CN101613820B - Aluminum-zirconium-phosphorus master alloy and preparation method thereof - Google Patents
Aluminum-zirconium-phosphorus master alloy and preparation method thereof Download PDFInfo
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- CN101613820B CN101613820B CN2009100168340A CN200910016834A CN101613820B CN 101613820 B CN101613820 B CN 101613820B CN 2009100168340 A CN2009100168340 A CN 2009100168340A CN 200910016834 A CN200910016834 A CN 200910016834A CN 101613820 B CN101613820 B CN 101613820B
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- aluminum
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- zirconium
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 72
- 239000000956 alloy Substances 0.000 title claims abstract description 72
- -1 Aluminum-zirconium-phosphorus Chemical compound 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 29
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 26
- 239000011574 phosphorus Substances 0.000 claims abstract description 26
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 23
- URRHWTYOQNLUKY-UHFFFAOYSA-N [AlH3].[P] Chemical compound [AlH3].[P] URRHWTYOQNLUKY-UHFFFAOYSA-N 0.000 claims abstract description 23
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 21
- 230000008018 melting Effects 0.000 claims abstract 3
- 238000002844 melting Methods 0.000 claims abstract 3
- 238000003756 stirring Methods 0.000 claims description 13
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 239000011591 potassium Substances 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 3
- QDIYZGWZTHZFNM-UHFFFAOYSA-N [F].[K] Chemical compound [F].[K] QDIYZGWZTHZFNM-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 9
- 229910052710 silicon Inorganic materials 0.000 abstract description 8
- 239000010703 silicon Substances 0.000 abstract description 8
- 238000005266 casting Methods 0.000 abstract description 7
- 230000005496 eutectics Effects 0.000 abstract description 6
- 238000007670 refining Methods 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 239000007769 metal material Substances 0.000 abstract description 2
- BJZIJOLEWHWTJO-UHFFFAOYSA-H dipotassium;hexafluorozirconium(2-) Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[K+].[K+].[Zr+4] BJZIJOLEWHWTJO-UHFFFAOYSA-H 0.000 abstract 2
- 239000000203 mixture Substances 0.000 abstract 2
- 229910001021 Ferroalloy Inorganic materials 0.000 abstract 1
- 239000004411 aluminium Substances 0.000 description 22
- 238000005516 engineering process Methods 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 238000003723 Smelting Methods 0.000 description 6
- 239000004615 ingredient Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 229910018182 Al—Cu Inorganic materials 0.000 description 2
- 229910000676 Si alloy Inorganic materials 0.000 description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- KMWBBMXGHHLDKL-UHFFFAOYSA-N [AlH3].[Si] Chemical compound [AlH3].[Si] KMWBBMXGHHLDKL-UHFFFAOYSA-N 0.000 description 1
- RIRXDDRGHVUXNJ-UHFFFAOYSA-N [Cu].[P] Chemical compound [Cu].[P] RIRXDDRGHVUXNJ-UHFFFAOYSA-N 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention belongs to the field of metal materials, relating to an aluminum-zirconium-phosphorus master alloy used for refining eutectic and primary silicon in hypereutectic Al-siliceous ferroalloy and a preparation method thereof. In a master alloy system, P exists in a mode of a ZrP compound which contains the following components by weight percent 78.0 percent to 94.0 percent of aluminum, 3.0 percent to 20.0 percent of zirconium and 1.0 percent to 6.0 percent of phosphorus. The preparation method comprises the following steps: preparing industrial pure aluminum, aluminum-phosphorus master alloy, sponge zirconium or potassium fluorozirconate according to the ratio; melting the industrial pure aluminum to 900 DEG C to 1300 DEG C in a melting furnace; firstly adding the aluminum-phosphorus master alloy to mix for 10 to 20 min; and then adding the sponge zirconium or the potassium fluorozirconate to fully react and uniformly mix, and directly casting the mixture to form a ingot or prepare a wire. The aluminum-zirconium-phosphorus master alloy has favorable refining effect, and can remarkably improve the high temperature mechanical properties of the alloy.
