US20140023547A1 - Magnesium alloy chips and process for manufacturing molded article using same - Google Patents
Magnesium alloy chips and process for manufacturing molded article using same Download PDFInfo
- Publication number
- US20140023547A1 US20140023547A1 US14/009,861 US201214009861A US2014023547A1 US 20140023547 A1 US20140023547 A1 US 20140023547A1 US 201214009861 A US201214009861 A US 201214009861A US 2014023547 A1 US2014023547 A1 US 2014023547A1
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- United States
- Prior art keywords
- chips
- molded article
- magnesium alloy
- carbon
- weight
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- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims description 26
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- 230000008569 process Effects 0.000 title claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 96
- 238000001746 injection moulding Methods 0.000 claims abstract description 68
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 41
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052799 carbon Inorganic materials 0.000 claims description 49
- 239000006229 carbon black Substances 0.000 claims description 24
- 238000010521 absorption reaction Methods 0.000 claims description 11
- 238000002844 melting Methods 0.000 claims description 11
- 230000004907 flux Effects 0.000 claims description 9
- 239000011164 primary particle Substances 0.000 claims description 9
- 239000011777 magnesium Substances 0.000 claims description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 239000011159 matrix material Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 3
- 238000005452 bending Methods 0.000 abstract description 24
- 238000012360 testing method Methods 0.000 description 42
- 229910052751 metal Inorganic materials 0.000 description 17
- 239000002184 metal Substances 0.000 description 17
- 239000011701 zinc Substances 0.000 description 17
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 16
- 238000009864 tensile test Methods 0.000 description 16
- 229910052725 zinc Inorganic materials 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 12
- 230000007797 corrosion Effects 0.000 description 10
- 238000005260 corrosion Methods 0.000 description 10
- 238000006073 displacement reaction Methods 0.000 description 10
- 229910052790 beryllium Inorganic materials 0.000 description 9
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 9
- 238000009826 distribution Methods 0.000 description 8
- 239000011572 manganese Substances 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 7
- 239000000956 alloy Substances 0.000 description 7
- 229910052748 manganese Inorganic materials 0.000 description 7
- 238000000465 moulding Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 238000013507 mapping Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- 239000004594 Masterbatch (MB) Substances 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000005204 segregation Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000010119 thixomolding Methods 0.000 description 3
- 229910016384 Al4C3 Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 241000219094 Vitaceae Species 0.000 description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 description 2
- 239000005539 carbonized material Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000006232 furnace black Substances 0.000 description 2
- 235000021021 grapes Nutrition 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- VHHHONWQHHHLTI-UHFFFAOYSA-N hexachloroethane Chemical compound ClC(Cl)(Cl)C(Cl)(Cl)Cl VHHHONWQHHHLTI-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000004154 testing of material Methods 0.000 description 2
- 229910018137 Al-Zn Inorganic materials 0.000 description 1
- 229910018573 Al—Zn Inorganic materials 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 101001108245 Cavia porcellus Neuronal pentraxin-2 Proteins 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229910003023 Mg-Al Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 238000006664 bond formation reaction Methods 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000006231 channel black Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 239000012768 molten material Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000004151 quinonyl group Chemical group 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Images
Classifications
-
- B22F1/0055—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D17/00—Pressure die casting or injection die casting, i.e. casting in which the metal is forced into a mould under high pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D21/00—Casting non-ferrous metals or metallic compounds so far as their metallurgical properties are of importance for the casting procedure; Selection of compositions therefor
- B22D21/02—Casting exceedingly oxidisable non-ferrous metals, e.g. in inert atmosphere
- B22D21/04—Casting aluminium or magnesium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D23/00—Casting processes not provided for in groups B22D1/00 - B22D21/00
- B22D23/06—Melting-down metal, e.g. metal particles, in the mould
-
- 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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/06—Metallic powder characterised by the shape of the particles
- B22F1/068—Flake-like particles
-
- 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
- B22F3/02—Compacting only
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
- C22C23/02—Alloys based on magnesium with aluminium as the next major constituent
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2991—Coated
Definitions
- the present invention relates to magnesium alloy chips for injection molding and a process for manufacturing a molded article using same.
- a magnesium alloy has a high specific strength since it is most lightweight among practically used metals, and exhibits excellent heat radiation and better recyclability than a resin.
- molded articles made of a magnesium alloy are used in a wide variety of applications such as electric devices, automobiles and leisure goods.
- Injection molding is a common molding methods for a magnesium alloy.
- a magnesium alloy is injection-molded by heating chips made of a magnesium alloy in a cylinder into a molten or semi-molten state (coexistence of a solid and a liquid phases) and then injecting the molten or semi-molten magnesium alloy into a mold.
- injection-molding is preferable for forming a thin-wall article such as a casing of an electric device.
- a so-called thixomolding method that is, inter alia, a molding method in which a semi-molten material is injected into a mold, is a typical injection molding method for a magnesium alloy and is used for producing various molded articles.
- a Mg—Al alloy having excellent mechanical properties particularly a Mg—Al—Zn alloy being well-balanced between mechanical properties and processability and exhibiting improved corrosion resistance have been widely used as a magnesium alloy for injection molding.
- a Mg—Al alloy having excellent mechanical properties particularly a Mg—Al—Zn alloy being well-balanced between mechanical properties and processability and exhibiting improved corrosion resistance have been widely used as a magnesium alloy for injection molding.
- further improvement in mechanical properties of a molded article has been needed in order to allow for thinning of a molded article made of a magnesium alloy and increasing an yield.
- a known alternative method for adding carbon to an aluminum-containing magnesium alloy is addition of carbon powder (for example, see Patent Reference Nos. 1 and 2).
- carbon powder when carbon powder, is directly added to a molten magnesium alloy, the carbon powder tends to agglutinate, so that a molded article obtained may have insufficiently improved or have varied mechanical properties.
