ingot casting surface, obtain containing vanadium titanium aluminium intermediate alloy fining agent 0.82%V-0.6%Ti-0.34%C-98.24%Al.
Embodiment 11
The present embodiment is raw materials used and processing step is as follows:
Raw material is aluminium powder 90g, V
2o
3powder 2g, TiO
2powder 4g, carbon black or wood charcoal powder 2.9g, calcium powder 1g.By the V measured
2o
3powder, TiO
2powder, carbon black or wood charcoal powder and calcium powder carry out rolling ball milling, and ball material mass ratio is 6: 1, and Ball-milling Time mixes be limited (approximately 10 hours) with raw material, and then, by the raw material compression moulding mixed, pressed compact is of a size of Φ 1.0cm * 2.0cm.The aluminium powder measured is placed in to retort furnace and adds 1300 ℃ of molten aluminum liquids of thermosetting, then pressed compact is dried in the retort furnace that is placed on the molten aluminum liquid that is equipped with 1300 ℃ (utilizing the temperature trigger self-propagating reaction of molten aluminum liquid), in 1300 ℃ of insulation 0.1h, be cast into ingot casting after after insulation finishes, be cooled to after room temperature the oxide skin of removing the ingot casting surface, obtain containing vanadium titanium aluminium intermediate alloy fining agent 1.44%V-1.9%Ti-1.61%C-95.05%Al.
Embodiment 12
The present embodiment is raw materials used and processing step is as follows:
Raw material is aluminium powder 1kg, the master alloy fining agent 10.22%V-30.65%Ti-10.09%C-8.17%N-40.87%Al0.2g of embodiment 8 preparations.The aluminium powder measured is placed in to process furnace; and pass into argon shield; then heating makes it form the molten aluminum liquid of 650 ℃; again the master alloy fining agent is added in aluminium liquid stir after in 650 ℃ the insulation 2h; continue after aluminium alloy is cast into to ingot casting; be cooled to after room temperature the oxide skin of removing the ingot casting surface, obtain the aluminium containing the vanadium titanium: 0.002%V-0.006%Ti-0.002%C-0.0016%N-99.9884%Al.
Embodiment 13
The present embodiment is raw materials used and processing step is as follows:
Raw material is aluminium powder 35kg, (V
0.9ti
0.1) C powder 0.4kg, insulating covering agent sodium-chlor 175g.The aluminium powder measured is placed in to process furnace, and adds insulating covering agent sodium-chlor to be protected, then heating makes its molten aluminum liquid that forms 1200 ℃, then by (V
0.9ti
0.1) the C powder add in aluminium liquid stir after in 1200 ℃ of insulation 0.1h, continue after aluminium alloy is cast into to ingot casting, be cooled to after room temperature the oxide skin of removing the ingot casting surface, obtain the aluminium containing the vanadium titanium: 0.83%V-0.09%Ti-0.22%C-98.86%Al.
Embodiment 14
The present embodiment is raw materials used and processing step is as follows:
Raw material is aluminium powder 35kg, (V
0.1ti
0.9) N powder 0.4kg, insulating covering agent sodium-chlor 175g.The aluminium powder measured is placed in to process furnace, and adds insulating covering agent sodium-chlor to be protected, then heating makes its molten aluminum liquid that forms 1200 ℃, then by (V
0.1ti
0.9) the N powder add in aluminium liquid stir after in 1200 ℃ of insulation 0.1h, continue after aluminium alloy is cast into to ingot casting, be cooled to after room temperature the oxide skin of removing the ingot casting surface, obtain the aluminium containing the vanadium titanium: 0.09%V-0.79%Ti-0.25%N-98.87%Al.
