CN110396614A - A kind of Al-V (C, N) intermediate alloy and preparation method thereof - Google Patents
A kind of Al-V (C, N) intermediate alloy and preparation method thereof Download PDFInfo
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- CN110396614A CN110396614A CN201910676565.4A CN201910676565A CN110396614A CN 110396614 A CN110396614 A CN 110396614A CN 201910676565 A CN201910676565 A CN 201910676565A CN 110396614 A CN110396614 A CN 110396614A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/06—Making non-ferrous alloys with the use of special agents for refining or deoxidising
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/10—Alloys containing non-metals
- C22C1/1036—Alloys containing non-metals starting from a melt
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/10—Alloys containing non-metals
- C22C1/1036—Alloys containing non-metals starting from a melt
- C22C1/1047—Alloys containing non-metals starting from a melt by mixing and casting liquid metal matrix composites
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
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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
- C22C32/0047—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 carbides, nitrides, borides or silicides as the main non-metallic constituents
Abstract
The invention belongs to aluminum grain refiner preparation technical fields, and in particular to a kind of Al-V (C, N) intermediate alloy and its preparation method and application.The present invention is used by that will be dehydrated V (C, N) short-cut method that aluminum melt is added in powder stirring solves V (C, N) the problem of powder and molten aluminum wetability difference, and prepared Al-V (C, N) V (C in intermediate alloy, N) particle is evenly distributed in aluminum substrate, and good with aluminum substrate interface cohesion.New A l-V (the C prepared in the present invention, N) aluminum grain refiner, which can not only refine fine aluminium, can also refine cast aluminium alloy gold, solve element titanium in current common grain refiner (such as Al-B, Al-Ti-B intermediate alloy), boron occurs " poisoning " with silicon, the strontium element in alloy and reacts, the problem of the decline of Yi Yinqi thinning effect.This method preparation process is easy, pollution-free, has a vast market application prospect.
Description
Technical field
The invention belongs to aluminum grain refiner preparation technical fields, and in particular to a kind of Al-V (C, N) intermediate alloy
And its preparation method and application.
Background technique
Aluminium and aluminium alloy have lower density, higher specific strength, good electrical and thermal conductivity, corrosion resistance etc. excellent
Point is widely used in automobile, aerospace and people's daily life.Crystal grain refinement is to improve aluminium and aluminium alloy comprehensive performance
There are many method of one of effective ways, aluminium and aluminum grain refinement, and the cooling velocity, machinery when including control metal freezing are stirred
It mixes, apply outfield (electromagnetism, ultrasound etc.) and the various grain refiners of addition.Industrial most-often used method is to aluminium at present
Various fining agents are added in melt, most-often used grain refiner (Al-Ti-B intermediate alloy) is in melt micronization processes process
In, the elements such as Zr, Cr, Si (when Si content is higher than 4-5wt%) for being easy to appear in grain refining element Ti and alloy occur
" poisoning " reaction, and second phase particles in alloy (TiAl3And TiB2) during standing, since its density ratio aluminium conference produces
Raw aggregate and precipitate, weakens thinning effect.Although TiC in Al-Ti-C intermediate alloy in terms of the nucleation rate more than Al-Ti-B among
TiB in alloy2, but TiC stability in aluminum melt is poor, and there is the problems such as preparation is complicated, at high cost.Therefore, novel
Aluminum grain refiner must have stable chemical property and efficient refining efficiency, and preparation process has innovation,
The features such as low cost, low pollution.
V (C, N) has fusing point height, stability good and anti-toxicity energy.And V (C, N) and aluminium belong to face-centered cubic point
The lattice constant of battle array, the two differs very little, respectively 0.4139nm and 0.4049nm.It is therefore possible to as the different of primary aluminium phase
Matter forming core core promotes forming core and the refinement of primary aluminium phase.And existing technical literature (101618454 A of CN) is used for aluminium and aluminium
The preparation process of the fining agent containing vanadium of alloy still remains deficiency below: (1) sintering and self-spread synthesizing method preparation process are numerous
It is trivial, preparation cost is high, and with both techniques prepare fining agent be difficult to sufficiently, rapidly incorporate molten aluminum in；(2) directly molten
Base materials powder containing vanadium is added in molten aluminum liquid, powder can be made to be difficult to enter molten aluminum, alloying is difficult, it is difficult to realize industrialized production with
Using.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of grain refiner as aluminium and aluminium alloy
The simple preparation method of (Al-V (C, N) intermediate alloy), using the letter that aluminum melt will be added by the way that the stirring of V (C, N) powder will be dehydrated
Just method prepares new A l-V (C, N) aluminum grain refiner, and the novel aluminum alloy grain refiner developed can refine
Fine aluminium can also refine cast aluminium alloy gold, can be applied to the batch production of aluminium casting, provide for aluminium and aluminum grain refinement new
Selection.
