EP2669028A1 - Agent d'affinage de grain cristallin pour coulage et son procédé de production - Google Patents

Agent d'affinage de grain cristallin pour coulage et son procédé de production Download PDF

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Publication number
EP2669028A1
EP2669028A1 EP12738824.7A EP12738824A EP2669028A1 EP 2669028 A1 EP2669028 A1 EP 2669028A1 EP 12738824 A EP12738824 A EP 12738824A EP 2669028 A1 EP2669028 A1 EP 2669028A1
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EP
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Prior art keywords
aluminum
grain refiner
casting
powder
grain
Prior art date
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EP12738824.7A
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German (de)
English (en)
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EP2669028B1 (fr
EP2669028A4 (fr
Inventor
Yoshimi Watanabe
Hisashi Sato
Takahiro Matsuoka
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Nagoya Institute of Technology NUC
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Nagoya Institute of Technology NUC
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
    • 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
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/0408—Light metal alloys
    • C22C1/0416—Aluminium-based alloys
    • 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
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/047—Making non-ferrous alloys by powder metallurgy comprising intermetallic compounds
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps

Definitions

  • the present invention relates to a grain refiner for casting and a production method thereof.
  • Melt processing is one of representative processes for metals and alloys.
  • the melt processing advantageously gives complicated, smooth-shaped products and is applicable to any hard-to-work metals and alloys.
  • Solidification is a most important phase change in the melt processing.
  • the solidification is associated with nucleation which includes homogeneous nucleation and heterogeneous nucleation.
  • Heterogeneous nuclei when added, refine the solidified microstructure, i.e., cast microstructure.
  • the material structure refinement is one of material strengthening techniques and is known as a technique for strengthening a material without impairing its ductility/toughness.
  • ⁇ y ⁇ 0 + k d - 1 / 2
  • ⁇ 0 a friction stress for dislocation movement
  • k a so-called Hall-Petch coefficient
  • both ⁇ 0 and k are material specific.
  • NPL Non Patent Literature 1
  • the degree of mismatching ⁇ is defined in crystal lattice in a low-index plane of an atomic arrangement toward one direction.
  • the degree of mismatching ⁇ is specified by Mathematical Expression (2) expressed as follows.
  • ⁇ a - a 0 / a 0 ⁇ 100 %
  • a is the lattice constant of a low-index plane of the heterogeneous nucleator
  • a 0 is the lattice constant of a low-index plane of the cast material.
  • Al 3 Ti, TiB 2 , and Al 3 Zr are known as substances to possibly serve as heterogeneous nucleators in aluminum grains.
  • PTL Patent Literature
  • the intermetallic compounds Al 3 Ti and Al 3 Zr have D0 22 and D0 23 structures, respectively.
  • Al 3 Ti having the D0 22 structure is highly valued as a grain refiner.
  • pure aluminum and Al 3 Ti having the D0 22 structure have lattice constants of 0.40496 nm and 0.384 nm, respectively, with a degree of mismatching ⁇ between them of about 5%.
  • the grain refining performance of a grain refiner depends on the number of heterogeneous nuclei in the grain refiner.
  • PTL 1 indicates that the number of heterogeneous nuclei can be controlled by applying severe plastic deformation to a grain refiner to allow the grain refiner to exhibit better grain refining performance.
  • D0 22 -structure intermetallic compounds have poor crystal symmetry, as illustrated in FIG. 1B .
  • investigations have been intensively made to allow them to have a satisfactorily symmetric L1 2 structure ( FIG. 1C ) by adding an additional element thereto (e.g., NPL 2, 3 and 4).
  • Ll 2 -structure intermetallic compounds having various lattice constants have been found based on the investigations.
  • Unfortunately these Ll 2 -structureintermetallic compounds have not yet been in practical use. This is because they suffer from pores formed upon solidification and exhibit insufficient tensile ductility.
  • the Ll 2 -structure intermetallic compounds if to be used in bulk, fail to exhibit strengths at expected level.