Embodiment 15
The present embodiment is raw materials used and processing step is as follows:
Raw material is aluminum silicon alloy (22%Si, 2%Cu, 1%Mg, 0.9%Mn, 0.35%Ti, 73.75%Al) 99Kg, (V
0.7ti
0.3) (C
0.5n
0.5) powder 1kg.The aluminum silicon alloy measured is placed in to process furnace, and passes into nitrogen protection, flow is 3L/min, and then heating makes its melting aluminum aluminium alloy that forms 800 ℃, then by (V
0.8ti
0.2) (C
0.5n
0.5) powder add in aluminum-silicon alloy liquid stir after in 800 ℃ the insulation 1.5h, continue after aluminium alloy is cast into to ingot casting, be cooled to after room temperature the oxide skin of removing the ingot casting surface, obtain the aluminum silicon alloy containing the vanadium titanium: 21.76%Si-1.98%Cu-0.99%Mg-0.89%Mn-0.56%Ti-0.55%V-0.12%C-0 .14%N-73.01%Al.
Embodiment 16
The present embodiment is raw materials used and processing step is as follows:
Raw material is aluminum silicon alloy (22%Si, 2%Cu, 1%Mg, 0.9%Mn, 0.35%Ti, 73.75%Al) 100Kg, master alloy fining agent (10.22%V-30.65%Ti-10.09%C-8.17%N-40.87%Al) 20g of preparation in embodiment 8.The aluminum silicon alloy measured is placed in to process furnace; and pass into nitrogen protection; flow is 1L/min; then heating makes it form the melting aluminum aluminium alloy of 800 ℃; again the master alloy fining agent is added in aluminum-silicon alloy liquid stir after in 800 ℃ the insulation 1.5h; continue after aluminium alloy is cast into to ingot casting; be cooled to after room temperature the oxide skin of removing the ingot casting surface, obtain the aluminum silicon alloy containing the vanadium titanium: 21.996%Si-2%Cu-1%Mg-0.9%Mn-0.35%Ti-0.002%V-0.002%C-0.001 6%N-73.7484%Al.
Embodiment 17
The present embodiment is raw materials used and processing step is as follows:
Raw material is aluminum-copper alloy (8%Cu, 1.0%Si, 0.25%Mg, 1.2%Mn, 0.15%Ti, 89.4%Al) 2kg, embodiment 8 preparation containing vanadium titanium aluminium intermediate alloy fining agent (15.09%V-0.95%Ti-2.02%C-2.4%N-79.3%Al) 0.4g, insulating covering agent Repone K or lithium chloride 10g.
Be placed in process furnace by aluminum-copper alloy with containing vanadium titanium aluminium intermediate alloy fining agent; and add Repone K or lithium chloride to be protected; then heating makes it form the molten aluminum copper alloy liquid of 900 ℃; be incubated 1h in 900 ℃ after stirring; continue after aluminium alloy is cast into to ingot casting; be cooled to after room temperature the oxide skin of removing the ingot casting surface, obtain the aluminum-copper alloy containing the vanadium titanium: 8%Cu-1%Si-0.25%Mg-1.2%Mn-0.156%Ti-0.002%V-0.002%C-0.0016 %N-89.3884%Al.
Embodiment 18
The present embodiment is raw materials used and processing step is as follows:
Raw material is aluminum magnesium alloy (4.5%Mg, 0.7%Si, 1.5%Zn, 1.4%Mn, 0.2%Ti, 91.7%Al) 9.99kg, insulating covering agent sodium pyrosulfate or Potassium monofluoride 5g, (V
0.7ti
0.3) (C
0.5n
0.5) powder 10g.
The aluminum magnesium alloy measured is placed in to process furnace, and heating makes its molten aluminum liquid magnesium alloy that forms 900 ℃, then by (V
0.7ti
0.3) (C
0.5n
0.5) powder adds in aluminum magnesium alloy liquid after stirring and add sodium pyrosulfate or Potassium monofluoride in 900 ℃ of insulation 1h in 900 ℃, continue after aluminium alloy is cast into to ingot casting, be cooled to after room temperature the oxide skin of removing the ingot casting surface, obtain the aluminum magnesium alloy containing the vanadium titanium: 4.45%Mg-0.69%Si-1.49%Zn-1.39%Mn-0.42%Ti-0.55%V-0.12%C-0. 14%N-90.75%Al.
