CN105714144A - Calcium removal method for aluminum-silicon series alloys - Google Patents
Calcium removal method for aluminum-silicon series alloys Download PDFInfo
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- CN105714144A CN105714144A CN201610213001.3A CN201610213001A CN105714144A CN 105714144 A CN105714144 A CN 105714144A CN 201610213001 A CN201610213001 A CN 201610213001A CN 105714144 A CN105714144 A CN 105714144A
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- aluminum
- calcium
- phosphorus
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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
- C22C21/00—Alloys based on aluminium
- C22C21/02—Alloys based on aluminium with silicon as the next major constituent
Abstract
The invention belongs to the field of metal materials, and relates to a calcium removal method for aluminum-silicon series alloys. The calcium removal method comprises the steps that an aluminum-phosphorus intermediate alloy is adopted as a calcium remover, and argon refining is used in combination for calcium removal. Phosphorus in the aluminum-phosphorus intermediate alloy accounts for 2.5% to 5.5%, impurities account for not larger than 0.5%, and phosphorus exists in the form of dispersively distributed AlP particles. A calcium removal process comprises the steps that the aluminum-silicon series alloys needing to be subjected to calcium removal are molten and heated to 750 DEG C to 850 DEG C, the preheated aluminum-phosphorus intermediate alloy is added, and heat preservation is carried out for 10-45 minutes to enable the aluminum-phosphorus intermediate alloy to be dissolved and react; the melt is slightly stirred in the heat preservation process to accelerate dissolving and reacting of AlP; and then high-purity argon is blown into the melt for refining, the refining time ranges from 5 minutes to 20 minutes, surface-layer dross is removed after refining treatment is finished, and calcium impurities in the aluminum-silicon series alloys can be remarkably reduced. The calcium removal method has the beneficial effects that high efficiency and environment friendliness are achieved, and the process is simple and convenient.
Description
Technical field
The invention belongs to metal material field, particularly to a kind of aluminum-Si system alloy calcium removal methods.
Background technology
Eutectic and hypereutectic aluminum-Si system alloy with its light weight, high abrasion, high intensity, low thermal coefficient of expansion and
The outstanding representations such as good heat conductivity, become the ideal material manufacturing the auto parts and components such as piston, cylinder.It is full
Full border serviceability requirement, it is necessary to it is carried out phosphorus modification process.
Calcium is impurity element common in silicon metal, inevitably contains from raw material in aluminum-Si system alloy
Impurity calcium in pure silicon and fine aluminium, and have extremely strong affinity between calcium and phosphorus, therefore when in aluminum-Si system alloy
When impurity calcium content is higher, phosphorus modification can be made " to be poisoned ".Moreover, the existence of calcium also can make aluminum-silicon system close
Gold fluidity of molten is deteriorated, and easy air-breathing results in casting flaw, makes casting wasted product rate increase.Therefore, exist
Melt must be carried out deliming before Metamorphism treatment.Use high-purity crystallized silicon and aluminum can avoid this problem but make raw
Product cost is greatly improved, and quiescence in high temperature is also effective solution, but can increase energy consumption and improve production cost and
Reduce production efficiency.The domestic method commonly used most is to use the chloride refining agents such as hexachlorethane to carry out refine to remove
Calcium.Make as document (Materials science and technology, 2003,19 (7): 915-918.) also reports
With chloride (Ti2Cl6) can effectively control calcium content, but chlorination process can discharge a large amount of chlorine, seriously
Pollute environment and health is had huge injury.Document (internal combustion engine part, 2005,5:24) is had to propose to use
Aluminum-carbon intermediate alloy with deliming, but can must be added to this intermediate alloy a large amount of and can be only achieved preferable deliming effect.
Document (Rare Metals, 2013,32 (3): 247-251.) reports the solution of a kind of more environmental protection, i.e.
Add boron and calcium reaction formation six calcium borides thus calcium is removed, make phosphorus thinning effect recover, but in alloy melt
If containing more titanium, then boron can cause the method to lose efficacy with titanium reaction.Patent No. 201010593187.2
Chinese patent open report a kind of novel calcium remover, cardinal principle is fluorination deliming, simultaneously boron carbon deliming phase
In conjunction with, but this calcium remover carries out deliming mainly for nearly eutectic aluminum-Si system alloy, to hypereutectic aluminum-Si system alloy
Not being preferable calcium remover, the scope of application has certain limitation, and there is problem of environmental pollution.
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art, it is provided that a kind of efficiently, environmental protection, simple process
Aluminum-Si system alloy calcium removal methods.
