EP3247812B1 - Grain refining method for aluminium alloys - Google Patents

Grain refining method for aluminium alloys Download PDF

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Publication number
EP3247812B1
EP3247812B1 EP15728214.6A EP15728214A EP3247812B1 EP 3247812 B1 EP3247812 B1 EP 3247812B1 EP 15728214 A EP15728214 A EP 15728214A EP 3247812 B1 EP3247812 B1 EP 3247812B1
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EP
European Patent Office
Prior art keywords
added
aluminum alloy
grain
strontium
alloys
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EP15728214.6A
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German (de)
French (fr)
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EP3247812A1 (en
Inventor
Özgür Yavuz TOPÇUOGLU
Halil Emre ÇUBUKLUSU
Yunus ERCAN
Ömer Burak ÇE
Özgür ILTER
Mehmet KIZILKAYA
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Cms Jant Ve Makine Sanayi AS
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Cms Jant Ve Makine Sanayi AS
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
    • C22F1/05—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon of alloys of the Al-Si-Mg type, i.e. containing silicon and magnesium in approximately equal proportions
    • 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
    • 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
    • C22C1/026—Alloys based on aluminium
    • 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
    • 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
    • C22C21/04—Modified aluminium-silicon alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
    • C22F1/043—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon of alloys with silicon as the next major constituent

