CN101838759A - 4032 alloy alterant and use method thereof - Google Patents
4032 alloy alterant and use method thereof Download PDFInfo
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- CN101838759A CN101838759A CN201010301095A CN201010301095A CN101838759A CN 101838759 A CN101838759 A CN 101838759A CN 201010301095 A CN201010301095 A CN 201010301095A CN 201010301095 A CN201010301095 A CN 201010301095A CN 101838759 A CN101838759 A CN 101838759A
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Abstract
本发明涉及一种4032合金的变质剂及其使用方法，该变质剂采用Al-P和Al-5Ti-B中间合金组成，各元素重量百分比组成为：P：0.028-0.056％，Ti：0.01-0.07％，B：0.002-0.014％，余量为铝。其使用方法的关键为：4032合金初精炼后在750-850℃加入4032合金配料重量的0.6-1.6％A1-3.5％P变质剂，搅拌均匀，保温15-100min；再精炼；在750-770℃，加入4032合金重量的0.3-1.6％Al-5Ti-B，保温5-12min。采用本发明的变质剂及其使用方法，可使4032合金在热加工及热处理之前，初晶硅细化到18μm，球化率超过50％，力学性能大大提高。本发明实现了对4032合金的有效变质，同时为共晶型铝硅合金的变质技术拓展了新思路。
The present invention relates to a 4032 alloy modifier and its application method. The modifier is composed of Al-P and Al-5Ti-B master alloy, and the weight percentage of each element is composed of: P: 0.028-0.056%, Ti: 0.01- 0.07%, B: 0.002-0.014%, the balance is aluminum. The key to its use is: after initial refining of the 4032 alloy, add 0.6-1.6% A1-3.5% P modifier of the weight of the 4032 alloy ingredients at 750-850 ° C, stir evenly, and keep warm for 15-100 minutes; re-refining; at 750-770 ℃, add 0.3-1.6% Al-5Ti-B by weight of 4032 alloy, and keep warm for 5-12min. By adopting the modificator and its application method of the present invention, the primary crystal silicon can be refined to 18 μm, the spheroidization rate exceeds 50%, and the mechanical properties are greatly improved before the thermal processing and heat treatment of the 4032 alloy. The invention realizes the effective modification of the 4032 alloy, and at the same time expands a new idea for the modification technology of the eutectic aluminum-silicon alloy.
Description
Technical field
The invention belongs to field of metallurgy, particularly a kind of alterant of 4032 aluminium alloys and using method thereof.
Background technology
Aluminum silicon alloy has high strength, high abrasion and low-expansion coefficient, and advantages of good casting, and wide application prospect is arranged in mechanical industry, automotive industry, aviation and war industry.The main component of 4032 alloys is Al, Si, Cu, Mg, Ni, and average silicon content is 12.2%, near the eutectic point of aluminium silicon phasor, is a kind of nearly cocrystallized Al-Si alloy.The characteristic of the existing cast aluminium alloy of 4032 alloys has the characteristics of wrought aluminium alloy again, is usually used in processing forging and forging stock, as high-abrasive material for making piston and at other parts of hot operation.Uninoculated 4032 alloys, primary silicon is thick and present irregular bulk, causes unit elongation and tensile strength lower.Therefore, when producing 4032 alloys, must carry out respective handling, refinement silicon phase and its shape of change.The method of refinement silicon phase is a lot, and stable and the most feasible method is to add alterant element in the industrial production, as rare earth, P, Sr, Na etc., and be equipped with other technology assist measures, as viscous deformation and thermal treatment, and the shape of change primary silicon makes the research of its nodularization also fewer.At present, industrial general employing Sr 4032 alloys that go bad, because Sr is better to the Eutectic Silicon in Al-Si Cast Alloys modification effect, and rotten validity period is long, still, its modification process is difficult for grasping, specific absorption is low, latent period is long, pin hole appears in foundry goods easily.