  • the D0 22 -structure Al 3 Ti has a degree of mismatching ⁇ of about 5% as described above.
  • a compound having a degree of mismatching ⁇ of equal to or less than this level can serve as a refiner (refining additive) having higher performance than that of Al 3 Ti.
  • Aluminum alloys have lattice constants different from that of pure aluminum, and there should be optimal refining additives for respective aluminum alloys.
  • the D0 22 -structure Al 3 Ti has lattice constants differing from a crystal face to another, i.e., has lattice constants a of 0.384 nm and c of 0.8596 nm as illustrated in FIG. 1B .
  • This means that the D0 22 -structure Al 3 Ti has degrees of mismatching ⁇ differing from a crystal face to another and has functions as a heterogeneous nucleus differing from a crystal face to another.
  • Exemplary process variables that affect the grain refinement of cast materials include the molten metal temperature, amount of the grain refiner, as well as holding time (retention time) after the addition of the grain refiner to a molten metal.
  • Al 3 Ti heterogeneous nuclei fail to exist in equilibrium in the molten metal (see FIG. 2 ).
  • Heterogeneous nuclei in nonequilibrium are utilized in the practical production of cast aluminum by regulating the holding time. After further consideration, this indicates that a grain refiner itself does not have to be a system in equilibrium. Namely, even an intermetallic compound that originally fails to exist stably in equilibrium should be usable as heterogeneous nuclei.
  • an object of the present invention is to provide a refining additive (refiner) including heterogeneous nuclei which have a lower degree of mismatching ⁇ than those of heterogeneous nuclei of existing grain refiners and which have a minimized degree of mismatching ⁇ with respect to pure aluminum or aluminum alloys.
  • Another object of the present invention is to provide a method for producing the refining additive.
  • the present invention employs an Ll 2 -structure intermetallic compound from a viewpoint entirely different from that of the investigations of Ll 2 -structure intermetallic compounds.
  • a 1st aspect of the present invention provides a grain refiner for casting which is a bulk solid and includes a matrix mainly comprising aluminum; and particles of an intermetallic compound dispersed in the matrix, the intermetallic compound having an L1 2 structure and represented by Formula (1) expressed as follows: Al Y 3 ⁇ Z where Y is one element selected from the group consisting of Cu, Fe, Ni, Zn, Pd, Cr, Mn, Co, Ag, Rh, Pt, Au, and Hf; and Z is one element selected from the group consisting of Ti, Zr, and Zn (claim 1).
  • Z in Formula (1) may be Ti (claim 2).
  • the intermetallic compound may be Al 5 CuTi 2 , Al 22 Fe 3 Ti 8 , or Al 67 Ni 8 Ti 25 (claim 3, 4, or 5).
  • An intermetallic compound can have a varying lattice constant by replacing part of aluminum in the D0 22 -structure Al 3 Ti or replacing Ti in the D0 22 -structure Al 3 Ti each with another element, as indicated in the L1 2 structure of Formula (1). This allows the intermetallic compound to have a lattice constant nearer to that of pure aluminum than the D0 22 -structure Al 3 Ti does. Appropriate selection of the other element to be replaced allows the intermetallic compound to have a lattice constant near to that of a specific aluminum alloy.
  • D0 22 -structure Al 3 Ti when combined with a third element Y, gives L1 2 -structure(Al,Y) 3 Ti intermetallic compounds as illustrated in FIG. 1(c) .
  • the intermetallic compounds have lattice constants a and degrees of mismatching ⁇ with respect to pure aluminum as follows.
  • the intermetallic compounds have lattice constants nearer to that of pure aluminum than the D0 22 -structure Al 3 Ti does. This demonstrates that the intermetallic compounds serve as heterogeneous nuclei having degrees of mismatching ⁇ smaller than that of the D0 22 -structure Al 3 Ti.
  • the grain refiner for casting can be produced through spark plasma sintering.
  • the grain refiner for casting may be not a dense sintered compact but a semi-sintered compact.
  • the present invention provides, in an embodiment, a grain refiner including a heterogeneous nucleator with a small degree of mismatching (i.e. disregistry).
  • the heterogeneous nucleator may have a degree of mismatching of 5 or less and preferably 4 or less.