Embodiment 19
The present embodiment is raw materials used and processing step is as follows:
Raw material is aluminum magnesium alloy (4.5%Mg, 0.7%Si, 1.5%Zn, 1.4%Mn, 0.2%Ti, 91.7%Al) 1kg, embodiment 8 preparation containing vanadium titanium aluminium intermediate alloy fining agent (15.09%V-0.95%Ti-2.02%C-2.4%N-79.3%Al) 0.2g, insulating covering agent sodium pyrosulfate or Potassium monofluoride 5g.
Be placed in process furnace by the aluminum magnesium alloy that measures with containing vanadium titanium aluminium intermediate alloy fining agent; and add sodium pyrosulfate or Potassium monofluoride to be protected; then heating makes it form the molten aluminum liquid magnesium alloy of 900 ℃; be incubated 1h in 900 ℃ after stirring; continue after aluminium alloy is cast into to ingot casting; be cooled to after room temperature the oxide skin of removing the ingot casting surface, obtain the aluminum magnesium alloy containing the vanadium titanium: 4.5%Mg-0.7%Si-1.5%Zn-1.4%Mn-0.216%Ti-0.002%V-0.002%C-0.0 016%N-91.6784%Al.
Embodiment 20
The present embodiment is raw materials used and processing step is as follows:
Raw material is aluminium powder 99g, ammonium meta-vanadate or poly ammonium vanadate powder 0.04g, titanyl sulfate powder 0.03g, gac 0.05g, Graphite Powder 99 0.015g.The ammonium meta-vanadate or poly ammonium vanadate powder, titanyl sulfate powder, gac and the Graphite Powder 99 that measure are carried out to rolling ball milling, ball material mass ratio is 6: 1, Ball-milling Time mixes be limited (approximately 10 hours) with raw material, then will after the raw material stoving mixed, with aluminium foil, wrap up, form blank.The aluminium powder measured is placed in to retort furnace and adds 700 ℃ of molten aluminum liquids of thermosetting, then blank is placed in to the retort furnace of the molten aluminum liquid that is equipped with 700 ℃, be warming up to again 1000 ℃ of insulation 40min, insulation is cast into ingot casting after finishing, remove the ingot casting surface scale after being cooled to room temperature, obtain the aluminium containing the vanadium titanium: 0.016%V-0.014%Ti-0.01%C-99.96%Al.
Embodiment 21
The present embodiment is raw materials used and processing step is as follows:
Raw material is aluminum-copper alloy (8%Cu, 1.0%Si, 0.25%Mg, 1.2%Mn, 0.15%Ti, 89.4%Al) 99g, ammonium vanadate powder 1.85g, titanium acid ammonium 1g, carbon black or wood charcoal powder 1.5g.The ammonium vanadate powder, titanium acid ammonium powder, gac or the Graphite Powder 99 that measure are carried out to rolling ball milling, ball material mass ratio is 6: 1, Ball-milling Time mixes be limited (approximately 10 hours) with raw material, then by the raw material compression moulding the oven dry that mix, pressed compact is of a size of Φ 1.0cm * 2.0cm.The aluminium alloy measured is placed in to process furnace, pass into nitrogen, flow is 0.5L/min, and be heated to 1200 ℃, then pressed compact is added in molten aluminum liquid and stirs, and, at 1200 ℃ of insulation 0.4h, insulation is cast into ingot casting after finishing, be cooled to after room temperature the oxide skin of removing the ingot casting surface, obtain the aluminium alloy containing the vanadium titanium: 7.88%Cu-0.99%Si-0.25%Mg-1.18%Mn-0.55%Ti-0.8%V-0.29%C-0.3 %N-87.76%Al;
Embodiment 22
The present embodiment is raw materials used and processing step is as follows:
Raw material is aluminium powder 750g, sodium metavanadate powder 17.63g, sodium titanate powder 15g, glucose 10g, sucrose 15g.The sodium metavanadate powder, sodium titanate powder, glucose, the sucrose that measure are carried out to rolling ball milling, ball material mass ratio is 6: 1, Ball-milling Time mixes be limited (approximately 24 hours) with raw material, then the raw material mixed is wrapped to form to blank with aluminium foil; The aluminium powder measured is placed in to process furnace, the molten aluminum liquid that adds 700 ℃ of thermosettings, blank is placed in to the retort furnace of the molten aluminum liquid that is equipped with 700 ℃, be incubated 2h in 700 ℃ after stirring, insulation is cast into ingot casting after finishing, be cooled to after room temperature the oxide skin of removing the ingot casting surface, obtain the aluminium containing the vanadium titanium: 0.96%V-0.78%Ti-0.35%C-97.91%Al.