The alterant of cocrystallizing type aluminum silicon alloy is mainly Na salt, strontium, phosphorus, rare earth and oxide compound thereof.Na salt is mainly by NaF, NaCl, KCl, the Na of different proportionings
3AlF
6Be composited, strontium mainly adds with the form of Al-Sr master alloy, and phosphorus has also experienced the development course of red phosphorus, Cu-P master alloy, Al-Cu-P master alloy, Al-P master alloy.Na salt pair crucible infringement is bigger, and fluorion wherein pollutes the environment, and strontium is rotten air-breathing serious, the rare earth modification effect is limited and cost an arm and a leg, these a few class alterants are because above-mentioned former thereby given up by most of producer, take all factors into consideration and have only Al-P environmental protection and validity period long, and modification effect is better.But Al-P also can only be with the primary silicon refinement and the polygonization that becomes, and spheroidization is not obvious.Titaniferous, the master alloy of boron is often as grain-refining agent, add chute in the melting final stage, seldom cooperate the Al-P master alloy rotten as alterant it to primary silicon, Chinese patent CN101058855A has reported a kind of hypereutectic type aluminum silicon alloy fibrous tissue thinning process, add earlier and contain the Ti grain-refining agent, the back has added Phosphorus alterant (powder) refinement primary silicon, CN1861820A has reported a kind of thin silk ribbon shape alterant and application method thereof by Cu-P and the preparation of Al-5Ti-B master alloy, " Special Processes of Metal Castings and non-ferrous alloy " 2006 the 26th 5 phases of volume have reported that human 0.8%Al-P such as Liu Xiang Fa of Shandong University and 0.1-0.2%Al-5Ti-B are 780 ℃ of rotten ZL 109 alloy, primary silicon has been obtained modification effect preferably, and concrete technology is not described in detail, and 780 ℃ of maintenances are constant when adding Al-5Ti-B, do not adjust furnace body temperature because add different alterants, the primary silicon of more than having reported all refinements, but nodularization DeGrain.At present, 4032 alloy modifications are handled the less of research,, only contain P by interpolation and the allometamorphism agent just makes primary silicon be refined to below the 18 μ m and 50% above nodularization in smelt stage without follow-up distortion and thermal treatment, such alterant and modification process thereof are not also reported at present.
Summary of the invention
The objective of the invention is to overcome the defective of 4032 alloy modification technology, propose a kind of 4032 alloys comparatively ideal alterant and using method, its nodularization effect is obvious; Just can improve the alloy organizing performance preferably before hot-work and heat treatment step, the rotten processing for the cocrystallizing type aluminum silicon alloy simultaneously provides new approaches.
Main contents of the present invention are: on the basis of 4032 alloys, add the Al-3.5%P master alloy of trace at a certain temperature earlier, add trace of Al-5Ti-B master alloy, casting ingot-forming after rotten for some time.Alterant composition provided by the present invention (weight percent, wt%) scope is: 0.028-0.056%P, 0.01-0.07%Ti, 0.002-0.014%B, surplus is Al.
The alterant using method of above-mentioned 4032 alloys realizes as follows:
(1) batching: the fine aluminium with 99.9% and other master alloys shape that is cut into small pieces, remove surface impurity and oven dry, it is standby that the ratio of forming in alloy prepares starting material;
(2) alloy melting: smelting temperature is set at 755-765 ℃, and fusing fine aluminium and Al-Si, Al-Cu, Al-Ni master alloy in resistance furnace fully stir;
(3) add Mg: treat that alloy all melts the back at insulating covering agent (45%NaCl+30%KCl+25%Na
3AlF
6) protect and use the bell jar plunging to add the bigger metal M g of scaling loss down,
(4) refining just: adopt C
2Cl
6+ Na
2SiF
6Gas and impurity in the melt are removed in the degasification refining, leave standstill 10 minutes, take surface scum off;
(5) add phosphorus modification:, stir insulation 15-100min at 750-850 ℃ of 0.6-1.6%Al-3.5%P alterant that adds above-mentioned alloying ingredient weight;
(6) refining again: remove gas and impurity in the melt, left standstill 5 minutes, take surface scum off, refining transfers to temperature 750-770 ℃ simultaneously, prepares for adding titanium boron alterant;
(7) adding titanium boron goes bad: add above-mentioned alloying ingredient weight 0.3-1.6%Al-5Ti-B, insulation 5-12min;
(8) ingot casting: at 730-750 ℃ of cast, ingot casting.
Above-mentioned using method, its preferred version have following 3 kinds:
1, the 0.9-1.3%Al-3.5%P that adds 4032 alloying ingredient weight in the above-mentioned metamorphic process that phosphorates is at 775-790 ℃ of insulation 70-90min down, refining and add in the titanium boron metamorphic process and be incubated 8-10min at 760 ℃ of 1.0-1.4%Al-5Ti-B that add 4032 alloying ingredient weight.