- Patent Reference No. 3 has described a process for manufacturing a carbon-containing magnesium alloy comprising mixing 5 to 30 parts by weight of at least one of carbon powder, carbon nanofiber and carbon nanotube with 100 parts by weight of a magnesium alloy to prepare a master batch and then mixing the master batch with a 3- to 20-fold parts by weight of a magnesium alloy.
- the magnesium alloy thus produced contains uniformly dispersed carbon and has improved tensile strength and a higher Young's modulus. The process is, however, troublesome and thus at a disadvantage in terms of cost.
- an objective of the present invention is to provide chips for injection molding allowing for forming a molded article made of a magnesium alloy which has excellent bending properties and tensile strength which vary in a small range.
- Another objective of the invention is to provide a process for manufacturing a molded article made of a magnesium alloy using such chips for injection molding.
- a content of the carbon powder is preferably 0.01 to 3% by weight.
- the carbon powder is preferably carbon black.
- the carbon black more preferably has an average primary particle diameter of from 5 to 100 nm and a DBP absorption of from 40 to 200 mL/100 g.
- the above problems can be also solved by providing a process for manufacturing the chips for injection molding, comprising mixing chips made of an aluminum-containing magnesium alloy with the carbon powder.
- a preferable embodiment of the present invention is a process for manufacturing a molded article made of a magnesium alloy, comprising charging the chips for injection molding in an injection-molding machine and then injection-molding the chips.
- a complex of aluminum and carbon is dispersed in a magnesium matrix.
- Another preferable embodiment of the present invention is a process for manufacturing an ingot made of a magnesium alloy, comprising heat-melting a scrap formed during injection-molding of the chips for injection molding in the presence of a flux and then cooling it.
- a ratio (C 2 /C 1 ) of a carbon content C 2 (% by weight) in said ingot to a carbon content C 1 (% by weight) in said scrap is 0.1 or less.
- a molded article produced by injection-molding of chips for injection molding of the present invention has excellent bending properties and tensile strength which vary in a small range. Furthermore, a process for manufacturing a molded article made of a magnesium alloy of the present invention can conveniently provide a molded article made of a magnesium alloy having excellent bending properties and tensile strength which vary in a small range. It thus allows for making a molded article thinner and improving an yield. Furthermore, a scrap formed during injection-molding of the chips for injection molding has improved recyclability.
- FIG. 1 shows an exterior photo of a test piece in a tensile test and an exterior photo of a testing machine on which the test piece is set.
- FIG. 2 shows an exterior photo of a testing machine on which the test piece is set, in a bending test.
- FIG. 3 shows micrograms of a cross section of a molded article cut in a direction vertical to a flowing direction of a molten metal in Example 1 and Comparative Example 1.
- FIG. 4 shows a relationship between a displacement and a load at break of a test piece as determined by a tensile test in Example 1 and Comparative Example 1.
- FIG. 5 shows a relationship between a displacement and a load at break of a test piece as determined by a bending test in Example 1 and Comparative Example 1.
- FIG. 6 shows an elemental map of an area containing a complex of aluminum and carbon in the surface of a molded article in Example 1.
- FIG. 7 shows measurement points in determination of content distribution of each of aluminum and zinc in a molded article in Example 1 and Comparative Example 1.
- FIG. 8 shows content distribution of aluminum in a molded article in Example 1 and Comparative Example 1.
- FIG. 9 shows content distribution of zinc in a molded article in Example 1 and Comparative Example 1.
- FIG. 10 shows a 0.2% proof stress of a molded article in Examples 1 to 3 and Comparative Example 1 as determined by a tensile test.
- the present invention provides chips for injection molding wherein the surfaces of chips made of an aluminum-containing magnesium alloy are coated with carbon powder.
- the chips to be coated with carbon powder must be made of an aluminum-containing magnesium alloy.
- the chips must be made of an alloy containing aluminum as a component in addition to magnesium.
- Aluminum is effective for improving tensile strength and corrosion resistance of a magnesium alloy.
- a complex of aluminum and carbon is formed in a molded article produced by the present invention. Formation of the complex would lead to a molded article having excellent bending properties and tensile strength.
- An aluminum content in a magnesium alloy used in the present invention is preferably 1 to 15% by weight. If an aluminum content is less than 1% by weight, tensile strength and corrosion resistance of a molded article produced may be reduced. Furthermore, formation of a complex of aluminum and carbon may be inhibited in a molded article produced, thus bending properties and tensile strength may not improve. An aluminum content of more than 15% by weight may lead to brittle failure.
- the magnesium alloy can contain zinc, wherein a zinc content is 3% by weight or less. In a case that zinc is contained therein, toughness of magnesium alloy and fluidity during molding further improve.
- a zinc content is preferably 0.1 to 3% by weight. If a zinc content is less than 0.1% by weight, toughness of a molded article produced and fluidity during molding may be reduced. If a zinc content is more than 3% by weight, hot tearing may occur.
- the magnesium alloy can contain manganese, in which a manganese content is 1% by weight or less. In a case that manganese is contained therein, corrosion resistance of a magnesium alloy further improves.
- a manganese content is preferably 0.05 to 1% by weight. If a manganese content is less than 0.05% by weight, corrosion resistance of a molded article produced may be reduced. If a manganese content is more than 1% by weight, compression strength and tensile strength may be reduced.
- the magnesium alloy can contain beryllium, in which a beryllium content is 0.003% by weight or less. In a case that beryllium is contained therein, flame resistance during melting of a magnesium alloy improves. In a case that beryllium is contained therein, brightness of a molded article produced also improves.
- a beryllium content is preferably 0.0001 to 0.003% by weight. If a beryllium content is less than 0.0001% by weight, it may fail to improve flame resistance or brightness. If a beryllium content is more than 0.003% by weight, crystals may be coarse, leading to reduction of tensile strength and a higher cost.
- the magnesium alloy can contain calcium, in which a calcium content is 3% by weight or less. In a case that calcium is contained therein, flame retardancy of a magnesium alloy improves.