  • This grain refiner is a bulk solid (solid mass) and includes a matrix and particles of an intermetallic compound dispersed in the matrix, in which the matrix mainly includes Al, and the intermetallic compound serves as a heterogeneous nucleator, has an L1 2 -structure, and is expressed by Formula (1).
  • the intermetallic compound originally fails to exist stably in equilibrium with Al.
  • These intermetallic compounds have lattice constants near to that (0.40496 nm) of pure aluminum.
  • matrix mainly including Al refers to a matrix including Al in a largest amount as a component and containing pure aluminum or an aluminum alloy.
  • the matrix preferably has the same composition with that of the cast material.
  • pure aluminum is preferably used as the matrix.
  • an aluminum alloy having the same composition with that of the target cast material is preferably used as the matrix.
  • a powdery L1 2 -structure intermetallic compound represented by Formula (1) if directly added as particles to the molten metal, is not mixed with the molten metal and floats thereon because of its poor wettability.
  • the present invention employs a grain refiner which has a solid structure (bulk or mass) and includes a matrix; and particles of an L1 2 -structure intermetallic compound represented by Formula (1) dispersed in the matrix. This allows the Ll 2 -structure intermetallic compound represented by Formula (1) in the grain refiner to disperse in the molten metal and to effectively serve as heterogeneous nuclei.
  • the particles of the intermetallic compound if contained in an excessively large volume fraction based on the total volume of the grain refiner, may fail to satisfactorily disperse in the molten metal; whereas if contained in an excessively small volume fraction, may require a large amount of the grain refiner to be added, thus being industrially undesirable.
  • the particles of the intermetallic compound may be present in a volume fraction of 5% to 40% of the entire grain refiner.
  • An intermetallic compound represented by Formula (1) such as L1 2 structure (Al,Y) 3 Ti, cannot exist in equilibrium with Al.
  • sintering should be performed at a low temperature in a short time such that the intermetallic compound does not decompose.
  • spark plasma sintering enables rapid and low-temperature sintering and can give a bulk even in a nonequilibrium system.
  • a grain refiner for casting can be produced by mixing a powder of the intermetallic compound with a powder of the matrix to give a powder mixture; compacting the powder mixture to give a powder compact; and sintering the powder compact through SPS.
  • a material powder compact when fired at a low temperature in a short time through another sintering technique than SPS, generally gives a sintered compact having low mechanical strengths.
  • Such semi-sintered compact can serve as a grain refiner, because the mechanical strengths of the (semi-)sintered compact do not affect properties of the cast material.
  • the grain refiner for casting may also be produced through not SPS but another sintering technique such as hot pressing, or atmospheric sintering after hot or cold isostatic compaction.
  • the term "semi-sintered compact” refers to a compact having a packing density of 70% to 90%.
  • the "packing density” is determined by taking an image of the microstructure under an optical microscope, analyzing the image to measure an area fraction of pores; and subtracting the area fraction from 100%.
  • the term “hot isostatic compaction” refers to a technique in which a work is isostatically compressed using a high-temperature high-pressure gas as a medium to densify the work.
  • the term “cold isostatic compaction” refers to a technique in which a powder is filled in a rubber mold, and hydrostatic pressure is applied thereto to compact the powder.
  • the grain refiner for casting is added to a molten pure aluminum or aluminum alloy, the resulting molten metal is poured into a mold and yields a pure-aluminum or aluminum-alloy cast material. This allows the pure-aluminum or aluminum-alloy cast material to have a refined and uniformized microstructure.
  • the grain refinement of the cast material can be optimized by regulating the holding time in this process, as demonstrated by Examples 1 to 10 mentioned below.
  • Example 1 employed Al 5 CuTi 2 as a sample to be prepared.
  • Al 5 CuTi 2 has a relatively wide compositional range in the equilibrium diagram among Ll 2 -structure intermetallic compounds. This compound is illustrated merely by way of example and is not intended to limit heterogeneous nucleators to be used.