Definitions

  • Invention relates to a method which ensures that grain refinement can be made more efficiently in aluminum cast alloys.
  • the invention particularly relates to a method which ensures grain refinement of aluminum alloys by adding sufficient amount of strontium (Sr) and boron (B) into the ladle containing aluminum alloy while the rotor is rotating after flux effect neutralized in degassing process.
  • Al-Ti-B master alloys are commonly used for grain refinement in Al-Si cast alloys. Nucleating mechanism in alloy is provided by TiB 2 and Al 3 Ti compounds as a result of using Al-Ti-B master alloys.
  • SrB 6 has positive effect on the modification of eutectic phase as well.
  • Mechanical and metallurgical characteristics of the material are improved through grain structure with finer grain size and well-modified eutectic phase. Higher number of grains and finer size of grain particularly cause the elongation values to be improved.
  • the other positive effect is that the impact strength of alloy increases with the increase in toughness of the material. Improvements occur in mechanical properties.
  • the grain size may vary depending on cooling speed in the range specified above and type of grain refining master alloys used.
  • Grain size on commercial vehicles aluminum alloy wheels in the market are as mentioned above.
  • Minimum grain size which can be formed by present commercial grain refiners, aluminum alloy wheels which are produced with low pressure die casting, metallurgical and mechanical properties have reached the limit in current design inputs and section thickness. Additionally, current grain size does not allow designs with higher strength to be made or finer and complex designs to be made.
  • Present average grain size which is in the range of 500 ⁇ m - 1000 ⁇ m causes the porosities to be present on the product with larger and segregated form.
  • the invention relates to a pressure casting alloy comprised of a suitable aluminum alloy for pressure casting of structure parts having high expansion character in case of casting, in addition to aluminum and unpreventable contamination, silicon with a weight percentage of 8.5 and 10.5, manganese with a weight percentage of 0.3 and 0.8, magnesium with maximum weight percentage of 0.06, iron with maximum weight percentage of 0.15, copper with maximum weight percentage of 0.03, zinc with maximum weight percentage of 0.10, titanium with maximum weight percentage of 0.15, molybdenum with a weight percentage of 0.05 and 0.5 and 30 and 300 ppm strontium for continuous enrichment or 5 and 30 ppm sodium and/or 1 and 30 ppm calcium.
  • the invention relates to a method for grain refinement and structure modification for Al-Mg-Si alloys used in sand casting containing Ca, Na and Sr less than 0.001%, 5.0-10.0% Mg, 1.0-5.0% Si, 0.001-1.0% Mn, 0.01-0.2% Ti as main alloy or hard casting.
  • Objective of the invention is to introduce an embodiment having different technical properties introducing a new development in this field considering the applications used in present art.
  • Another objective of the invention is to obtain an embodiment having finer grain size in aluminum alloys with Sr and B elements.
  • Another objective of the invention is that grain sizes, obtained in production of aluminum alloy wheels by low pressure casting method, are in the range of 50 ⁇ m-500 ⁇ m.
  • Another objective of the invention is that aluminum alloy is formed in homogeneous macrostructure.
  • Another objective of the invention is reduction of defects in casting such as shrinkage and gas porosity in alloy.
  • Another objective of the invention is increase in fluidity during casting process and capability of cast feeding.
  • Another objective of the invention is filling narrow sections easier during casting process.
  • Another objective of the invention is reduction of shrinkage-distortion problems depending on contraction during thermal process.
  • Another objective of the invention is to reduce the number of scrap ratio in production.
  • Another objective of the invention is to be able to reduce heat treatment process time by increase in surface area of grain boundaries due to grain refining; in other words, increase in the number of grains in per unit volume.
  • Another objective of the invention is to obtain improvements in energy consumption and production period regarding to reduction in heat treatment process time.
  • Another objective of the invention is increase in mechanical properties of final product and accordingly, improvement and moderation in design as a result of finer grain structure of aluminum alloys.
  • Another objective of the invention is to obtain commercially successful product with higher mechanical properties according to all these improvements.
  • Another objective of the invention is reducing the amount of additive elements for the aluminum alloy grain refinement up to 1/5-1/7 ratio.
  • the invention relates to a method which ensures refining of grain structure of aluminum alloys. It is comprised of process steps for grain refining which sufficient amount of strontium (Sr) is added to the ladle containing aluminum alloy and boron (B) is added to said ladle after flux influence in degassing process is completed while the rotor is still rotating.
  • Sr strontium
  • B boron
  • this method follows the steps in which total titanium content of aluminum alloy is controlled under 0.005% by weight, SrB 6 is formed by binding of boron(B) and strontium (Sr) in aluminum alloy at the rate of 1:1.35 by weight, free strontium (Sr) at the rate of 0.015% or more by weight remain in aluminum alloy for eutectic modification following SrB 6 formation.
  • Boron (B) is added to the aluminum alloy as AIB compound.
  • Strontium (Sr) is added to the aluminum alloy as AlSr compound.
  • Invention relates to a method which ensures refining of grain structure of aluminum casting alloys. It comprises the processes in which sufficient amount of strontium (Sr) is added to the ladle containing aluminum alloy and boron (B) is added to the ladle after flux effect in degassing process is finished while the rotor continues rotating for grain refining.
  • Sr strontium
  • B boron
  • This method follows the steps in which total titanium content of aluminum alloy is controlled under 0.005% by weight, SrB 6 is formed by binding of boron(B) and strontium (Sr) in aluminum alloy at the rate of 1:1.35 by weight, free strontium (Sr) at the rate of 0.015% or more by weight remain in aluminum alloy for eutectic modification following SrB 6 formation.
  • Boron (B) is added to the aluminum alloy as AIB compound.
  • Strontium (Sr) is added to the aluminum alloy as AlSr compound.
  • AlSi7Mg is used as common aluminium alloy in wheel manufacturing.
  • this process is likely to be successful in Al-Si, Al-Cu and Al-Mg alloys too.
  • the Boron amount in the cast piece can be examined via spectrometer to have a better understanding of SrB 6 amount in the alloy but the obtained value comprises also AlB 2 and TiB 2 phases.
  • minimum 35ppm B and 150 ppm Sr should be measured in any section of cast piece.
  • any existing Ti element in the master alloy leads to form TiB 2
  • TiB 2 is known to be one of the existing grain refining methods in aluminum alloys, the SrB6 formation is reduced significantly by the existence of Ti in the master alloy resulting loss in grain refining effectiveness. Therefore rather Ti free master alloys or master alloys containing Ti below 50ppm should be preferred to have an accomplished grain refining by SrB6.
  • This method can be used in aluminum alloys which includes Titanium element by an appropriate holding ladle and mixing system.
  • AlSr is added to the ladle beforehand and then, AIB is added after flux effect passes in degassing process while rotor is rotating. Afterwards, this ladle is transferred to casting bench.
  • Desired fine grained and modified structure can be maintained in a single charge. Totally, Xppm B + 1.35XppmSr + 100-200 ppm Sr (for modification) is added to the ladle.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Description