- a calcium content is generally 0.5 to 3% by weight.
- the magnesium alloy can contain elements other than those described above as long as they do not reduce the effect of the present invention. Such elements can be willingly added or contained as inevitable impurities. A content of such elements is generally 1% by weight or less.
- the balance of a magnesium alloy used for the chips is magnesium, whose content is generally 80% by weight or more.
- the magnesium alloy can be specifically selected from magnesium alloys such as AZ91, AM50, AM60 and AZ31 in accordance with the ASTM Standard.
- AZ91 is preferable, which is well-balanced between mechanical properties and processability and exhibits higher corrosion resistance.
- chips there are no particular restrictions to a process for manufacturing the chips. Generally, an ingot made of the above magnesium alloy can be cut into the chips. There are no particular restrictions to the shape or the size of the chips, which can be appropriately selected, depending on, for example, the specifications of an injection-molding machine used for producing a molded article. Chips with a length of from 1 to 10 mm is generally used. Herein, a length of a chip denotes a distance between the furthest positions in the chip.
- the carbon powder used in the present invention can be selected from, but not limited to, carbon black, graphite such as scaly graphite, coke or the like.
- the carbon powder is preferably carbon black.
- carbon black and the chips are mixed by, for example, a mixer to coat the surfaces of the chips with carbon black.
- the use of chips for injection molding coated with carbon powder in injection molding would allow carbon powder to easily disperse in a magnesium alloy.
- carbon black there are no particular restrictions to the type of the carbon black. Examples which can be used include furnace black, thermal black, channel black, acetylene black ketjen black and the like, which can be used in combination.
- the carbon black has an average primary particle diameter of from 5 to 100 nm and a DBP absorption of from 40 to 200 mL/100 g.
- a DBP absorption is a parameter corresponding to a volume of voids in a bunch of grapes when fused primary particles of carbon black, so-called “aggregate”, is assumed to be a bunch of grapes. As the aggregate grows, the void volume increases and thus a DBP absorption increases.
- Formation of a complex of aluminum and carbon may be influenced by a primary particle diameter of carbon black and also a growing state of the aggregate. It is, therefore, preferable that an average primary particle diameter and a DBP absorption are within a certain range.
- a DBP absorption can be determined in accordance with JIS K6217.
- the carbon black preferably has a DBP absorption of from 40 to 200 mL/100 g, more preferably 60 to 200 mL/100 g, further preferably 80 to 200 mL/100 g.
- the carbon black can have functional groups in its surface.
- functional groups include hydroxy groups such as phenolic hydroxy group, carboxyl groups and quinone groups.
- the surfaces of the chips are coated with the carbon powder to produce chips for injection molding having surfaces coated with the carbon powder.
- the chips and the carbon powder can be mixed using a mixer to produce chips for injection molding having the surfaces coated with the carbon powder.
- a mixing ratio of the chips to the carbon powder can be appropriately adjusted, depending on the amount of carbon contained in a molded article to be produced.
- the amount of the carbon powder in the chips for injection molding coated with the carbon powder is preferably 0.01 to 3% by weight, more preferably 0.01 to 0.5% by weight.
- the chips for injection molding having surfaces coated with the carbon powder are charged in an injection-molding machine and then injection-molded to provide a molded article.
- the chips for injection molding charged in an injection-molding machine are heated in a cylinder while being fed via a screw in the cylinder to an injection nozzle.
- a molten or semi-molten (coexistence of a solid and a liquid phases) magnesium alloy fed to the vicinity of the injection nozzle is injected into a mold to be shaped.
- a cylinder temperature in an injection-molding machine is 530 to 700° C. and a mold temperature is 160 to 240° C.
- the use of the chips for injection molding having surfaces coated with the carbon powder allows the carbon powder to be homogeneously dispersed in the molten or semi-molten magnesium alloy in the injection-molding machine, so that a molded article in which a complex of aluminum and carbon is homogeneously dispersed is obtained.
- a magnesium alloy molten or semi-molten by heating could be so efficiently stirred by rotation of a screw that the carbon powder can be homogeneously dispersed in the molten or semi-molten magnesium alloy.
- the carbon powder is homogeneously dispersed in a magnesium alloy in spite that a cylinder temperature is not so high and a time taken for injection after charging the chips in the cylinder.
- preferred is a molding process where chips introduced in an injection-molding machine are semi-molten and then injected in a mold, a so-called thixomolding method.
- a complex of aluminum and carbon is dispersed in a magnesium matrix.
- a complex of aluminum and carbon can be observed by element mapping using, for example, an X-ray microanalyzer. In the complex region, aluminum and carbon are detected in higher levels than surrounding regions.
- a magnesium matrix denotes regions other than the complex of aluminum and carbon, and the major part of the matrix contains magnesium as a main component.
- a complex of aluminum and carbon would be formed by bond formation between the carbon powder and aluminum in the chips during injection molding.
- Our analysis of a molded article produced have confirmed that a large part of carbon in the molded article forms a complex with aluminum.
- Al 4 C 3 is formed in the complex
- formation of such a complex would allow a molded article of the present invention to have excellent bending properties and tensile strength.
- the carbon powder can be homogeneously dispersed in a magnesium alloy, so that the complex is homogeneously dispersed in a molded article. Therefore, variation in bending properties and tensile strength in the molded article is reduced.
- defects are reduced and a segregation level for each component is low. It would be because fluidity is improved by dispersing carbon powder in a molten or semi-molten magnesium alloy during injection molding. Reduction of defects and a lower segregation level also contribute to smaller variation in bending properties and tensile strength.
- a carbon content in a molded article produced according to the present invention is preferably 0.01 to 3% by weight. If a carbon content is less than 0.01% by weight, bending properties and tensile strength of the molded article may be insufficiently improved and fluidity may be insufficiently improved. If a carbon content is more than 3% by weight, carbon powder may agglutinate, leading to tendency to crack formation and thus causing variation in tensile strength. A carbon content is more preferably 0.5% by weight or less.