Description
One, technical field
The invention belongs to metal material field, particularly a kind of aluminum-zirconium-phosphorus master alloy that is used for refining eutectic and hypereutectic aluminium-Si system alloy primary silicon and preparation method thereof.
Two, background technology
At present, the refinement of primary silicon mainly is to adopt the method for adding master alloy in eutectic and the hypereutectic aluminium-Si system alloy.Since the patent of last century the '30s Sterner and Rainer invention phosphorus refinement primary silicon, the research of phosphorous master alloy has obtained bigger progress, as copper-phosphorus, Solder for Al-Cu Joint Welding-phosphorus, aluminium-iron-phosphorus and aluminium-silicon-master alloys such as phosphorus.Copper-phosphorus master alloy density is bigger, easily precipitates segregation, and the modification effect instability is not suitable for leaving standstill stove production, and brings copper component to pollute.Solder for Al-Cu Joint Welding-phosphorus master alloy is rotten, thinning effect is comparatively stable, but its preparation cost height, fails the application that puts it in actual production.The use of aluminium-iron-phosphorus master alloy then can be introduced the impurity iron element in alloy.Application number is that 200510044827 Chinese patent has been reported a kind of novel master alloy that contains aluminium, silicon, phosphorus, contain a large amount of preformed AlP particles in this master alloy, it has good rotten, thinning effect, and has obtained aborning to apply.But three kinds of above-mentioned aluminium base master alloys, P all is present in the master alloy system with the AlP form, because AlP is easy to the oxidation with airborne water vapour reaction, hydrolysis, thereby causes the phosphorus content in the master alloy progressively to reduce in the preservation process.Therefore, press for a kind of new phosphorous aluminium base master alloy of invention in the production, when reaching good thinning effect, in melt, do not introduce other impurity elements, also be convenient to prolonged preservation and use.
Three, summary of the invention
The objective of the invention is to overcome above-mentioned the deficiencies in the prior art, a kind of aluminum-zirconium-phosphorus master alloy that can play efficient refinement to the primary silicon in eutectic and the hypereutectic aluminum-silicon alloy and significantly improve the alloy high-temp mechanical property is provided, provides simultaneously that a kind of production cost is low, technology is easy, be fit to the preparation method of suitability for industrialized production.
The present invention realizes in the following manner:
A kind of aluminum-zirconium-phosphorus master alloy is characterized in that: the mass percent of contained component is aluminium 78.0-94.0%, zirconium 3.0-20.0%, phosphorus 1.0-6.0%; P is present in the master alloy system with the ZrP form.And the ZrP particle in joining eutectic and hypereutectic aluminum-silicon alloy melt after, the reaction of ZrP and molten aluminium generates AlP, for primary silicon provides heterogeneous core.Simultaneously, also introduce the Zr element thereupon, can significantly improve the mechanical behavior under high temperature of alloy.
The preparation method of above-mentioned a kind of aluminum-zirconium-phosphorus master alloy is characterized in that may further comprise the steps:
(1) at first is ready to prepare aluminum-zirconium-required raw material of phosphorus master alloy: zirconium sponge 3.0-20% or potassium fluozirconate 9.4-62.5% by following mass percent, aluminium-phosphorus master alloy 13.3-80.0%, surplus is commercial-purity aluminium, and wherein the phosphorus content of aluminium-phosphorus master alloy is 2.0-7.8%;
(2) in smelting furnace, commercial-purity aluminium is melted to 900 ℃-1300 ℃, adds aluminium-phosphorus master alloy earlier, after stirring 10-20 minute, add zirconium sponge or potassium fluozirconate again;
(3) the directly casting ingot-forming or be prepared into wire rod of back that reacts completely and stir.
The preparation method of above-mentioned aluminum-zirconium-phosphorus master alloy is characterized in that in the step (1), the phosphorus content of aluminium-phosphorus master alloy is 2.0-7.8%.