2, the 0.7-0.9%Al-3.5%P that adds 4032 weight alloy in the above-mentioned metamorphic process that phosphorates is at 790-820 ℃ of insulation 70-90min, refining and add in the titanium boron metamorphic process and be incubated 8-10min at 760 ℃ of 1.2-1.5%Al-5Ti-B that add 4032 alloying ingredient weight.
3, the 0.9-1.3%Al-3.5%P that adds 4032 weight alloy in the above-mentioned metamorphic process that phosphorates is at 775-790 ℃ of insulation 20-30min, refining and add titanium boron metamorphic process and be incubated 8-10min at 760 ℃ of 0.3-0.5%Al-5Ti-B that add 4032 alloying ingredient weight.
Beneficial effect
Alterant of the present invention and using method thereof have realized need not other subsequent techniques just to the effect of the improvement of 4032 alloy structure performances.P adds in the molten aluminium can form the AlP particle, its fusing point is than primary silicon formation temperature height, and it is similar to silicon crystalline structure, lattice parameter is close, can be used as heterogeneous core, thereby make the nucleus number increase refinement primary silicon to a certain extent: the Al-5Ti-B alloy adds behind the rotten molten aluminium of P can form a kind of TiB
2Particle, this particle can adsorb the AlP particle, has limited the AlP particle in the distribution of silicon outside mutually, has improved the rotten efficient of P to primary silicon, existing basic enterprising step refining, nodularization primary silicon.But, TiB
2Particle is gathered into bigger group sometimes, and some the time TiB
2Particle distribution is relatively disperseed again and is even.TiB
2The size of particle is by proportioning and Al-P deterroration and the soaking time acting in conjunction decision of Al-5Ti-B and Al-P.Work as TiB
2When particle is bigger, though can improve the utilization ratio of Al-P master alloy, also make the crystallization nuclei of primary silicon become bigger simultaneously, these two kinds of effects are cancelled out each other, thereby primary silicon there is no considerable change in the microtexture.Work as TiB
2Particle distribution is relatively disperseed and evenly the time, except can improving the Al-P utilization ratio, can also be made AlP distribution of particles homodisperse more, thereby it is played a role.Therefore reasonably alterant proportioning and deterroration and soaking time can improve AlP and TiB greatly
2Coordinative role, i.e. crystal grain thinning refinement nodularization primary silicon again, thereby structure property all is improved.The composition proportion of this alterant, the deterroration when using and the synthetic setting of soaking time are the keys that concerns modification effect, and the variation of any one condition all may cause the very big difference of effect.The contriver finds out the alterant and the using method that are fit to 4032 alloy modifications according to the characteristics of 4032 alloys self.The present invention is before hot-work and heat treatment step, the size of alloy primary silicon is reached below the 18um, best rotten scheme can make the primary silicon size reach below the 10um, the as-cast structure unit elongation can reach 2-6%, tensile strength can reach 240-320MPa, by follow-up extruding or forging and thermal treatment the alloy structure performance is improved greatly again.In addition, the present invention is effective to the nodularization of primary silicon, can make 50% above primary silicon nodularization, and all the other primary silicons also all go bad to polygon-shaped, no bulk or lath-shaped primary silicon.
4032 alloy inoculants of the present invention have directly adopted Al-P and two kinds of master alloys of grain-refining agent Al-5Ti-B of using always in the industry, alterant is easy to obtain, it is synthetic to need not the special process preparation, provide cost savings, technology is simple, using method is easy, and not needing increases special-purpose utility appliance, and industrial operation is convenient in use.
4032 alloy inoculants of the present invention adopt the master alloy form to add, but not powder type has been avoided a large amount of dust and P
2O
5The diffusion of gas, and the Al-P alloy itself is exactly a kind of green alterant, so environmental protection is little to environmental influence.
4032 alloy inoculants of the present invention do not contain air-breathing serious elements such as Sr, and do not destroy the oxide film of aluminium liquid surface compact, can not break oxide film and ambient atmos and inside [H] three's balance, ingot casting pin hole rate is lower, and its scope is between 0.001-0.272%.
Description of drawings
Fig. 1 organizes photo by the rotten 4032 alloys gold picture of embodiment 1 method;
Fig. 2 organizes photo by the rotten 4032 alloys gold picture of embodiment 2 methods;
Fig. 3 organizes photo by the rotten 4032 alloys gold picture of embodiment 3 methods;
Fig. 4 organizes photo by the rotten 4032 alloys gold picture of comparative example's 1 method.