    Technical Field
  • Invention relates to a method which ensures that grain refinement can be made more efficiently in aluminum cast alloys.
  • The invention particularly relates to a method which ensures grain refinement of aluminum alloys by adding sufficient amount of strontium (Sr) and boron (B) into the ladle containing aluminum alloy while the rotor is rotating after flux effect neutralized in degassing process.
    • Prior Art
  • In present practice, Al-Ti-B master alloys are commonly used for grain refinement in Al-Si cast alloys. Nucleating mechanism in alloy is provided by TiB2 and Al3Ti compounds as a result of using Al-Ti-B master alloys.
  • However, since Si element easily reacts with Ti element, TiB2 and Al3Ti loose the efficiency of grain refinement after a while and joins in main matrix by forming a compound with Si. This limits the refinement of the grain size of Aluminium Alloys to a certain level.
  • Search for higher mechanical durability and more competitive designs require the necessity for having a finer grain structure at macrostructure level in Aluminum Alloys. This causes a finer grain size which is formed by AlB2 and SrB6 compounds.
  • SrB6 has positive effect on the modification of eutectic phase as well. Mechanical and metallurgical characteristics of the material are improved through grain structure with finer grain size and well-modified eutectic phase. Higher number of grains and finer size of grain particularly cause the elongation values to be improved. The other positive effect is that the impact strength of alloy increases with the increase in toughness of the material. Improvements occur in mechanical properties.
  • Grain size in aluminum alloy wheels manufactured by low-pressure die casting method, hypoeutectic aluminum alloys, on present practices average grain size varies between 500µm-1000µm. The grain size may vary depending on cooling speed in the range specified above and type of grain refining master alloys used. Grain size on commercial vehicles aluminum alloy wheels in the market are as mentioned above. Minimum grain size which can be formed by present commercial grain refiners, aluminum alloy wheels which are produced with low pressure die casting, metallurgical and mechanical properties have reached the limit in current design inputs and section thickness. Additionally, current grain size does not allow designs with higher strength to be made or finer and complex designs to be made. Present average grain size which is in the range of 500 µm - 1000 µm causes the porosities to be present on the product with larger and segregated form.
  • Also, fluidity in current grain size may be insufficient and cause feeding inadequacy in thin sections. In such cases, cooling speed of concerned section may only be reduced and thus, section is completely filled and fed. But finally, because of the lower solidification rate, grain size increase and mechanical properties decrease.
  • Manufacturing method of aluminum alloy wheels by present low-pressure casting and grain refining activities carried out by Al-B. However eutectic modification does not occur due to the loss of free Sr. Considering the examinations conducted, boron (B) element added for grain refining combines necessary strontium (Sr) element for modification and forms SrB6. Since Sr is essential for eutectic modification in Aluminum Alloys, absence of Sr results in unmodified eutectic.
  • In patent researches carried out pertaining to grain refinement methods applied in aluminum alloys, a patent no: EP1443122B1 has been found. The invention relates to a pressure casting alloy comprised of a suitable aluminum alloy for pressure casting of structure parts having high expansion character in case of casting, in addition to aluminum and unpreventable contamination, silicon with a weight percentage of 8.5 and 10.5, manganese with a weight percentage of 0.3 and 0.8, magnesium with maximum weight percentage of 0.06, iron with maximum weight percentage of 0.15, copper with maximum weight percentage of 0.03, zinc with maximum weight percentage of 0.10, titanium with maximum weight percentage of 0.15, molybdenum with a weight percentage of 0.05 and 0.5 and 30 and 300 ppm strontium for continuous enrichment or 5 and 30 ppm sodium and/or 1 and 30 ppm calcium.
  • According to another patent no: AT511397B1 , the invention relates to a method for grain refinement and structure modification for Al-Mg-Si alloys used in sand casting containing Ca, Na and Sr less than 0.001%, 5.0-10.0% Mg, 1.0-5.0% Si, 0.001-1.0% Mn, 0.01-0.2% Ti as main alloy or hard casting.
  • In the US2008/299001 A1 patent, Ti excess amount is given as 0.005% however total amount of Ti is given as 0.015%. In our study we stated that total Ti amount must be below 0.005% in order to get successful grain refining results. Besides, the corresponding example in the document is the analysis in which total amount of Ti is reported as 0.005%. However, even in this analysis the ratio between B and Sr is given as 0.5 and in our study the relation between B and Sr is calculated as in the mentioned formula. Furthermore, the alloys used in the document are master alloys and amount of Si reported is substantially lower.
  • In the patent US2014017115 A1 patent, An aluminum alloy consisting essentially of, by weight percentage, from 11% to 13.5% Silicon, up to 0.5% Copper, from 0.4 to 0.55% Magnesium, up to 0.3% Iron, up to 0.3% Manganese, up to 0.1% Titanium, up to 0.4% Zinc, from about 0.015% to 0.08% Strontium, from 0.03% to 0.05% Boron, and the balance aluminum.
  • Inventions briefly summarized above are similar to the present art in terms of grain refining processes. Standard addition elements are added to aluminum master alloys. It contains the disadvantages in present art.
  • In conclusion, improvements are made particularly in production of aluminum alloy wheels in grain refinement methods applied in production of aluminum alloy and new configurations are required for elimination of the abovementioned disadvantages and a solution to the present art.