The present invention is achieved in the following ways:
A kind of aluminum-Si system alloy calcium removal methods, is characterized in that with aluminum-phosphorus intermediate alloy as calcium remover, in conjunction with high
Pure argon refine carries out deliming；The mass percent of the phosphorus in aluminum-phosphorus intermediate alloy is 2.5-5.5%, impurity≤
0.5%, phosphorus exists with the AlP particulate forms of disperse；Aluminum-phosphorus intermediate alloy is added in aluminum-Si system alloy melt
After, the AlP particle and the lysigenous AlP cluster thereof that discharge are reacted with the calcium in aluminum-Si system alloy melt
Generate rich calcium-phosphorus ratio thing, by argon refine, richness calcium-phosphorus ratio thing is removed from aluminum-Si system alloy melt.
Above-mentioned aluminum-Si system alloy calcium removal methods, is characterized in that comprising the following steps:
(1) first aluminum-phosphorus intermediate alloy is got out by the 0.2-1.0% of calcic aluminum-Si system alloy gross mass, and
It is preheated to 150 DEG C；
(2) calcic aluminum-Si system alloy melted and be warming up to 750-850 DEG C, adding the aluminum-phosphorus through preheating
Intermediate alloy, is incubated and within 10-45 minute, makes it dissolve and react, insulating process need gentle agitation with
Ensure to dissolve and react fully to carry out；
(3) being blown into the high-purity argon gas that drying processed in melt and carry out refine, refining time 5-20 divides
Clock；
(4) after refining treatment terminates, top layer scum silica frost is removed.
The know-why of the present invention is phosphatization deliming, i.e. reacts generation calcium phosphide by aluminum phosphate and calcium, its reaction
Formula is as follows:
AlP(s)+[Ca]→Ca3P2(s)+[Al]
The calcium phosphide generated belongs to high-melting-point particle, can be taken out of by argon refine.Phosphorus and the chemical affinity of calcium
Extremely strong, therefore deliming effect is the most notable.In the method, calcium is utilized to make phosphorus modification " be poisoned " this phenomenon,
Make aluminum-phosphorus intermediate alloy be not only alterant, be also calcium remover, thus without additionally preparing special calcium remover.
This is the most cost-effective also simplify the technological process of production, it also avoid the introducing of other impurity elements simultaneously, full
Foot requires higher occasion to alloy degree of purity, makes the method more general applicability.Additionally, the aluminum added
-phosphorus intermediate alloy is shaft-like or wire rod, and addition is easily controllable, and easy and simple to handle.Therefore, the present invention is one
Kind efficiently, environmental protection, technique is simple, have the aluminum-Si system alloy calcium removal methods of universality.
Detailed description of the invention
Five most preferred embodiments of the present invention are given below:
Embodiment 1
(1) first it is ready in the middle of Al-2.5%P close by the 0.2% of the relatively low Al-13Si alloy gross mass of calcium content
Gold, and it is preheated to 150 DEG C；
(2) by Al-13Si alloy melting relatively low for calcium content, and melt temperature is risen to 760 DEG C, add and pass through
The Al-2.5%P intermediate alloy of the 0.2% of preheating, is incubated and makes it dissolve and react for 10 minutes, insulation
During gentle agitation melt；
(3) in melt, it is blown into the high-purity argon gas that drying processed carries out refine, refining time 5 minutes；
(4) after refining treatment terminates, top layer scum silica frost is removed.
Carry out deliming according to above-mentioned process, its calcium content of alloy by mass percentage from 31ppm reduce to
2ppm。
Embodiment 2
(1) first it is ready in the middle of Al-3.0%P close by the 0.2% of the relatively low Al-14Si alloy gross mass of calcium content
Gold, and it is preheated to 150 DEG C；
(2) by Al-14Si alloy melting relatively low for calcium content, and melt temperature is risen to 770 DEG C, add and pass through
The Al-3.0%P intermediate alloy of the 0.2% of preheating, is incubated and makes it dissolve and react for 12 minutes, insulation
During gentle agitation melt；
(3) in melt, it is blown into the high-purity argon gas that drying processed carries out refine, refining time 8 minutes；
(4) after refining treatment terminates, top layer scum silica frost is removed.
Carry out deliming according to above-mentioned process, its calcium content of alloy by mass percentage from 57ppm reduce to
3ppm。
Embodiment 3
(1) first Al-3.5%P intermediate alloy is got out by 1% of the Al-16Si alloy gross mass containing a certain amount of calcium,
And it is preheated to 150 DEG C；
(2) by the Al-16Si alloy melting containing a certain amount of calcium, and melt temperature is risen to 800 DEG C, add and pass through
The Al-3.5%P intermediate alloy of the 1% of preheating, is incubated and makes it dissolve and react for 20 minutes, be incubated
Gentle agitation melt in journey；
(3) in melt, it is blown into the high-purity argon gas that drying processed carries out refine, refining time 10 minutes；
(4) after refining treatment terminates, top layer scum silica frost is removed.