- a molded article thus produced has excellent bending properties and tensile strength which vary in a small range.
- a molded article can be, therefore, thinner and produced in an improved yield.
- a molded article produced by a manufacturing process of the present invention can be suitably used in a variety of applications including electric devices such as a cell phone, a personal computer, a video camera, an optical disk player, a display and a projector; automobiles; welfare devices such as a wheel chair; and leisure goods such as fishing goods and a bicycle.
- a scrap produced during injection molding after feeding the chips to the injection-molding machine is heat-molten in the presence of a flux and then cooled to produce an ingot made of a magnesium alloy.
- Such a manufacturing process can provide an ingot with a reduced carbon content.
- Examples of a scrap produced during injection molding include alloys solidified inside of the injection-molding machine such as a sprue, a runner and an overflow unit, and non-standard molded articles.
- the scrap is charged in a melting furnace to be molten.
- the scrap is preferably charged in a pre-heated melting furnace.
- a molten-metal temperature is preferably adjusted to 600 to 750° C.
- timing of adding a flux to a scrap is preferably added after the scrap charged in a melting furnace has been molten.
- a molten metal is preferably refined by stirring.
- a refining temperature is preferably 600 to 750° C. and a refining time is preferably 3 to 300 min.
- a flux used in a manufacturing process for an ingot of the present invention there are no particular restrictions to a flux used in a manufacturing process for an ingot of the present invention, and those commonly used for refinement of a magnesium alloy can be used.
- An example is a flux containing a halide of a metal belonging to Group 1 or 2 in the periodic table as a main component.
- the term “main component” as used herein means a component contained in a content of generally 50% by weight or more, preferably 80% by weight or more.
- the metal halide is preferably at least one selected from magnesium chloride, calcium chloride, barium chloride, potassium chloride, sodium chloride and calcium fluoride.
- the amount of a flux to be added is preferably 0.3 to 45 parts by weight to 100 parts by weight of a scrap.
- a molten metal after refinement is preferably allowed to stand.
- a settling temperature is preferably 600 to 750° C. and a settling time is preferably 3 to 300 min.
- a clean part in the upper layer in the molten metal after refinement is cast in a mold and then cooled to give an ingot.
- a ratio (C 2 /C 1 ) of a carbon content C 2 (% by weight) in the ingot to a carbon content C 1 (% by weight) in the scrap is preferably 0.1 or less, more preferably 0.06 or less.
- a scrap produced during molding the chips for injection molding of the present invention can be generated into an ingot having a low carbon content by a convenient method as described above. Chips produced from such an ingot has a low carbon content, so that it can be used in combination with chips free from carbon and can be used after being again coated with carbon powder with higher recyclability. Furthermore, a molded article produced from an ingot of the present invention exhibits good corrosion resistance and excellent mechanical properties.
- a tensile test was conducted using a universal material testing machine “3382 Floor Model Testing System” from Instron Japan Company Ltd.
- a test piece was a plate-type molded article with a thickness of 2 mm which has a parallel portion with a width of 20 mm and a length of 60 mm in the center and grips at both ends.
- the test piece was prepared by injection molding using a mold for forming a test piece which has a shape corresponding to that of the test piece.
- FIG. 1 shows an exterior photo of the test piece in the tensile test and an exterior photo of the testing machine in which the test piece is set. Measurement was conducted at a tension rate of 5 mm/min.
- a bending test was conducted using a universal material testing machine “3382 Floor Model Testing System” from Instron Japan Company Ltd.
- a test piece used in the bending test was a plate having a width of 20 mm, a length of 70 mm and a thickness of 2 mm prepared by partly cutting the grips in the molded article formed by using a mold for forming a test piece for the tensile test.
- FIG. 2 shows an exterior photo of a testing machine in which the test piece was set in the bending test. A distance between two supports was set to 60 mm.
- a test was conducted by pushing down a former at a rate of 5 mm/min. The test was terminated either when the test piece was broken or when a displacement of the former reached 20 mm.
- Element mapping in the surface of a molded article was conducted by using an X-ray microanalyzer “JXA-8500FS” from JEOL Ltd.
- An acceleration voltage and a sample irradiation current were set to 15 kV and 1 ⁇ 10 ⁇ 8 A, respectively for measurement.
- a chemical composition of a molded article was determined using an optical emission spectrometer “PDA-7000” from Shimadzu Corporation. A diameter of a measuring spot was 5 mm. However, a carbon content was measured as described below.
- a carbon content in a molded article was measured by using a carbon/sulfur analyzer “EMIA-920V” from HORIBA Ltd. Measurement was conducted in accordance with JIS Z2615 “General rules for determination of carbon in metallic materials” (infrared absorption spectrometry (integration)).
- a molded article was cut vertically to a flow direction of a molten metal. After the piece obtained was embedded in a resin, the cut surface was polished. The cross section after polishing was observed using a light microscope.
- An ingot made of AZ91D (specifications; Al: 8.5 to 9.5% by weight, Zn: 0.45 to 0.9% by weight, Mn: 0.17 to 0.4% by weight, Be: 0.0008 to 0.0012% by weight, Si: 0.05% by weight or less, Fe: 0.004% by weight or less, Cu: 0.025% by weight or less, Ni: 0.001% by weight or less, balance: Mg) was cut into cylindrical magnesium alloy chips with a radius of about 0.5 mm and a length of about 4 mm.
- a melting temperature and a mold temperature were set to 610° C. and 225° C., respectively.
- the mold used was a mold for producing a test piece for a tensile test.
- a plate-type molded article with a thickness of 2 mm which had a parallel portion with a width of 20 mm and a length of 60 mm in the center and grips at both ends was produced.
- the molded article obtained had an aluminum content of 8.9% by weight, a zinc content of 0.68% by weight, a manganese content of 0.26% by weight, a beryllium content of 0.0011% by weight, an iron content of 0.002% by weight, a copper content of 0.003% by weight, a nickel content of 0.001% by weight and a carbon content of 0.085% by weight.