Embodiment 23
Put into respectively the 300g aluminium block in two box type heaters, then the furnace temperature of two box-type furnaces all is warming up to 725 ℃, after the complete melting of aluminium block, add 1.5g fining agent 71.70%Ti-8.09%B-20.21%Al in a box-type furnace, add 1.5g fining agent 76.30%V-3.78%Ti-18.92%C-1%Al (present patent application embodiment 1 preparation is containing vanadium titanium aluminium intermediate alloy fining agent) in another box-type furnace, be cast into aluminium ingot after insulation 2min, be cooled to after room temperature the oxide skin of removing the aluminium ingot surface, taken pictures in the cross section of aluminium ingot respectively, institute's photo that obtains is as Fig. 1, shown in Fig. 2, Fig. 1 is the apparent pattern photo of aluminium ingot that adds the Al-Ti-B fining agent, Fig. 2 adds the apparent pattern photo of aluminium ingot containing vanadium titanium aluminium intermediate alloy fining agent of the present invention.Two photos are compared and can find out, the coarse grains that the crystal grain that in Fig. 1, the aluminium ingot cross section shows obviously shows than aluminium ingot cross section in Fig. 2.This experiment shows, of the present inventionly containing vanadium titanium aluminium intermediate alloy fining agent, the grain refining effect of aluminium and aluminium alloy is better than to the Al-Ti-B fining agent.
Claims (5)
1. the preparation method containing the master alloy fining agent of vanadium titanium aluminium, the component that it is characterized in that described fining agent is aluminium, vanadium, titanium, carbon or/and nitrogen, and the weight percentage of each component is: aluminium 1～99%, vanadium 0.01～77%, titanium 0.01～77%, carbon 0～20%, nitrogen 0～23%; Wherein, carbon, nitrogen have a kind of existence at least in described master alloy fining agent; Processing step is as follows:
(1) batching
Raw material is aluminium and containing vanadium titanium base-material, according to the component aluminium of described fining agent, vanadium, titanium, carbon or/and the weight percentage of nitrogen calculate and the described raw material of weighing;
(2) mixing and moulding
The aluminium that step (1) is prepared and carry out ball milling containing vanadium titanium base-material, Ball-milling Time mixes and is limited with above-mentioned raw materials, then by the raw material compression moulding that mixes or compression moulding after drying, forms pressed compact;
(3) sintering
Pressed compact prepared by step (2) is placed in heat treatment furnace, sintering under the atmosphere that passes into nitrogen or argon gas or hydrogen, 300～750 ℃ of sintering temperatures, soaking time 0.5～4 hour, insulation cools to the furnace below 100 ℃ and comes out of the stove after finishing, and obtains the aluminium intermediate alloy fining agent containing the vanadium titanium;
Described is (V containing vanadium titanium base-material
1-xti
x) C
y, (V
1-xti
x) N
y, (V
1-xti
x) (C
1-y, N
y) at least one, or be VC
y, VN
y, V (C
1-y, N
y) at least one and TiC
y, TiN
y, Ti (C
1-y, N
y) at least one, described VC
y, VN
y, TiC
y, TiN
y, (V
1-xti
x) C
y(V
1-xti
x) N
yin, 0<x<1,0<y≤1, described (V
1-xti
x) (C
1-y, N
y), V (C
1-y, N
y), Ti (C
1-y, N
y) in, 0<x<1,0<y<1;
Or processing step is as follows:
(1) batching
Raw material is aluminum or aluminum alloy and containing vanadium titanium base-material, according to the component aluminium of described fining agent, vanadium, titanium, carbon or/and the weight percentage of nitrogen calculate and the described raw material of weighing;
(2) fusing