Carry out deliming according to above-mentioned process, its calcium content of alloy by mass percentage from 163ppm reduce to
8ppm。
Embodiment 4
(1) first Al-5.0%P intermediate alloy is got out by the 1% of the higher Al-18Si alloy gross mass of calcium content,
And it is preheated to 150 DEG C；
(2) by Al-18Si alloy melting higher for calcium content, and melt temperature is risen to 820 DEG C, add and pass through
The Al-5.0%P intermediate alloy of the 1% of preheating, is incubated and makes it dissolve and react for 30 minutes, be incubated
Gentle agitation melt in journey；
(3) in melt, it is blown into the high-purity argon gas that drying processed carries out refine, refining time 18 minutes；
(4) after refining treatment terminates, top layer scum silica frost is removed.
Carry out deliming according to above-mentioned process, its calcium content of alloy by mass percentage from 238ppm reduce to
2ppm。
Embodiment 5
(1) first Al-5.5%P intermediate alloy is got out by the 1% of the higher Al-25Si alloy gross mass of calcium content,
And it is preheated to 150 DEG C；
(2) by Al-25Si alloy melting higher for calcium content, and melt temperature is risen to 850 DEG C, add and pass through
The Al-5.5%P intermediate alloy of the 1% of preheating, is incubated and makes it dissolve and react for 40 minutes, be incubated
Gentle agitation melt in journey；
(3) in melt, it is blown into the high-purity argon gas that drying processed carries out refine, refining time 20 minutes；
(4) after refining treatment terminates, top layer scum silica frost is removed.
Carry out deliming according to above-mentioned process, its calcium content of alloy by mass percentage from 293ppm reduce to
6ppm。
Claims (2)
1. aluminum-Si system alloy calcium removal methods, is characterized in that with aluminum-phosphorus intermediate alloy as calcium remover, in conjunction with high
Pure argon refine carries out deliming；In aluminum-phosphorus intermediate alloy, the mass percent of phosphorus is 2.5-5.5%, impurity≤
0.5%, phosphorus exists with the AlP particulate forms of Dispersed precipitate；Aluminum-phosphorus intermediate alloy is added aluminum-silicon system close
After in gold melt, the AlP particle discharged and lysigenous AlP cluster thereof and aluminum-Si system alloy melt
In calcium reaction generate rich calcium-phosphorus ratio thing, by argon refine by richness calcium-phosphorus ratio thing from aluminum-Si system alloy melt
Middle removing.
A kind of aluminum-Si system alloy calcium removal methods the most according to claim 1, is characterized in that comprising the following steps:
(1) first aluminum-phosphorus intermediate alloy is got out by the 0.2-1.0% of calcic aluminum-Si system alloy gross mass, and in advance
Heat is to 150 DEG C；
(2) calcic aluminum-Si system alloy melted and be warming up to 750-850 DEG C, adding in the aluminum-phosphorus of preheating
Between alloy, be incubated and within 10-45 minute, make it dissolve and react, insulating process gentle agitation melt is molten to ensure
Solve and fully carry out with course of reaction；
(3) being blown into the high-purity argon gas that drying processed in melt and carry out refine, refining time is that 5-20 divides
Clock；
(4) after refining treatment terminates, melt top layer scum silica frost is removed.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610213001.3A CN105714144A (en) | 2016-04-07 | 2016-04-07 | Calcium removal method for aluminum-silicon series alloys |
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| CN201610213001.3A CN105714144A (en) | 2016-04-07 | 2016-04-07 | Calcium removal method for aluminum-silicon series alloys |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103831422A (en) * | 2012-11-27 | 2014-06-04 | 中国兵器科学研究院宁波分院 | Nanometer refining method of Al-Si system aluminum alloy structure |
-
2016
- 2016-04-07 CN CN201610213001.3A patent/CN105714144A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103831422A (en) * | 2012-11-27 | 2014-06-04 | 中国兵器科学研究院宁波分院 | Nanometer refining method of Al-Si system aluminum alloy structure |
Non-Patent Citations (2)
| Title |
|---|
| 乔进国等: "Al-P中间合金的变质特性及变质机理探讨", 《内燃机配件》 * |
| 刘相法等: "Al-P 中间合金在Al-Si活塞合金中的应用", 《特种铸造及有色合金》 * |
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