- FIG. 3 shows a microgram of a cross section of a molded article cut in a direction vertical to a flowing direction of a molten metal. As shown in FIG. 3 , there were no large cavities in the molded article.
- FIG. 4 shows a relationship between a displacement and a load at break of the test piece as determined by the tensile test.
- FIG. 5 shows a relationship between a displacement and a load at break of the test piece as determined by the bending test.
- FIG. 6 shows an elemental map of an area containing a complex of aluminum and carbon.
- FIG. 7 shows measurement points in determination of content distribution of each of aluminum and zinc in the molded article.
- FIG. 8 shows content distribution of aluminum in a molded article while
- FIG. 9 shows content distribution of zinc. The number of sample was three for each.
- FIG. 3 shows a microgram of a cross section of the molded article cut in a direction vertical to a flowing direction of the molten metal. As shown in FIG. 3 , relatively larger cavities were observed in the molded article.
- FIG. 4 shows a relationship between a displacement and a load at break of the test piece as determined by the tensile test.
- FIG. 5 shows a relationship between a displacement and a load at break of the test piece as determined by the bending test.
- FIG. 10 shows a 0.2% proof stress as determined by the tensile test. Furthermore, distribution of a content of each of aluminum and zinc in the surface of the molded article was determined as described in Example 1.
- FIG. 8 shows relationship between a measurement point and an aluminum content
- FIG. 9 shows a relationship between a measurement point and a zinc content.
- the molded article in Example 1 produced by the manufacturing process of the present invention had excellent tensile strength. Furthermore, variation of tensile strength between samples was small. In contrast, the molded article in Comparative Example 1 produced using the chips for injection molding which were not coated with carbon black exhibited large variation of tensile strength between samples. Furthermore, as shown in FIG. 5 , the molded article in Example 1 had excellent bending properties. In the test, any of the measured samples (four) was not broken at the maximum displacement (20 mm). In contrast, the molded article in Comparative Example 1 was broken even at a small displacement and variation of bending properties between samples was large.
- Example 1 Element mapping of the molded article in Example 1 was conducted, and a complex of aluminum and carbon as shown in FIG. 6 was observed. Such a complex was substantially homogeneously dispersed in the surface of the molded article.
- Example 1 had lower level of segregation of aluminum ( FIG. 8 ) and zinc ( FIG. 9 ) than the molded article in Comparative Example 1.
- Example 2 A molded article was produced as described in Example 1, except that a different type of carbon black was used.
- Example 2 carbon black “#45L” from Mitsubishi Chemical. Corporation (average primary particle diameter: 24 nm and DBP absorption: 53 mL/100 g) was used.
- Example 3 carbon black “#3050B” from Mitsubishi Chemical Corporation (average primary particle diameter: 50 nm and DBP absorption 175 mL/100 g) was used.
- a tensile test was conducted as described in Example 1.
- FIG. 10 shows a 0.2% proof stress as determined by the tensile test.
- An ingot was produced using a scrap formed during injection-molding chips introduced in an injection-molding machine as described in Example 1.
- 100 kg of an alloy carbon content: 0.16% by weight
- a temperature was regulated to make a temperature of the molten metal 650 to 700° C.
- 2 kg of a flux (Dow 310 : MgCl 2 50 parts by weight, KCl 2 20 parts by weight, CaF 2 15 parts by weight and MgO 15 parts by weight.) was added to the molten metal. After stirring for 30 min, the molten metal was allowed to stand for 30 min.
- a clean part in the upper layer in the molten metal was cast in a mold and then cooled to give an ingot.
- a carbon content in the ingot was 0.003% by weight.
- the molded article produced from chips obtained by cutting the ingot had comparable corrosion resistance and mechanical properties to those in the molded article in Comparative Example 1.
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Abstract
Description
- The present invention relates to magnesium alloy chips for injection molding and a process for manufacturing a molded article using same.
- A magnesium alloy has a high specific strength since it is most lightweight among practically used metals, and exhibits excellent heat radiation and better recyclability than a resin. Thus, molded articles made of a magnesium alloy are used in a wide variety of applications such as electric devices, automobiles and leisure goods.
- Injection molding is a common molding methods for a magnesium alloy. In general, a magnesium alloy is injection-molded by heating chips made of a magnesium alloy in a cylinder into a molten or semi-molten state (coexistence of a solid and a liquid phases) and then injecting the molten or semi-molten magnesium alloy into a mold. Here, since the magnesium alloy is injected into a mold at a relatively higher pressure, injection-molding is preferable for forming a thin-wall article such as a casing of an electric device. A so-called thixomolding method, that is, inter alia, a molding method in which a semi-molten material is injected into a mold, is a typical injection molding method for a magnesium alloy and is used for producing various molded articles.
- Conventionally, a Mg—Al alloy having excellent mechanical properties, particularly a Mg—Al—Zn alloy being well-balanced between mechanical properties and processability and exhibiting improved corrosion resistance have been widely used as a magnesium alloy for injection molding. Recently, further improvement in mechanical properties of a molded article has been needed in order to allow for thinning of a molded article made of a magnesium alloy and increasing an yield.
- There has been known a method for adding carbon to an alloy for the purpose of improving mechanical properties of a molded article made of an aluminum-containing magnesium alloy. Addition of carbon to a magnesium alloy makes crystals finer, resulting in improved mechanical properties. It is believed that such reduction in a crystal size may be caused by Al4C3 formed by a reaction between carbon and aluminum which are added to a magnesium alloy. Conventionally, carbon is added to a magnesium alloy by adding C2Cl6 to a molten magnesium alloy. Such a method, however, has an environmental disadvantage that C2Cl6 added is decomposed to generate harmful substances such as chlorine gas, and thus an alternative method has been needed.