The aluminum or aluminum alloy that step (1) is prepared is placed in process furnace, logical rare gas element forms protective atmosphere or adds insulating covering agent, then heating makes it form molten aluminum liquid or the aluminum alloy melt of 650 ℃～1200 ℃, add in aluminium liquid or aluminum alloy melt and, after stirring, at 650 ℃～1200 ℃, be incubated 0.1～2 hour containing vanadium titanium base-material load weighted in step (1) again;
(3) casting is solidified
Aluminium alloy prepared by step (2) is cast into ingot casting, is cooled to after room temperature the oxide skin of removing the ingot casting surface, obtains the aluminium intermediate alloy fining agent containing the vanadium titanium;
Described is (V containing vanadium titanium base-material
1-xti
x) C
y, (V
1-xti
x) N
y, (V
1-xti
x) (C
1-y, N
y) at least one, or be VC
y, VN
y, V (C
1-y, N
y) at least one and TiC
y, TiN
y, Ti (C
1-y, N
y) at least one, described VC
y, VN
y,, TiC
y, TiN
y, (V
1-xti
x) C
y(V
1-xti
x) N
yin, 0<x<1,0<y≤1, described (V
1-xti
x) (C
1-y, N
y), V (C
1-y, N
y), Ti (C
1-y, N
y) in, 0<x<1,0<y<1; Described insulating covering agent is at least one in Repone K, sodium-chlor, lithium chloride, Potassium monofluoride, sodium pyrosulfate;
Or processing step is as follows:
(1) batching
Raw material is aluminium, containing vanadium base-material, titaniferous base-material and carbonaceous reducing agent, according to the weight percentage of the component aluminium of described fining agent, vanadium, titanium, carbon, calculate and the described raw material of weighing;
(2) mixing and moulding
The aluminium powder that step (1) is prepared, containing vanadium base-material, titaniferous base-material and carbonaceous reducing agent, carry out ball milling, Ball-milling Time mixes and is limited with above-mentioned raw materials, then by the raw material compression moulding that mixes or compression moulding after drying, forms pressed compact;
(3) sintering
Pressed compact prepared by step (2) is placed in reduction reaction furnace, or pressed compact prepared by step (2) is placed in reduction reaction furnace and passes into nitrogen or ammonia or its mixed gas, furnace air to be got rid of is warming up to 500 ℃～650 ℃ insulations 0.5 hour～2 hours later, then be heated to 900 ℃～1300 ℃ insulations 1～4 hour, insulation cools to the furnace below 100 ℃ and comes out of the stove after finishing, and obtains the aluminium intermediate alloy fining agent containing the vanadium titanium;
Or pressed compact prepared by step (2) is placed in reduction reaction furnace, be warming up to 500 ℃～650 ℃ insulations 0.1～2 hour under vacuum condition, or add nitrogen or ammonia or its mixed gas while being warming up to 500 ℃～650 ℃ under vacuum condition and in 500 ℃～650 ℃ insulations 0.1～2 hour, then be heated to 900 ℃～1300 ℃ insulations 1～4 hour, insulation cools to the furnace below 100 ℃ and comes out of the stove after finishing, and obtains the aluminium intermediate alloy fining agent containing the vanadium titanium;
Described is V containing the vanadium base-material
2o
5, V
2o
3, at least one in ammonium meta-vanadate, described titaniferous base-material is TiO
2, at least one in metatitanic acid, described carbonaceous reducing agent is at least one in carbon black, gac, graphite, charcoal;
Or processing step is as follows:
(1) batching
Raw material is aluminium, contains vanadium base-material, titaniferous base-material, carbonaceous reducing agent and certainly spread inducer, aluminium, containing vanadium base-material, titaniferous base-material and carbonaceous reducing agent, according to the weight percentage of the component aluminium of described fining agent, vanadium, titanium, carbon, calculate and weighing, certainly to spread inducer be aluminium, containing 0.1～5% of vanadium base-material, titaniferous base-material and carbonaceous reducing agent gross weight;
(2) mixing and moulding