The technical scheme is that
Al-V (C, N) intermediate alloy of the invention, with commercial-purity aluminium, V (C, N) powder is raw material, is made in accordance with the following methods
It is standby to obtain:
Step 1: V (C, N) powder is placed in Muffle furnace in 500 DEG C of heat preservation 1h, its removal absorption water and the crystallization water are made, and
Loose grey black V (C, N) block is obtained, is placed in spare in drying basin, while commercial-purity aluminium being preheated in high temperature oven
200℃-250℃；
Step 2: in experimental resistance furnace by the commercial-purity aluminium after being preheated in the step 1 in 740 DEG C of -760 DEG C of fusings, heat preservation
20min~40min obtains aluminum melt；
Step 3: the aluminum melt obtained in the step 2 being cooled to 700 DEG C -730 DEG C, institute is added thereto while stirring
Loose V (C, N) block obtained in step 1 is stated, until all adding；
Step 4: melt finally obtained in step 3 is warming up to 800 DEG C of -900 DEG C of heat preservation 0.5h~1h, during which every
10-15min is stirred melt, and melt is then cooled to 720 DEG C -740 DEG C, is added into melt and accounts for molten aluminum mass fraction
The C of 0.3%-0.5%2Cl6Refining agent, stirring refining 5min~10min, stands heat preservation 8min~12min, finally will uniformly melt
Body pours into the metal type dies for being preheated to 200 DEG C -250 DEG C, obtains grain refiner after cooling.
V (C, the N) powder is known as vanadium carbide nitride powder, is a kind of product carbon containing in vanadium nitride product, wherein respectively at
The mass fraction divided: V 79%, N 12%, C 7%, surplus are impurity, are commercially available.Carbon-free nitridation can also be used
Vanadium substitution, but higher cost.
Further, in the preparation method of above-mentioned Al-V (C, N) intermediate alloy, the V (C, N) powder quality score is
The 5%-10% of melt gross mass.
Further, in the method for the present invention, using V (C, N) in 500 DEG C of dehydrations and the blocking characteristics of easy-sintering completely,
Its surface roughness is increased, specific surface area increases, and its surface-active is improved, its angle of wetting with molten aluminum is reduced, so as to
To be added in molten aluminum quickly.
V (C, N) has fusing point height, stability good and anti-toxicity energy in the present invention.And V (C, N) and aluminium belong to face
The lattice constant of heart cubic lattice, the two differs very little.It is therefore possible to the heterogeneous forming core cores as primary aluminium phase, promote just
The forming core of cast alumin(i)um phase and refinement.
In the method for the present invention, the roughness on surface is increased after high-temperature process using V (C, N), is formed in particle surface
Oxide layer improves surface-active, reduces its angle of wetting with molten aluminum so that specific surface area increases.In conjunction with while stirring plus
The mode of material solves the problem of the wetability difference of V (C, N) and molten aluminum, so as to so that it is soon added and is dissolved into aluminium
In liquid.
Compared with prior art, the invention has the following advantages:
(1) new A l-V (C, N) intermediate alloy that the present invention synthesizes can not only refine commercial-purity aluminium, moreover it is possible to preferably refinement
Cast aluminium alloy gold.Solve element titanium, boron and alloy in grain refiner (Al-B, Al-Ti-B intermediate alloy) common at present
In the elements such as silicon, strontium occur " poisoning " reaction, the problem of the decline of Yi Yinqi thinning effect.To improve the comprehensive of cast aluminium alloy gold
Mechanical property is closed, and its casting character can be improved.
(2) present invention obtains loose grey black V (C, N) block after 500 DEG C completely dehydration using V (C, N), in conjunction with
The mode to feed while stirring effectively avoids that V (C, N) powder is directly added to cause the powder directly to float on molten aluminum surface and need
Higher temperature, which can just melt, arrives the problems in molten aluminum.
(3) present invention prepares new A l-V using the short-cut method that aluminum melt will be added by that will be dehydrated the stirring of V (C, N) powder
(C, N) aluminum grain refiner, preparation process is pollution-free, V (C, N) in resulting Al-V (C, N) aluminum grain refiner
Particle is evenly distributed in aluminum substrate, and good with aluminum substrate interface cohesion.
Detailed description of the invention
Fig. 1 is that embodiment 1 prepares Al-6wt.%V (C, N) intermediate alloy microscopic structure.
Fig. 2 is that embodiment 1 obtains the macrocorrosion that (a) is not added with the commercial-purity aluminium of fining agent (b) plus fining agent of the present invention
Macrograph.