- A known alternative method for adding carbon to an aluminum-containing magnesium alloy is addition of carbon powder (for example, see Patent Reference Nos. 1 and 2). However, when carbon powder, is directly added to a molten magnesium alloy, the carbon powder tends to agglutinate, so that a molded article obtained may have insufficiently improved or have varied mechanical properties.
- Patent Reference No. 3 has described a process for manufacturing a carbon-containing magnesium alloy comprising mixing 5 to 30 parts by weight of at least one of carbon powder, carbon nanofiber and carbon nanotube with 100 parts by weight of a magnesium alloy to prepare a master batch and then mixing the master batch with a 3- to 20-fold parts by weight of a magnesium alloy. In the examples therein, there is described a magnesium alloy produced by processing magnesium alloy powder and carbon powder in a ball mill to prepare a mixed powder, sintering the mixed powder to prepare a master batch, adding the master batch to a molten metal and homogenizing the molten metal with stirring. There is described that the magnesium alloy thus produced contains uniformly dispersed carbon and has improved tensile strength and a higher Young's modulus. The process is, however, troublesome and thus at a disadvantage in terms of cost.
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- Patent Reference No. 1: Japanese published unexamined application No. 1994-73485.
- Patent Reference No. 2: Japanese published unexamined application No. 2004-156067.
- Patent Reference No. 3: Japanese published unexamined application No. 2007-291438.
- To solve the above problems, an objective of the present invention is to provide chips for injection molding allowing for forming a molded article made of a magnesium alloy which has excellent bending properties and tensile strength which vary in a small range. Another objective of the invention is to provide a process for manufacturing a molded article made of a magnesium alloy using such chips for injection molding.
- The above problems can be solved by providing chips for injection molding wherein the surfaces of chips made of an aluminum-containing magnesium alloy are coated with carbon powder.
- Herein, a content of the carbon powder is preferably 0.01 to 3% by weight. Furthermore, the carbon powder is preferably carbon black. Here, the carbon black more preferably has an average primary particle diameter of from 5 to 100 nm and a DBP absorption of from 40 to 200 mL/100 g.
- The above problems can be also solved by providing a process for manufacturing the chips for injection molding, comprising mixing chips made of an aluminum-containing magnesium alloy with the carbon powder.
- A preferable embodiment of the present invention is a process for manufacturing a molded article made of a magnesium alloy, comprising charging the chips for injection molding in an injection-molding machine and then injection-molding the chips.
- Here, in the molded article, a complex of aluminum and carbon is dispersed in a magnesium matrix.
- Another preferable embodiment of the present invention is a process for manufacturing an ingot made of a magnesium alloy, comprising heat-melting a scrap formed during injection-molding of the chips for injection molding in the presence of a flux and then cooling it. Here, it is preferable that a ratio (C2/C1) of a carbon content C2 (% by weight) in said ingot to a carbon content C1 (% by weight) in said scrap is 0.1 or less.
- A molded article produced by injection-molding of chips for injection molding of the present invention has excellent bending properties and tensile strength which vary in a small range. Furthermore, a process for manufacturing a molded article made of a magnesium alloy of the present invention can conveniently provide a molded article made of a magnesium alloy having excellent bending properties and tensile strength which vary in a small range. It thus allows for making a molded article thinner and improving an yield. Furthermore, a scrap formed during injection-molding of the chips for injection molding has improved recyclability.
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FIG. 1 shows an exterior photo of a test piece in a tensile test and an exterior photo of a testing machine on which the test piece is set. -
FIG. 2 shows an exterior photo of a testing machine on which the test piece is set, in a bending test. -
FIG. 3 shows micrograms of a cross section of a molded article cut in a direction vertical to a flowing direction of a molten metal in Example 1 and Comparative Example 1. -
FIG. 4 shows a relationship between a displacement and a load at break of a test piece as determined by a tensile test in Example 1 and Comparative Example 1. -
FIG. 5 shows a relationship between a displacement and a load at break of a test piece as determined by a bending test in Example 1 and Comparative Example 1. -
FIG. 6 shows an elemental map of an area containing a complex of aluminum and carbon in the surface of a molded article in Example 1. -
FIG. 7 shows measurement points in determination of content distribution of each of aluminum and zinc in a molded article in Example 1 and Comparative Example 1. -
FIG. 8 shows content distribution of aluminum in a molded article in Example 1 and Comparative Example 1. -
FIG. 9 shows content distribution of zinc in a molded article in Example 1 and Comparative Example 1. -
FIG. 10 shows a 0.2% proof stress of a molded article in Examples 1 to 3 and Comparative Example 1 as determined by a tensile test. - The present invention provides chips for injection molding wherein the surfaces of chips made of an aluminum-containing magnesium alloy are coated with carbon powder.
- The chips to be coated with carbon powder must be made of an aluminum-containing magnesium alloy. In other words, the chips must be made of an alloy containing aluminum as a component in addition to magnesium. Aluminum is effective for improving tensile strength and corrosion resistance of a magnesium alloy. Furthermore, as described in Examples later, a complex of aluminum and carbon is formed in a molded article produced by the present invention. Formation of the complex would lead to a molded article having excellent bending properties and tensile strength.
- An aluminum content in a magnesium alloy used in the present invention is preferably 1 to 15% by weight. If an aluminum content is less than 1% by weight, tensile strength and corrosion resistance of a molded article produced may be reduced. Furthermore, formation of a complex of aluminum and carbon may be inhibited in a molded article produced, thus bending properties and tensile strength may not improve. An aluminum content of more than 15% by weight may lead to brittle failure.
- The magnesium alloy can contain zinc, wherein a zinc content is 3% by weight or less. In a case that zinc is contained therein, toughness of magnesium alloy and fluidity during molding further improve. A zinc content is preferably 0.1 to 3% by weight. If a zinc content is less than 0.1% by weight, toughness of a molded article produced and fluidity during molding may be reduced. If a zinc content is more than 3% by weight, hot tearing may occur.