The aluminium that step (1) is prepared, containing vanadium base-material, titaniferous base-material, carbonaceous reducing agent with certainly spread inducer and carry out ball milling, Ball-milling Time mixes and is limited with described raw material, then by the raw material compression moulding or the rear compression moulding of oven dry that mix, form pressed compact;
(3) certainly spread synthetic
Pressed compact prepared by step (2) is placed in process furnace, or pressed compact prepared by step (2) is placed in process furnace and passes into nitrogen, bring out self-propagating reaction at 800 ℃～1300 ℃, after having reacted, cool to the furnace below 100 ℃ and come out of the stove, obtain the aluminium intermediate alloy fining agent containing the vanadium titanium;
Described containing the vanadium base-material be vanadium, containing at least one in barium oxide, described titaniferous base-material is at least one in titanium, titanium-containing oxide, described carbonaceous reducing agent is at least one in carbon black, gac, graphite, wood charcoal powder, and described is a kind of in magnesium, calcium chloride, calcium from spreading inducer;
Or processing step is as follows:
(1) batching
Raw material is aluminium, contains vanadium base-material, titaniferous base-material, carbonaceous reducing agent and certainly spread inducer, aluminium, containing vanadium base-material, titaniferous base-material and carbonaceous reducing agent, according to the weight percentage of the component aluminium of described fining agent, vanadium, titanium, carbon, calculate and the described raw material of weighing, certainly spread inducer and be aluminium, containing the 0.1-5% of vanadium base-material, titaniferous base-material and carbonaceous reducing agent gross weight;
(2) mixing and moulding
Ball milling is carried out in step (1) is prepared contain vanadium base-material, titaniferous base-material, carbonaceous reducing agent and certainly spread inducer, and Ball-milling Time mixes and is limited with described raw material, then, by the raw material compression moulding or the rear compression moulding of oven dry that mix, forms pressed compact;
(3) certainly spread synthetic
The aluminium of step (1) metering is placed in to the molten aluminum liquid that process furnace adds 800 ℃～1300 ℃ of thermosettings, or the aluminium of step (1) metering is placed in to process furnace and passes into nitrogen, then the molten aluminum liquid that adds 800 ℃～1300 ℃ of thermosettings, the pressed compact again prepared by step (2) is placed in the process furnace that above-mentioned molten aluminum liquid is housed, be cast into ingot casting 800 ℃～1300 ℃ insulations after 0.1 hour～2 hours, be cooled to after room temperature the oxide skin of removing the ingot casting surface, obtain the aluminium intermediate alloy fining agent containing the vanadium titanium;
Described containing the vanadium base-material be vanadium, containing at least one in barium oxide, described titaniferous base-material is at least one in titanium, titanium-containing oxide, described carbonaceous reducing agent is at least one in carbon black, gac, graphite, wood charcoal powder, and described is a kind of in magnesium, calcium chloride, calcium from spreading inducer.
2. containing vanadium-titanium-aluminum alloy, it is characterized in that containing the vanadium that weight percentage is 0.001～1% in described aluminium alloy, contain the titanium that weight percentage is 0.001～1%, vanadium, the existence form of titanium in described aluminium alloy are (V
1-xti
x) C
y, (V
1-xti
x) N
y, (V
1-xti
x) (C
1-y, N
y) at least one, or be VC
y, VN
y, V (C
1-y, N
y) at least one and TiC
y, TiN
y, Ti (C
1-y, N
y) at least one, described VC
y, VN
y, TiC
y, TiN
y,(V
1-xti
x) C
y(V
1-xti
x) N
yin, 0<x<1,0<y≤1, described (V
1-xti
x) (C
1-y, N
y), V (C
1-y, N
y), Ti (C
1-y, N
y) in, 0<x<1,0<y<1.