Compare with AlP, the ZrP compound is facile hydrolysis, oxidation not, and this compound can play solid phosphorus effect, and zirconium is the micro alloying element in the aluminium-silicon system, thereby can the reinforced aluminum matrix improves the mechanical behavior under high temperature of alloy.Therefore, when adopting aluminum-zirconium-phosphorus master alloy that eutectic and hypereutectic aluminium-Si system alloy are carried out thinning processing, when reaching good thinning effect, can significantly improve the mechanical property of alloy.This master alloy has advantages such as fusing point is low, add-on is little, and thinning effect is stable, long-acting.Under 15 minutes conditions of insulation, can make primary silicon size in the Al-18Si alloy by being refined to below the 25 μ m more than the 120 μ m, be a kind of efficient and environment-friendly type master alloy.The preparation of alloy can be carried out under lower temperature; Need not specific installation in the preparation process, preparation technology is simpler; Aluminum-zirconium-phosphorus the master alloy of preparation has favorable refining effect and strong anti-time fade performance, can improve the mechanical property of alloy simultaneously significantly, is fit to scale operation and application.
Four, embodiment
Provide several preferred example of the present invention below.
Embodiment 1
(1) mass percent by commercial-purity aluminium 9.7%, aluminium-phosphorus master alloy 73.3%, zirconium sponge 17.0% takes by weighing raw material, and wherein the phosphorus content of aluminium-phosphorus master alloy is 7.5%.
(2) in smelting furnace, commercial-purity aluminium is melted to 1100 ℃-1300 ℃, adds aluminium-phosphorus master alloy earlier, after stirring 10-20 minute, add zirconium sponge again.
(3) the directly casting ingot-forming or be prepared into wire rod of back that reacts completely and stir.
Obtain a kind of aluminum-zirconium-phosphorus master alloy of optimal components according to said ratio and technology, the mass percent of its chemical ingredients is: phosphorus 5.3-5.7, and zirconium 16.7-17.3, all the other are aluminium.
Embodiment 2
(1) mass percent by commercial-purity aluminium 20.3%, aluminium-phosphorus master alloy 66.7%, zirconium sponge 13% takes by weighing raw material, and wherein the phosphorus content of aluminium-phosphorus master alloy is 6.0%.
(2) in smelting furnace, commercial-purity aluminium is melted to 1000 ℃-1200 ℃, adds aluminium-phosphorus master alloy earlier, after stirring 10-20 minute, add zirconium sponge again.
(3) the directly casting ingot-forming or be prepared into wire rod of back that reacts completely and stir.
According to aluminum-zirconium-phosphorus master alloy that said ratio and technology are produced, the mass percent of its chemical ingredients is: phosphorus 3.8-4.1, and zirconium 12.7-13.2, all the other are aluminium.
Embodiment 3
(1) mass percent by commercial-purity aluminium 36.9%, aluminium-phosphorus master alloy 57.1%, zirconium sponge 6.0% takes by weighing raw material, and wherein the phosphorus content of aluminium-phosphorus master alloy is 3.5%.
(2) in smelting furnace, commercial-purity aluminium is melted to 900 ℃-1100 ℃, adds aluminium-phosphorus master alloy earlier, after stirring 10-20 minute, add zirconium sponge again.
(3) the directly casting ingot-forming or be prepared into wire rod of back that reacts completely and stir.
According to aluminum-zirconium-phosphorus master alloy that said ratio and technology are produced, the mass percent of its chemical ingredients is: phosphorus 1.8-2.2, and zirconium 5.9-6.2, all the other are aluminium.
Embodiment 4
(1) mass percent by commercial-purity aluminium 48.0%, aluminium-phosphorus master alloy 33.3%, potassium fluozirconate 18.7% takes by weighing raw material, and wherein the phosphorus content of aluminium-phosphorus master alloy is 6.0%.
(2) in smelting furnace, commercial-purity aluminium is melted to 900 ℃-950 ℃, adds aluminium-phosphorus master alloy earlier, after stirring 10-20 minute, add potassium fluozirconate again.
(3) the directly casting ingot-forming or be prepared into wire rod of back that reacts completely and stir.
According to aluminum-zirconium-phosphorus master alloy that said ratio and technology are produced, the mass percent of its chemical ingredients is: phosphorus 1.8-2.2, and zirconium 5.7-6.3, all the other are aluminium.