    • Explanation of the Invention
  • Objective of the invention is to introduce an embodiment having different technical properties introducing a new development in this field considering the applications used in present art.
  • Another objective of the invention is to obtain an embodiment having finer grain size in aluminum alloys with Sr and B elements.
  • Another objective of the invention is that grain sizes, obtained in production of aluminum alloy wheels by low pressure casting method, are in the range of 50µm-500µm.
  • Another objective of the invention is that aluminum alloy is formed in homogeneous macrostructure.
  • Another objective of the invention is reduction of defects in casting such as shrinkage and gas porosity in alloy.
  • Another objective of the invention is increase in fluidity during casting process and capability of cast feeding.
  • Another objective of the invention is filling narrow sections easier during casting process.
  • Another objective of the invention is reduction of shrinkage-distortion problems depending on contraction during thermal process.
  • Another objective of the invention is to reduce the number of scrap ratio in production.
  • Another objective of the invention is to be able to reduce heat treatment process time by increase in surface area of grain boundaries due to grain refining; in other words, increase in the number of grains in per unit volume.
  • Another objective of the invention is to obtain improvements in energy consumption and production period regarding to reduction in heat treatment process time.
  • Another objective of the invention is increase in mechanical properties of final product and accordingly, improvement and moderation in design as a result of finer grain structure of aluminum alloys.
  • Another objective of the invention is to obtain commercially successful product with higher mechanical properties according to all these improvements.
  • Another objective of the invention is reducing the amount of additive elements for the aluminum alloy grain refinement up to 1/5-1/7 ratio.
  • For the purpose achieving the mentioned objectives above; the invention relates to a method which ensures refining of grain structure of aluminum alloys. It is comprised of process steps for grain refining which sufficient amount of strontium (Sr) is added to the ladle containing aluminum alloy and boron (B) is added to said ladle after flux influence in degassing process is completed while the rotor is still rotating.
  • Additionally, this method follows the steps in which total titanium content of aluminum alloy is controlled under 0.005% by weight, SrB6 is formed by binding of boron(B) and strontium (Sr) in aluminum alloy at the rate of 1:1.35 by weight, free strontium (Sr) at the rate of 0.015% or more by weight remain in aluminum alloy for eutectic modification following SrB6 formation.
  • Boron (B) is added to the aluminum alloy as AIB compound. Strontium (Sr) is added to the aluminum alloy as AlSr compound.
    • Detailed Explanation of the Invention
  • Invention relates to a method which ensures refining of grain structure of aluminum casting alloys. It comprises the processes in which sufficient amount of strontium (Sr) is added to the ladle containing aluminum alloy and boron (B) is added to the ladle after flux effect in degassing process is finished while the rotor continues rotating for grain refining.
  • This method follows the steps in which total titanium content of aluminum alloy is controlled under 0.005% by weight, SrB6 is formed by binding of boron(B) and strontium (Sr) in aluminum alloy at the rate of 1:1.35 by weight, free strontium (Sr) at the rate of 0.015% or more by weight remain in aluminum alloy for eutectic modification following SrB6 formation. Boron (B) is added to the aluminum alloy as AIB compound. Strontium (Sr) is added to the aluminum alloy as AlSr compound.
  • In SrB6 compound, nearly 4ppm Sr binds 3 ppm Boron. This is equivalent to 1:1.35 mass ratio. When Sr is added at a rate that is more than enough to saturate the existing B to Sr, the remaining free Sr yields the eutectic modification while the combined SrB6 provides grain refining.
  • Preferably AlSi7Mg is used as common aluminium alloy in wheel manufacturing. However, this process is likely to be successful in Al-Si, Al-Cu and Al-Mg alloys too.
  • Prior to degassing, sufficient amount of AlSr is added to the ladle containing aluminum alloy and B is added during degassing period after the flux is activated completely. Since it is important to have an even distribution of B in the alloy it is important to keep the degassing rotor running for a required time after the B addition.
  • The Boron amount in the cast piece can be examined via spectrometer to have a better understanding of SrB6 amount in the alloy but the obtained value comprises also AlB2 and TiB2 phases. Thus in order to achieve a successful grain refining and successor eutectic modification; minimum 35ppm B and 150 ppm Sr should be measured in any section of cast piece.
  • Since the B affinity to Ti is higher than B affinity to Sr, any existing Ti element in the master alloy leads to form TiB2 Although TiB2 is known to be one of the existing grain refining methods in aluminum alloys, the SrB6 formation is reduced significantly by the existence of Ti in the master alloy resulting loss in grain refining effectiveness. Therefore rather Ti free master alloys or master alloys containing Ti below 50ppm should be preferred to have an accomplished grain refining by SrB6.
  • This method can be used in aluminum alloys which includes Titanium element by an appropriate holding ladle and mixing system.
  • AlSr is added to the ladle beforehand and then, AIB is added after flux effect passes in degassing process while rotor is rotating. Afterwards, this ladle is transferred to casting bench.
  • Desired fine grained and modified structure can be maintained in a single charge. Totally, Xppm B + 1.35XppmSr + 100-200 ppm Sr (for modification) is added to the ladle.