- The magnesium alloy can contain manganese, in which a manganese content is 1% by weight or less. In a case that manganese is contained therein, corrosion resistance of a magnesium alloy further improves. A manganese content is preferably 0.05 to 1% by weight. If a manganese content is less than 0.05% by weight, corrosion resistance of a molded article produced may be reduced. If a manganese content is more than 1% by weight, compression strength and tensile strength may be reduced.
- The magnesium alloy can contain beryllium, in which a beryllium content is 0.003% by weight or less. In a case that beryllium is contained therein, flame resistance during melting of a magnesium alloy improves. In a case that beryllium is contained therein, brightness of a molded article produced also improves. A beryllium content is preferably 0.0001 to 0.003% by weight. If a beryllium content is less than 0.0001% by weight, it may fail to improve flame resistance or brightness. If a beryllium content is more than 0.003% by weight, crystals may be coarse, leading to reduction of tensile strength and a higher cost.
- The magnesium alloy can contain calcium, in which a calcium content is 3% by weight or less. In a case that calcium is contained therein, flame retardancy of a magnesium alloy improves. A calcium content is generally 0.5 to 3% by weight.
- The magnesium alloy can contain elements other than those described above as long as they do not reduce the effect of the present invention. Such elements can be willingly added or contained as inevitable impurities. A content of such elements is generally 1% by weight or less. The balance of a magnesium alloy used for the chips is magnesium, whose content is generally 80% by weight or more.
- The magnesium alloy can be specifically selected from magnesium alloys such as AZ91, AM50, AM60 and AZ31 in accordance with the ASTM Standard. Among others, AZ91 is preferable, which is well-balanced between mechanical properties and processability and exhibits higher corrosion resistance.
- There are no particular restrictions to a process for manufacturing the chips. Generally, an ingot made of the above magnesium alloy can be cut into the chips. There are no particular restrictions to the shape or the size of the chips, which can be appropriately selected, depending on, for example, the specifications of an injection-molding machine used for producing a molded article. Chips with a length of from 1 to 10 mm is generally used. Herein, a length of a chip denotes a distance between the furthest positions in the chip.
- The carbon powder used in the present invention can be selected from, but not limited to, carbon black, graphite such as scaly graphite, coke or the like.
- In the present invention, the carbon powder is preferably carbon black. When carbon black is used as the carbon powder, carbon black and the chips are mixed by, for example, a mixer to coat the surfaces of the chips with carbon black. The use of chips for injection molding coated with carbon powder in injection molding would allow carbon powder to easily disperse in a magnesium alloy.
- There are no particular restrictions to the type of the carbon black. Examples which can be used include furnace black, thermal black, channel black, acetylene black ketjen black and the like, which can be used in combination.
- Preferably, the carbon black has an average primary particle diameter of from 5 to 100 nm and a DBP absorption of from 40 to 200 mL/100 g. A DBP absorption is a parameter corresponding to a volume of voids in a bunch of grapes when fused primary particles of carbon black, so-called “aggregate”, is assumed to be a bunch of grapes. As the aggregate grows, the void volume increases and thus a DBP absorption increases. Formation of a complex of aluminum and carbon may be influenced by a primary particle diameter of carbon black and also a growing state of the aggregate. It is, therefore, preferable that an average primary particle diameter and a DBP absorption are within a certain range. A DBP absorption can be determined in accordance with JIS K6217.
- In the light of higher proof stress of a molded article produced, the carbon black preferably has a DBP absorption of from 40 to 200 mL/100 g, more preferably 60 to 200 mL/100 g, further preferably 80 to 200 mL/100 g.
- The carbon black can have functional groups in its surface. Examples of such functional groups include hydroxy groups such as phenolic hydroxy group, carboxyl groups and quinone groups.
- The surfaces of the chips are coated with the carbon powder to produce chips for injection molding having surfaces coated with the carbon powder. There are no particular restrictions to a method for coating the surface of the chips with the carbon powder. Generally, the chips and the carbon powder can be mixed using a mixer to produce chips for injection molding having the surfaces coated with the carbon powder. A mixing ratio of the chips to the carbon powder can be appropriately adjusted, depending on the amount of carbon contained in a molded article to be produced. The amount of the carbon powder in the chips for injection molding coated with the carbon powder is preferably 0.01 to 3% by weight, more preferably 0.01 to 0.5% by weight.
- The chips for injection molding having surfaces coated with the carbon powder are charged in an injection-molding machine and then injection-molded to provide a molded article. Generally, the chips for injection molding charged in an injection-molding machine are heated in a cylinder while being fed via a screw in the cylinder to an injection nozzle. Then, a molten or semi-molten (coexistence of a solid and a liquid phases) magnesium alloy fed to the vicinity of the injection nozzle is injected into a mold to be shaped. In general, a cylinder temperature in an injection-molding machine is 530 to 700° C. and a mold temperature is 160 to 240° C.
- Thus, the use of the chips for injection molding having surfaces coated with the carbon powder allows the carbon powder to be homogeneously dispersed in the molten or semi-molten magnesium alloy in the injection-molding machine, so that a molded article in which a complex of aluminum and carbon is homogeneously dispersed is obtained. In the injection-molding machine, it seems that a magnesium alloy molten or semi-molten by heating could be so efficiently stirred by rotation of a screw that the carbon powder can be homogeneously dispersed in the molten or semi-molten magnesium alloy. It is surprising that the carbon powder is homogeneously dispersed in a magnesium alloy in spite that a cylinder temperature is not so high and a time taken for injection after charging the chips in the cylinder. In the present invention, preferred is a molding process where chips introduced in an injection-molding machine are semi-molten and then injected in a mold, a so-called thixomolding method.