3. according to claim 2 containing vanadium-titanium-aluminum alloy, it is characterized in that comprising with Types Below:
(1) weight percentage of component and each component following containing vanadium-titanium-aluminum alloy: 0.001～1%V, 0.001～1%Ti, 0～0.35%C, 0～0.35%N, surplus is Al, wherein, carbon, nitrogen have a kind of existence at least in described aluminium alloy;
(2) weight percentage of component and each component following containing vanadium titanium aluminum silicon alloy: 4～22%Si, 0～3.5%Cu, 0～1.3%Mg, 0～0.9%Mn, 0.001～1%Ti, 0.001～1%V, 0～0.35%C, 0～0.35%N, surplus is Al, wherein, carbon, nitrogen have a kind of existence at least in described aluminum silicon alloy;
(3) weight percentage of component and each component following containing vanadium titanium aluminum-copper alloy: 4.0～11%Cu, 0～2.0%Si, 0～0.25%Mg, 0～1.2%Mn, 0.001～1%Ti, 0.001～1%V, 0～0.35%C, 0～0.35%N, surplus is Al, wherein, carbon, nitrogen have a kind of existence at least in described aluminum-copper alloy;
(4) weight percentage of component and each component following containing vanadium titanium aluminum magnesium alloy: 4.5～11.0%Mg, 0～1.3%Si, 0～1.5%Zn, 0～1.4%Mn, 0.001～1%Ti, 0.001～1%V, 0～0.35%C, 0～0.35%N, surplus is Al, wherein, carbon, nitrogen have a kind of existence at least in described aluminum magnesium alloy.
4. the preparation method containing vanadium-titanium-aluminum alloy is characterized in that processing step is as follows:
(1) batching
Raw material is aluminum or aluminum alloy and ,Tai source, vanadium source, according to the described chemical composition containing vanadium-titanium-aluminum alloy of claim 2 or 3, calculates and the described raw material of weighing;
(2) fusing
The aluminum or aluminum alloy that step (1) is prepared is placed in process furnace and passes into rare gas element or add insulating covering agent, then heating makes its molten aluminum liquid or aluminum alloy melt that forms 650 ℃～1200 ℃, then by ,Tai source, load weighted vanadium source in step (1) add in aluminium liquid or aluminum alloy melt stir after in 650 ℃～1200 ℃ insulations 0.1～2 hour;
(3) casting is solidified
Aluminium alloy prepared by step (2) is cast into ingot casting, is cooled to after room temperature the oxide skin of removing the ingot casting surface, obtains the aluminium alloy containing the vanadium titanium;
,Tai source, described vanadium source is the master alloy fining agent containing vanadium titanium aluminium prepared by the described method of claim 1, or is (V
1-xti
x) C
y, (V
1-xti
x) N
y, (V
1-xti
x) (C
1-y, N
y) at least one, or be VC
y, VN
y, V (C
1-y, N
y) at least one and TiC
y, TiN
y, Ti (C
1-y, N
y) at least one, described VC
y, VN
y, TiC
y, TiN
y, (V
1-xti
x) C
y(V
1-xti
x) N
yin, 0<x<1,0<y≤1, described (V
1-xti
x) (C
1-y, N
y), V (C
1-y, N
y), Ti (C
1-y, N
y) in, 0<x<1,0<y<1;
Described insulating covering agent is at least one in Repone K, sodium-chlor, lithium chloride, Potassium monofluoride, sodium pyrosulfate.