Claims (2)

  1. An invention relates to a method which ensures grain refinement of aluminum casting alloys, It is comprised of process steps in which sufficient amount of strontium (Sr) is added to the ladle containing aluminum alloy characterized in that;
    boron (B) is added to the ladle after flux effect is neutralized in degassing process as the rotor continues rotating
    totally, Xppm B + 1.35XppmSr + 100-200 ppm Sr (for modification) is added to the ladle, SrB6 is formed by combination of boron (B) and strontium (Sr) in aluminum alloy at the rate of 1:1.35 by weight and free strontium (Sr) at the rate of 0.015% or more by weight remain in aluminum alloy for eutectic modification following SrB6 formation,
    B is added in the form of an AIB compound and Sr is added in the form of an AlSr compound and the presence of Ti in the master alloy should be limited to less than 50 ppm,
    successful grain refining and eutectic modification is only achieved when the B and Sr contents of the cast piece are at a minimum 35ppm and 150 ppm respectively.
  2. The method according to Claim 1 wherein, Ti free master alloys should be preferred to have an accomplished grain refining by SrB6.
EP15728214.6A 2015-03-10 2015-03-10 Grain refining method for aluminium alloys Active EP3247812B1 (en)

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PL15728214T PL3247812T3 (en) 2015-03-10 2015-03-10 Grain refining method for aluminium alloys

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PCT/TR2015/000097 WO2016144274A1 (en) 2015-03-10 2015-03-10 Grain refining method for aluminum alloys

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EP3247812B1 true EP3247812B1 (en) 2019-03-20

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Publication number Priority date Publication date Assignee Title
CN111289514B (en) * 2020-03-16 2022-02-11 中国兵器科学研究院宁波分院 Method for displaying aluminum alloy macroscopic crystal grains and streamline
CN111996409B (en) * 2020-09-02 2021-07-02 湘潭大学 Grain refining method for preventing silicon poisoning of aluminum-silicon alloy
CN115896552A (en) * 2022-12-13 2023-04-04 兰州理工大学 Alloy additive and application thereof, al-Si alloy and refining and modification method thereof
CN117210724B (en) * 2023-09-13 2024-04-02 山东迈奥晶新材料有限公司 Al-MB for reducing transition group element content in aluminum alloys 6 Alloy and preparation method thereof
CN117660792B (en) * 2024-02-01 2024-04-19 北京航空航天大学 Metal smelting composite stirring degassing device

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DE502004009801D1 (en) 2003-01-23 2009-09-10 Rheinfelden Aluminium Gmbh Die casting alloy of aluminum alloy
US20080299001A1 (en) * 2007-05-31 2008-12-04 Alcan International Limited Aluminum alloy formulations for reduced hot tear susceptibility
AT511397B1 (en) 2011-05-03 2013-02-15 Sag Motion Ag METHOD OF REFINING AND PERMITTING MODIFICATION OF AIMGSI ALLOYS
US9771635B2 (en) * 2012-07-10 2017-09-26 GM Global Technology Operations LLC Cast aluminum alloy for structural components
CN103981386B (en) * 2014-04-30 2016-04-06 苏州有色金属研究院有限公司 Hypoeutectic and cocrystallized Al-Si alloy go bad and the method for refinement

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ES2724953T3 (en) 2019-09-18
EP3247812A1 (en) 2017-11-29
PL3247812T3 (en) 2019-08-30
WO2016144274A1 (en) 2016-09-15

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