  • a bulk Al-40 percent by mass Cu alloy, powdery pure aluminum, and powdery pure titanium were used as materials to prepare the sample, but they are not intended to limit starting materials to be used. These materials were subjected to arc melting in an argon atmosphere and yielded a bulk sample. To give a uniform sample, melting in the arc melting was performed at least seven times after the respective materials were melted and mixed with each other.
  • the as-melted sample was cut into a rectangular solid.
  • the cut sample was placed on an aluminum plate, arranged at the center of a soaking zone in an infrared gold image furnace, and homogenized at 1100°C in a vacuum for one hour.
  • FIG. 3 illustrates X-ray diffractometric data of the homogenized sample.
  • the sample had an Al 5 CuTi 2 peak pattern, as illustrated in FIG. 3 .
  • the sample was found to have a lattice constant a of 0.3917 nm as calculated from the result, which approximates the literature value.
  • the compound should be pulverized into a powder so as to have smaller particle sizes.
  • the powdery Al 5 CuTi 2 if directly added to the aluminum molten metal, may highly possibly fail to disperse therein because the powder is not mixed with the molten metal but floats thereon due to its poor wettability.
  • Al 5 CuTi 2 particles were dispersed in an aluminum matrix through spark plasma sintering to give a grain refiner in the following manner.
  • the prepared bulk Al 5 CuTi 2 was pulverized into particles, sieved using sieves of 150 ⁇ m and 75 ⁇ m openings, and yielded a powder having particle sizes of 75 ⁇ m to 150 ⁇ m.
  • the prepared Al 5 CuTi 2 powder was mixed with a powdery pure aluminum to give a powder mixture having a volume fraction of the Al 5 CuTi 2 powder of 10%, and the powder mixture was compacted to give a powder compact.
  • the powder compact was sintered using a compact spark plasma sintering system (DR. SINTER Series, SPS-515S, Sumitomo Coal Mining Co., Ltd.) and yielded a bulk refiner. This process was performed at a compaction pressure of 45 MPa, a rate of temperature rise of 100°C per minute, a sintering temperature of 500°C, for a holding time of 5 minutes.
  • the prepared bulk grain refiner was subjected to X-ray diffractometry, the data of which are indicated in FIG. 4 .
  • the sample had an intense Al peak pattern with a volume fraction of 90% and also had a clear peak pattern of Al 5 CuTi 2 .
  • the data demonstrate that Al 5 CuTi 2 remained as unreacted in the sample.
  • FIG. 5B is a schematic view of FIG. 5A . These figures demonstrate that the sample included powdered Al 5 CuTi 2 particles as remained. The sample had clear grain boundaries, indicating that the Al 5 CuTi 2 particles did not react with the aluminum matrix.
  • the rapid and low-temperature sintering allowed the L1 2 -structure intermetallic compound Al 5 CuTi 2 to remain without reaction in the sample.
  • the remained L1 2 -structureintermetallic compound will serve as heterogeneous nuclei in an aluminum cast material. This enables production of a grain refiner including heterogeneous nuclei of the L1 2 -structure intermetallic compound Al 5 CuTi 2 .
  • the produced grain refiner was used in a casting experiment. Initially, 148.8 g of a pure aluminum ingot was melted at 750°C in a crucible and combined with 1.2 g (0.8 percent by mass) of the refiner. The amount of the refiner in this experiment was determined so that the resulting cast material had a sufficiently low Ti content as compared to the peritectic composition (0.12 percent by mass) in an Al-Ti binary system. The molten metal immediately after the grain refiner addition was stirred for 30 seconds without subsequent holding (held for a holding time of 0 second).
  • Comparative Example 1 An experiment as Comparative Example 1 was performed by the above procedure to give an aluminum cast material by melting 148.8 g of a pure aluminum ingot at 750°C in a crucible, except for adding 1.2 g of pure aluminum to the molten metal.
  • the aluminum cast material was cut at a position 5 mm high from the bottom, and a top face of which was defined as a face to be observed.
  • the observation face was chemically polished with emery paper of #80 to #4000, buffed with 1- ⁇ m alumina, and etched with a 10% hydrofluoric acid for 90 seconds.
  • FIGS. 6A and 7A depict photomicrographs of sample cross sections of Comparative Example 1 using no grain refiner and of Example 1 using the grain refiner, respectively.