5. the preparation method containing vanadium-titanium-aluminum alloy is characterized in that processing step is as follows:
(1) batching
Raw material comprises aluminum or aluminum alloy, vanadic salts, titanium salt and carbonaceous reducing agent, and aluminum or aluminum alloy, vanadic salts, titanium salt and carbonaceous reducing agent calculate and weighing according to the described chemical composition in addition of denitrogenating containing vanadium-titanium-aluminum alloy of claim 2 or 3;
(2) mixing and moulding
Vanadic salts, titanium salt and carbonaceous reducing agent that step (1) is prepared carry out ball milling, and Ball-milling Time mixes and is limited with vanadic salts, titanium salt and carbonaceous reducing agent, then by the raw material compression moulding that mixes or be wrapped to form blank with aluminium foil;
(3) fusing and casting
The aluminum or aluminum alloy of step (1) metering is placed in to process furnace, or the aluminum or aluminum alloy of step (1) metering is placed in to process furnace and passes into nitrogen, then be heated to 700 ℃～1200 ℃ and form aluminium liquid or aluminum alloy melt, the blank again prepared by step (2) is placed in the process furnace that above-mentioned molten aluminum liquid or aluminum alloy melt are housed, be cast into ingot casting in 700 ℃～1200 ℃ insulations after 0.4 hour～2 hours, be cooled to after room temperature the oxide skin of removing the ingot casting surface, obtain containing vanadium-titanium-aluminum alloy;
Described vanadic salts is at least one in vanadate, metavanadate, polyoxovanadate, described titanium salt is at least one in titanate, metatitanate, titanyl sulfate, and described carbonaceous reducing agent is at least one in carbon black, gac, graphite, wood charcoal powder, glucose, sucrose.
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| CN106350710A (en) * | 2016-09-30 | 2017-01-25 | 柳州增程材料科技有限公司 | Preparation method of aluminum-magnesium alloy applied to automobile engines |
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| CN109750180A (en) * | 2019-03-20 | 2019-05-14 | 安徽信息工程学院 | A kind of alloy auxiliary material and preparation method thereof |
| CN111424195B (en) * | 2020-05-19 | 2021-08-03 | 吉林大学 | Refiner, preparation method and application thereof, aluminum alloy and refining method thereof |
| CN112809013B (en) * | 2020-12-30 | 2022-05-27 | 中国科学院过程工程研究所 | Preparation method of Ti-6Al-4V alloy powder |
| CN115341116B (en) * | 2021-05-12 | 2023-04-18 | 中国科学院过程工程研究所 | Aluminum-titanium-carbon-nitrogen intermediate alloy refiner and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3625676A (en) * | 1969-03-28 | 1971-12-07 | Frederick H Perfect | Vanadium-aluminum-titanium master alloys |
| CN1258758A (en) * | 1999-12-17 | 2000-07-05 | 东南大学 | Iron-aluminium alloy resisting high-temperature corrosion and abrasion |
| CN101117678A (en) * | 2007-08-31 | 2008-02-06 | 成都银河动力股份有限公司 | Novel non-nickel high-titanium aluminum silicon alloy for piston and heat treatment process therefor |
| CN101397619A (en) * | 2007-09-26 | 2009-04-01 | 洛阳双瑞精铸钛业有限公司 | Novel casting titanium alloy ZTi-6Al-4V-0.01Y |
-
2009
- 2009-09-30 CN CN 200910167820 patent/CN101665882B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3625676A (en) * | 1969-03-28 | 1971-12-07 | Frederick H Perfect | Vanadium-aluminum-titanium master alloys |
| CN1258758A (en) * | 1999-12-17 | 2000-07-05 | 东南大学 | Iron-aluminium alloy resisting high-temperature corrosion and abrasion |
| CN101117678A (en) * | 2007-08-31 | 2008-02-06 | 成都银河动力股份有限公司 | Novel non-nickel high-titanium aluminum silicon alloy for piston and heat treatment process therefor |
| CN101397619A (en) * | 2007-09-26 | 2009-04-01 | 洛阳双瑞精铸钛业有限公司 | Novel casting titanium alloy ZTi-6Al-4V-0.01Y |
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