Fig. 3 is that embodiment 2 obtains (a) and be not added with fining agent (b) plus fining agent (c) of the present invention adding Al-5Ti-B fining agent
The macrocorrosion macrograph of A356 alloy.
Fig. 4 is that embodiment 3 obtains (a) and is not added with fining agent (b) plus fining agent of the present invention and with the change of Al-10Sr intermediate alloy
The A356 alloy microstructure photo of matter.
Specific embodiment
Below with reference to embodiment and Figure of description, the present invention is further illustrated.
Embodiment 1:
Prepare 500g Al-V (C, N) intermediate alloy grain refiner, constituent mass percentage are as follows: V (C, N) powder is
6%, commercial-purity aluminium 94%, preparation process is as follows:
(1) ingredient: V (C, N) powder 30g, commercial-purity aluminium 470g；
(2) V (C, N) powder is placed in Muffle furnace in 500 DEG C of heat preservation 1h, makes its removal absorption water and the crystallization water, and obtain
Loose V (C, N) block, be placed in spare in drying basin, while commercial-purity aluminium being preheated to 250 DEG C in high temperature oven；
(3) commercial-purity aluminium after preheating is melted in experimental resistance furnace at 760 DEG C, keeps the temperature 20min, obtain aluminum melt；
(4) aluminum melt is cooled to 700 DEG C, loose V (C, N) block is added thereto while stirring, until all adding；
(5) finally obtained melt is warming up to 850 DEG C of heat preservation 1h, during which melt is stirred every 15min, then
Melt is cooled to 740 DEG C, the C for accounting for molten aluminum mass fraction 0.3% is added into melt2Cl6Refining agent, stirring refines 5min, quiet
Set heat preservation 10min, finally improving uniformity of melt is poured into the steel mold for being preheated to 250 DEG C, after cooling obtain Al-6wt.%V (C,
N) grain refiner.Its microscopic structure is as shown in Figure 1, V (C, N) particle is evenly distributed in aluminum substrate.
Intermediate alloy grain refiner obtained above is added in commercial-purity aluminium, additional amount is 0.3% (quality percentage
Than), it is poured into steel mold after 750 DEG C of standing 30min, macrostructure is as shown in Figure 2.After adding fining agent, crystal grain group
It knits to have obtained apparent refinement.
Embodiment 2:
Prepare 500g Al-V (C, N) intermediate alloy grain refiner, constituent mass percentage are as follows: V (C, N) powder is
5%, commercial-purity aluminium 95%, preparation process is as follows:
(1) ingredient: V (C, N) powder 25g, commercial-purity aluminium 475g；
(2) V (C, N) powder is placed in Muffle furnace in 500 DEG C of heat preservation 1h, makes its removal absorption water and the crystallization water, and obtain
Loose V (C, N) block, be placed in spare in drying basin, while commercial-purity aluminium being preheated to 200 DEG C in high temperature oven；
(3) commercial-purity aluminium after preheating is melted in experimental resistance furnace at 750 DEG C, keeps the temperature 30min, obtain aluminum melt；
(4) aluminum melt is cooled to 720 DEG C, loose V (C, N) block is added thereto while stirring, until all adding；
(5) finally obtained melt is warming up to 800 DEG C of heat preservation 1h, during which melt is stirred every 10min, then
Melt is cooled to 740 DEG C, the C for accounting for molten aluminum mass fraction 0.4% is added into melt2Cl6Refining agent, stirring refines 6min, quiet
Set heat preservation 12min, finally improving uniformity of melt is poured into the steel mold for being preheated to 200 DEG C, after cooling obtain Al-5wt.%V (C,
N) grain refiner.
Intermediate alloy grain refiner obtained above is added in A356 alloy, additional amount is 0.5% (quality percentage
Than), it is poured into steel mold after 750 DEG C of standing 30min.At identical conditions, by the bulk of 0.5% (mass percent)
Al-5Ti-B intermediate alloy is added in A356 alloy.Compare the thinning effect of the two, macrostructure is as shown in Figure 3.Al-
5wt.%V (C, N) intermediate alloy is more preferable to A356 alloy refinement effect than block-like Al-5Ti-B intermediate alloy.