Embodiment
Below with reference to accompanying drawings, the present invention is further described by embodiment, and can not limit the present invention.
Embodiment 1:
By 1000 gram batching weighings, in the 5KW crucible electrical resistance furnace, put into the intensification of high purity graphite crucible and be preheated to 760 ℃, add 271.77 gram commercial-purity aluminiums (99.97%) and 613.2 gram Al-20.5%Si, 22.68 gram Al-40%Cu, 90 gram Al-10%Ni evenly are filled with by 45%NaCl+30%KCl+25%Na simultaneously
3AlF
6The flux of forming covers, and melting of metal after half an hour is depressed the pure Mg of the 10.5g that wraps with aluminium foil with bell jar and gone into the bottom, molten bath to fusing fully approximately, takes out bell jar, fully stirs, and leaves standstill 5min, the 8 gram C that will wrap with aluminium foil
2Cl
6With 2 gram Na
2SiF
6Mixed powder be pressed into the degasification refining of molten bath bottom with bell jar, leave standstill 10min, take surface scum off.Furnace temperature is transferred to 780 ℃, depress the 12 gram Al-3.5%P that wrap with aluminium foil, stir insulation 80-90min with bell jar.Degasification refining once more transfers to furnace temperature 760 ℃ simultaneously, leaves standstill 5min, and the back of skimming adds 10 gram Al-5Ti-B, behind the insulation 10min at 730-740 ℃ of casting ingot-forming.Figure 1 shows that the gold picture tissue of the ingot casting that embodiment 1 obtains, table 1 is its comprehensive evaluation form.
Table 1 4032 alloy modification comprehensive evaluation forms (embodiment 1)
Embodiment 2:
By 1000 gram batching weighings, in the 5KW crucible electrical resistance furnace, put into the intensification of high purity graphite crucible and be preheated to 760 ℃, add 271.77 gram commercial-purity aluminiums (99.97%) and 613.2 gram Al-20.5%Si, 22.68 gram Al-40%Cu, 90 gram Al-10%Ni evenly are filled with by 45%NaCl+30%KCl+25%Na simultaneously
3AlF
6The flux of forming covers, and melting of metal after half an hour is depressed the pure Mg of the 10.5g that wraps with aluminium foil with bell jar and gone into the bottom, molten bath to fusing fully approximately, takes out bell jar, fully stirs, and leaves standstill 5min, the 8 gram C that will wrap with aluminium foil
2Cl
6With 2 gram Na
2SiF
6Mixed powder be pressed into the degasification refining of molten bath bottom with bell jar, leave standstill 10min, take surface scum off.Furnace temperature is transferred to 800 ℃, depress the 8 gram Al-3.5%P that wrap with aluminium foil, stir insulation 80-90min with bell jar.Degasification refining once more transfers to furnace temperature 760 ℃ simultaneously, leaves standstill 5min, and the back of skimming adds 14 gram Al-5Ti-B, behind the insulation 10min at 730-740 ℃ of casting ingot-forming.Figure 2 shows that the gold picture tissue of the ingot casting that embodiment 2 obtains, table 2 is its comprehensive evaluation form.
Table 2 4032 alloy modification comprehensive evaluation forms (embodiment 2)
Embodiment 3:
By 1000 gram batching weighings, in the 5KW crucible electrical resistance furnace, put into the intensification of high purity graphite crucible and be preheated to 760 ℃, add 271.77 gram commercial-purity aluminiums (99.97%) and 613.2 gram Al-20.5%Si, 22.68 gram Al-40%Cu, 90 gram Al-10%Ni evenly are filled with by 45%NaCl+30%KCl+25%Na simultaneously
3AlF
6The flux of forming covers, and melting of metal after half an hour is depressed the pure Mg of the 10.5g that wraps with aluminium foil with bell jar and gone into the bottom, molten bath to fusing fully approximately, takes out bell jar, fully stirs, and leaves standstill 5min, the 8 gram C that will wrap with aluminium foil
2Cl
6With 2 gram Na
2SiF
6Mixed powder be pressed into the degasification refining of molten bath bottom with bell jar, leave standstill 10min, take surface scum off.Furnace temperature is transferred to 780 ℃, depress the 12 gram Al-3.5%P that wrap with aluminium foil, stir insulation 20-30min with bell jar.Degasification refining once more transfers to furnace temperature 760 ℃ simultaneously, leaves standstill 5min, and the back of skimming adds 4 gram Al-5Ti-B, behind the insulation 10min at 730-740 ℃ of casting ingot-forming.Figure 3 shows that the gold picture tissue of the ingot casting that embodiment 3 obtains, table 3 is its comprehensive evaluation form.