Embodiment 5
(1) mass percent by commercial-purity aluminium 24.1%, aluminium-phosphorus master alloy 57.1%, potassium fluozirconate 18.8% takes by weighing raw material, and wherein the phosphorus content of aluminium-phosphorus master alloy is 3.5%.
(2) in smelting furnace, commercial-purity aluminium is melted to 900 ℃-950 ℃, adds aluminium-phosphorus master alloy earlier, after stirring 10-20 minute, add potassium fluozirconate again.
(3) the directly casting ingot-forming or be prepared into wire rod of back that reacts completely and stir.
According to aluminum-zirconium-phosphorus master alloy that said ratio and technology are produced, the mass percent of its chemical ingredients is: phosphorus 1.8-2.2, and zirconium 5.7-6.3, all the other are aluminium.
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| CN2009100168340A CN101613820B (en) | 2009-07-15 | 2009-07-15 | Aluminum-zirconium-phosphorus master alloy and preparation method thereof |
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| CN2009100168340A CN101613820B (en) | 2009-07-15 | 2009-07-15 | Aluminum-zirconium-phosphorus master alloy and preparation method thereof |
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| CN101613820B true CN101613820B (en) | 2010-11-03 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102329998B (en) * | 2011-09-07 | 2013-02-06 | 山东大学 | Aluminium-magnesium-phosphorus intermediate alloy and preparation method thereof |
| CN102534312B (en) * | 2012-01-11 | 2013-12-11 | 山东大学 | Aluminum-lanthanum-cerium-phosphorus intermediate alloy and preparation method thereof |
| CN102634694B (en) * | 2012-04-25 | 2013-09-18 | 济南大学 | Aluminum-yttrium-phosphorus interalloy and preparation method thereof |
| CN103290271B (en) * | 2013-07-01 | 2014-12-24 | 山东大学 | Aluminum-titanium-phosphorus-carbon-boron intermediate alloy and preparation method thereof |
| CN109811174B (en) * | 2019-03-01 | 2019-08-30 | 山东大学 | A kind of aluminum-phosphorus-tin seed crystal alloy and its preparation method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6261390B1 (en) * | 2000-05-15 | 2001-07-17 | Hsien-Yang Yeh | Process for nodulizing silicon in casting aluminum silicon alloys |
| CN1317590A (en) * | 2001-01-04 | 2001-10-17 | 山东大学 | Al-P-Cu intermediate alloy and its preparing process |
| CN1410565A (en) * | 2002-11-25 | 2003-04-16 | 山东大学 | Aluminium-phosphorus intermediate alloy and its preparation method |
| CN1760392A (en) * | 2005-09-28 | 2006-04-19 | 山东大学 | Method for preparing intermediate alloy of aluminum, silicon and posphor |
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- 2009-07-15 CN CN2009100168340A patent/CN101613820B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6261390B1 (en) * | 2000-05-15 | 2001-07-17 | Hsien-Yang Yeh | Process for nodulizing silicon in casting aluminum silicon alloys |
| CN1317590A (en) * | 2001-01-04 | 2001-10-17 | 山东大学 | Al-P-Cu intermediate alloy and its preparing process |
| CN1410565A (en) * | 2002-11-25 | 2003-04-16 | 山东大学 | Aluminium-phosphorus intermediate alloy and its preparation method |
| CN1760392A (en) * | 2005-09-28 | 2006-04-19 | 山东大学 | Method for preparing intermediate alloy of aluminum, silicon and posphor |
Non-Patent Citations (1)
| Title |
|---|
| 孙瑜等.近共晶Al-Si合金的晶粒细化.中国有色金属学报.2004,14(8),1340-1347. * |
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Assignee: Shandong Al&Mg Melt Technology Co., Ltd. Assignor: Shandong University Contract record no.: 2011370000063 Denomination of invention: Aluminum-zirconium-phosphorus master alloy and preparation method thereof Granted publication date: 20101103 License type: Exclusive License Open date: 20091230 Record date: 20110325 |
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