  • FIGS. 6B and 7B depict schematic views of Areas A1 an A2 in FIGS. 6A and 7A , respectively.
  • the sample using no grain refiner included a regular solidified microstructure containing equiaxial grains and columnar grains as observed.
  • the sample using the refiner had a microstructure that is approximately uniform and refined as a whole, while partially having columnar grains.
  • That sample included approximately equiaxed grains even in a region including columnar grains.
  • the samples were subjected to average grain size measurement by the mean linear intercept technique.
  • the sample using no grain refiner had an average grain size of 1353 ⁇ m, whereas the sample using the grain refiner had an average grain size refined to 851 ⁇ m.
  • Example 2 to 5 casting experiments were performed under the conditions as in Example 1 using the grain refiner prepared in Example 1, except for holding the mixture for holding times of 120, 210, 300, and 600 seconds, respectively, after stirring the mixture for 30 seconds immediately after the grain refiner addition.
  • Example 6 a grain refiner was prepared by the procedure of Example 1, except for using the Al 5 CuTi 2 powder in a volume fraction of 20%. Using the prepared grain refiner, casting experiments were performed under the conditions as in Example 1, except for adding the refiner in an amount of 0.4 percent by mass and holding the resulting mixture for holding times of 0, 210, 300, 480, and 600 seconds, respectively, after stirring the mixture for 30 seconds immediately after the grain refiner addition.
  • FIG. 8 depicts average grain sizes of aluminum cast materials obtained in Examples 2 to 10, as well as those of Example 1 and after-mentioned Examples 11 and 12.
  • FIG. 9A depicts the cross section of the sample of Example 9; and FIG. 9B depicts a schematic view of Area A3 in FIG. 9A. These demonstrate that the sample of Example 9 had a microstructure being approximately uniform and refined as a whole.
  • Al 22 Fe 3 Ti 8 and Al 67 Ni 8 Ti 25 were prepared by arc melting. They were vacuum-encapsulated and homogenized in a muffle furnace at 1200°C for 24 hours and at 1100°C for 100 hours, respectively.
  • the bulk Al 22 Fe 3 Ti 8 and Al 67 Ni 8 Ti 25 were pulverized and classified to powders of 75 to 150 ⁇ m by the procedure of Example 1. These were mixed each in a volume fraction of 10% with a powdery pure aluminum (99.9%), from which refiners were prepared through SPS.
  • the prepared refiners were used in casting experiments under the conditions as in Example 1.
  • the aluminum cast materials of Examples 11 and 12 prepared using the refiner both had microstructures being approximately uniform and refined as a whole. Their average grain sizes were measured by the mean linear intercept technique. With reference to FIG. 8 , the aluminum cast material of Example 11 prepared using the refiner containing heterogeneous nuclei of Al 22 Fe 3 Ti 8 had an ⁇ -aluminum grain size of 642 ⁇ m. The aluminum cast material of Example 12 prepared using the refiner containing heterogeneous nuclei of Al 67 Ni 8 Ti 25 had an ⁇ -aluminum grain size of 260 ⁇ m. These data demonstrate that the refiners using Al 22 Fe 3 Ti 8 and Al 67 Ni 8 Ti 25 , respectively, exhibited satisfactory grain refining performance.
  • Titanium is a rare metal.
  • the technique according to the present invention may possibly allow another element to be used instead of titanium in heterogeneous nuclei. This provides grain refiners without influence by world situation on demand and supply of such rare metals.
  • the present invention allows arbitrary use of nonequilibrium heterogeneous nuclei and is applicable to all structural metal materials based on not only aluminum, but also on iron, titanium, and other metals.
  • the refining performance depends on the number of heterogeneous nuclei in a grain refiner.
  • the number of heterogeneous nuclei can be controlled by applying severe plastic deformation to the grain refiner according to the technique disclosed in PTL 1.
  • the present invention can employ this technique for the control of the number of heterogeneous nuclei.
  • the present invention helps all cast materials to have higher strengths. This contributes to weight reduction of transport equipment, resulting in higher fuel efficiencies. When applied to a cast die for use typically in resin foam production, the present invention contributes to wall-thickness reduction of the die. This allows heating-energy saving and suppresses carbon dioxide evolution.