Embodiment 3:
Prepare 500g Al-V (C, N) intermediate alloy grain refiner, constituent mass percentage are as follows: V (C, N) powder is
8%, commercial-purity aluminium 92%, preparation process is as follows:
(1) ingredient: V (C, N) powder 40g, commercial-purity aluminium 460g；
(2) V (C, N) powder is placed in Muffle furnace in 500 DEG C of heat preservation 1h, makes its removal absorption water and the crystallization water, and obtain
Loose V (C, N) block, be placed in spare in drying basin, while commercial-purity aluminium being preheated to 250 DEG C in high temperature oven；
(3) commercial-purity aluminium after preheating is melted in experimental resistance furnace at 740 DEG C, keeps the temperature 20min, obtain aluminum melt；
(4) aluminum melt is cooled to 710 DEG C, loose V (C, N) block is added thereto while stirring, until all adding；
(5) finally obtained melt is warming up to 900 DEG C of heat preservation 1h, during which melt is stirred every 15min, then
Melt is cooled to 740 DEG C, the C for accounting for molten aluminum mass fraction 0.3% is added into melt2Cl6Refining agent, stirring refines 5min, quiet
Set heat preservation 10min, finally improving uniformity of melt is poured into the steel mold for being preheated to 250 DEG C, after cooling obtain Al-8wt.%V (C,
N) grain refiner.
Intermediate alloy obtained above is added in the A356 alloy to be gone bad with Al-10Sr intermediate alloy, additional amount
For 0.5% (mass percent), it is poured into steel mold after 750 DEG C of standing 30min, metallographic structure is as shown in Figure 4.Addition
In A356 Solidification Structure after fining agent, isometry mutually takes place in primary aluminium, be in tiny petal-shaped, while Eutectic Silicon in Al-Si Cast Alloys according to
Tiny coralliform is so kept, illustrates that the element in grain refiner does not have to react with strontium " poisoning ".
Claims (7)
1. a kind of Al-V (C, N) intermediate alloy, it is characterised in that: the intermediate alloy with commercial-purity aluminium, V (C, N) powder be raw material,
The mass percent of each ingredient: V (C, N) powder is 5%-10%, and commercial-purity aluminium 90%-95% is prepared in accordance with the following methods
It obtains:
Step 1: V (C, N) powder, which is placed in Muffle furnace heat preservation, makes its removal absorption water and the crystallization water, and obtains loose greyish black
Color V (C, N) block, is placed in spare in drying basin, while commercial-purity aluminium being preheated in high temperature oven；
Step 2: the commercial-purity aluminium after preheating in the step 1 being melted in experimental resistance furnace, obtains aluminum melt after heat preservation；
Step 3: the aluminum melt obtained in the step 2 being cooled to 700 DEG C -730 DEG C, the step is added thereto while stirring
Loose grey black V (C, N) block obtained in rapid 1 obtains melt until all adding；
Step 4: melt finally obtained in step 3 being warming up to 800 DEG C of -900 DEG C of heat preservation 0.5h~1h, during which every 10-
15min is stirred melt, and melt is then cooled to 720 DEG C -740 DEG C, is added refining agent into melt, stirring refining,
Heat preservation is stood, finally improving uniformity of melt is poured into the metal type dies of preheating, obtains grain refiner after cooling.
2. a kind of Al-V (C, N) intermediate alloy as described in claim 1, it is characterised in that: in step 1, by V (C, N) powder
It is placed in Muffle furnace in 500 DEG C of heat preservation 1h, commercial-purity aluminium is preheated to 200 DEG C -250 DEG C in high temperature oven.
3. a kind of Al-V (C, N) intermediate alloy as described in claim 1, it is characterised in that: in step 2, commercial-purity aluminium fusing
Temperature is 740 DEG C -760 DEG C, and soaking time is 20min~40min.
4. a kind of Al-V (C, N) intermediate alloy as described in claim 1, it is characterised in that: in step 3, the V (C, N)
Powder quality score is the 5%-10% of melt gross mass.
5. a kind of Al-V (C, N) intermediate alloy as described in claim 1, it is characterised in that: in step 4, refining agent C2Cl6
Refining agent, additional amount account for molten aluminum mass fraction 0.3%-0.5%；Stirring refining 5min~10min, standing heat preservation 8min~
12min；The preheating temperature of metal type dies is 200 DEG C -250 DEG C.
6. a kind of Al-V (C, N) intermediate alloy as described in claim 1, it is characterised in that: V (C, the N) powder is known as carbon
Vanadium powder is nitrogenized, is a kind of product carbon containing in vanadium nitride product, wherein the mass fraction of each ingredient: V 79%, N 12%,
C is 7%, and surplus is impurity.
7. a kind of Al-V (C, N) intermediate alloy as described in claim 1, it is characterised in that: substitute V using carbon-free vanadium nitride
(C, N) powder.
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| CN115341116A (en) * | 2021-05-12 | 2022-11-15 | 中国科学院过程工程研究所 | Aluminum-titanium-carbon-nitrogen intermediate alloy refiner and preparation method thereof |
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