Table 3 4032 alloy modification comprehensive evaluation forms (embodiment 3)
The comparative example 1:
By 1000 gram batching weighings, in the 5KW crucible electrical resistance furnace, put into the intensification of high purity graphite crucible and be preheated to 760 ℃, add 271.77 gram commercial-purity aluminiums (99.97%) and 613.2 gram Al-20.5%Si, 22.68 gram Al-40%Cu, 90 gram Al-10%Ni evenly are filled with by 45%NaCl+30%KCl+25%Na simultaneously
3AlF
6The flux of forming covers, and melting of metal after half an hour is depressed the pure Mg of the 10.5g that wraps with aluminium foil with bell jar and gone into the bottom, molten bath to fusing fully approximately, takes out bell jar, fully stirs, and leaves standstill 5min, the 8 gram C that will wrap with aluminium foil
2Cl
6With 2 gram Na
2SiF
6Mixed powder be pressed into the degasification refining of molten bath bottom with bell jar, leave standstill 10min, take surface scum off.Furnace temperature is transferred to 760 ℃, depress the 4 gram Al-3.5%P that wrap with aluminium foil, stir insulation 80-90min with bell jar.Degasification refining once more transfers to furnace temperature 760 ℃ simultaneously, leaves standstill 5min, and the back of skimming adds 1 gram Al-5Ti-B, behind the insulation 10min at 730 ℃ of casting ingot-formings.This comparative example is the experiment outside application method scope of the present invention, and the gold picture tissue of the ingot casting that Fig. 4 obtains for comparative example 4, table 4 are its comprehensive evaluation form, and as can be seen, primary silicon is thick, and water caltrop is clearly demarcated, and mechanical property is not good yet.
Table 4 4032 alloy modification comprehensive evaluation forms (comparative example 4)
Claims (5)
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102296194A (en) * | 2011-09-05 | 2011-12-28 | 陕西理工学院 | Preparation method of internal grown silicon reinforced zinc-based abrasion resistant material |
| CN103471893A (en) * | 2013-09-22 | 2013-12-25 | 东北轻合金有限责任公司 | 4032 aluminum alloy spectroscopic and chemical standard sample and preparation method thereof |
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| CN107236875A (en) * | 2017-06-23 | 2017-10-10 | 常州大学 | A kind of phosphorus titanium dual metamorphism method of cocrystallized Al-Si alloy |
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| CN102296194A (en) * | 2011-09-05 | 2011-12-28 | 陕西理工学院 | Preparation method of internal grown silicon reinforced zinc-based abrasion resistant material |
| CN103471893A (en) * | 2013-09-22 | 2013-12-25 | 东北轻合金有限责任公司 | 4032 aluminum alloy spectroscopic and chemical standard sample and preparation method thereof |
| CN103471893B (en) * | 2013-09-22 | 2015-07-01 | 东北轻合金有限责任公司 | 4032 aluminum alloy spectroscopic and chemical standard sample and preparation method thereof |
| CN103643088A (en) * | 2013-11-29 | 2014-03-19 | 哈尔滨工业大学 | Alterant for ADC12 aluminum alloy and alteration method of alloy |
| CN107236875A (en) * | 2017-06-23 | 2017-10-10 | 常州大学 | A kind of phosphorus titanium dual metamorphism method of cocrystallized Al-Si alloy |
| CN109881055A (en) * | 2019-03-25 | 2019-06-14 | 常州大学 | A kind of one-step phosphorus-boron double modification method of eutectic aluminum-silicon alloy |
| CN109881055B (en) * | 2019-03-25 | 2021-06-22 | 常州大学 | A kind of one-step phosphorus-boron double modification method of eutectic aluminum-silicon alloy |
| CN115141958A (en) * | 2022-07-11 | 2022-10-04 | 顺博合金江苏有限公司 | Wear-resistant aluminum ingot and preparation method thereof |
| CN119061271A (en) * | 2024-07-24 | 2024-12-03 | 广东工程职业技术学院 | A kind of casting aluminum alloy refining modifier and preparation method thereof |
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