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EP12738824.7A 2011-01-25 2012-01-19 Agent d'affinage de grain cristallin pour coulage et son procédé de production Active EP2669028B1 (fr)

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JP2011013269 2011-01-25
PCT/JP2012/051050 WO2012102162A1 (fr) 2011-01-25 2012-01-19 Agent d'affinage de grain cristallin pour coulage et son procédé de production

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EP2669028A1 true EP2669028A1 (fr) 2013-12-04
EP2669028A4 EP2669028A4 (fr) 2016-08-24
EP2669028B1 EP2669028B1 (fr) 2019-07-17

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CN115627391B (zh) * 2022-09-29 2024-01-30 河北科技大学 一种铝及其合金用晶粒细化剂及其制备方法与应用

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4865666A (en) * 1987-10-14 1989-09-12 Martin Marietta Corporation Multicomponent, low density cubic L12 aluminides
JPH07188701A (ja) * 1993-12-27 1995-07-25 Suzuki Motor Corp Ａｌ３ Ｔｉ分散強化アルミニウム合金と、その粉末並びにそれらの製造方法
JPH10204555A (ja) * 1997-01-17 1998-08-04 Toyota Motor Corp アルミニウム鋳造合金の結晶粒微細化剤の製造方法
JPH10317083A (ja) * 1997-05-13 1998-12-02 Kobe Steel Ltd アルミニウム合金用結晶粒微細化剤
JP2001152263A (ja) * 1999-11-18 2001-06-05 Ueda Seni Kagaku Shinkokai ハイブリッド傾斜機能材料及びその製造方法
JP2004346368A (ja) * 2003-05-21 2004-12-09 Ngk Insulators Ltd 複合材料の製造方法、及び複合材料
JP4691735B2 (ja) 2004-05-20 2011-06-01 国立大学法人 名古屋工業大学 鋳造用結晶粒微細化剤及びその製造方法
TR200504376A2 (tr) * 2005-11-02 2008-05-21 T�B�Tak-T�Rk�Ye B�L�Msel Ve Tekn�K Ara�Tirma Kurumu Tane küçültücü ön alaşım üretmek için bir proses

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104439206A (zh) * 2014-11-29 2015-03-25 山东大学 一种硅晶粒异质形核强化剂在促进铝硅合金熔体中硅晶粒形核中的应用
CN105648251A (zh) * 2016-02-01 2016-06-08 东南大学 一种铸造铝合金用铝镧硼晶粒细化剂的制备方法
CN107419135A (zh) * 2017-07-27 2017-12-01 济南大学 锌‑铝‑钇中间合金细化剂及其制备方法和应用
CN107419135B (zh) * 2017-07-27 2018-09-25 济南大学 锌-铝-钇中间合金细化剂及其制备方法和应用
CN109420765A (zh) * 2017-08-25 2019-03-05 波音公司 使用晶粒细化剂对用于加成制造的高强度铝合金进行改性
CN109136599A (zh) * 2018-10-08 2019-01-04 兰州理工大学 高熵合金孕育亚共晶铝硅合金制备工艺
WO2021083385A1 (fr) * 2019-11-25 2021-05-06 河南科技大学 Procédé de préparation d'un matériau de cuivre ou d'alliage de cuivre et agent d'affinage pour l'affinage de ce matériau
CN111020248A (zh) * 2019-12-02 2020-04-17 上海航天精密机械研究所 一种Ag-Zr-Zn中间合金及其制备方法和应用

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