- In a molded article produced by a manufacturing process according to the present invention, a complex of aluminum and carbon is dispersed in a magnesium matrix. A complex of aluminum and carbon can be observed by element mapping using, for example, an X-ray microanalyzer. In the complex region, aluminum and carbon are detected in higher levels than surrounding regions. A magnesium matrix denotes regions other than the complex of aluminum and carbon, and the major part of the matrix contains magnesium as a main component.
- In the present invention, a complex of aluminum and carbon would be formed by bond formation between the carbon powder and aluminum in the chips during injection molding. Our analysis of a molded article produced have confirmed that a large part of carbon in the molded article forms a complex with aluminum. Although it is not confirmed whether Al4C3 is formed in the complex, formation of such a complex would allow a molded article of the present invention to have excellent bending properties and tensile strength. Furthermore, according to the manufacturing process of the present invention, the carbon powder can be homogeneously dispersed in a magnesium alloy, so that the complex is homogeneously dispersed in a molded article. Therefore, variation in bending properties and tensile strength in the molded article is reduced.
- Furthermore, in a molded article of the present invention, defects are reduced and a segregation level for each component is low. It would be because fluidity is improved by dispersing carbon powder in a molten or semi-molten magnesium alloy during injection molding. Reduction of defects and a lower segregation level also contribute to smaller variation in bending properties and tensile strength.
- A carbon content in a molded article produced according to the present invention is preferably 0.01 to 3% by weight. If a carbon content is less than 0.01% by weight, bending properties and tensile strength of the molded article may be insufficiently improved and fluidity may be insufficiently improved. If a carbon content is more than 3% by weight, carbon powder may agglutinate, leading to tendency to crack formation and thus causing variation in tensile strength. A carbon content is more preferably 0.5% by weight or less.
- A molded article thus produced has excellent bending properties and tensile strength which vary in a small range. A molded article can be, therefore, thinner and produced in an improved yield. A molded article produced by a manufacturing process of the present invention can be suitably used in a variety of applications including electric devices such as a cell phone, a personal computer, a video camera, an optical disk player, a display and a projector; automobiles; welfare devices such as a wheel chair; and leisure goods such as fishing goods and a bicycle.
- It is preferable that a scrap produced during injection molding after feeding the chips to the injection-molding machine is heat-molten in the presence of a flux and then cooled to produce an ingot made of a magnesium alloy. Such a manufacturing process can provide an ingot with a reduced carbon content.
- Examples of a scrap produced during injection molding include alloys solidified inside of the injection-molding machine such as a sprue, a runner and an overflow unit, and non-standard molded articles.
- The scrap is charged in a melting furnace to be molten. Here, the scrap is preferably charged in a pre-heated melting furnace. Furthermore, a molten-metal temperature is preferably adjusted to 600 to 750° C.
- There are no particular restrictions to timing of adding a flux to a scrap, but it is preferably added after the scrap charged in a melting furnace has been molten. After a flux is added, a molten metal is preferably refined by stirring. A refining temperature is preferably 600 to 750° C. and a refining time is preferably 3 to 300 min.
- There are no particular restrictions to a flux used in a manufacturing process for an ingot of the present invention, and those commonly used for refinement of a magnesium alloy can be used. An example is a flux containing a halide of a metal belonging to
1 or 2 in the periodic table as a main component. The term “main component” as used herein means a component contained in a content of generally 50% by weight or more, preferably 80% by weight or more. The metal halide is preferably at least one selected from magnesium chloride, calcium chloride, barium chloride, potassium chloride, sodium chloride and calcium fluoride. The amount of a flux to be added is preferably 0.3 to 45 parts by weight to 100 parts by weight of a scrap.Group - A molten metal after refinement is preferably allowed to stand. A settling temperature is preferably 600 to 750° C. and a settling time is preferably 3 to 300 min. A clean part in the upper layer in the molten metal after refinement is cast in a mold and then cooled to give an ingot.
- A ratio (C2/C1) of a carbon content C2 (% by weight) in the ingot to a carbon content C1 (% by weight) in the scrap is preferably 0.1 or less, more preferably 0.06 or less.
- It is generally difficult to remove carbon from a molten metal after melting of a scrap. For example, a carbon content is high in an ingot produced by heat-melting a scrap wherein carbonized materials adhere to its surface and then cooling it. Thus, a molded article produced from such an ingot has insufficient functions such as corrosion resistance. Carbon in such an ingot is not dispersed, so that properties such as corrosion resistance would be deteriorated. Thus, for example, when a scrap having carbonated materials on its surface is regenerated into an ingot, it is necessary to remove the carbonized materials before melting, leading to a high cost, and the carbonated materials cannot be adequately removed. In contrast, a scrap produced during molding the chips for injection molding of the present invention can be generated into an ingot having a low carbon content by a convenient method as described above. Chips produced from such an ingot has a low carbon content, so that it can be used in combination with chips free from carbon and can be used after being again coated with carbon powder with higher recyclability. Furthermore, a molded article produced from an ingot of the present invention exhibits good corrosion resistance and excellent mechanical properties.
- The present invention will be described with reference to Examples.
- A tensile test was conducted using a universal material testing machine “3382 Floor Model Testing System” from Instron Japan Company Ltd. A test piece was a plate-type molded article with a thickness of 2 mm which has a parallel portion with a width of 20 mm and a length of 60 mm in the center and grips at both ends. The test piece was prepared by injection molding using a mold for forming a test piece which has a shape corresponding to that of the test piece.
FIG. 1 shows an exterior photo of the test piece in the tensile test and an exterior photo of the testing machine in which the test piece is set. Measurement was conducted at a tension rate of 5 mm/min. - A bending test was conducted using a universal material testing machine “3382 Floor Model Testing System” from Instron Japan Company Ltd. A test piece used in the bending test was a plate having a width of 20 mm, a length of 70 mm and a thickness of 2 mm prepared by partly cutting the grips in the molded article formed by using a mold for forming a test piece for the tensile test.
FIG. 2 shows an exterior photo of a testing machine in which the test piece was set in the bending test. A distance between two supports was set to 60 mm. A test was conducted by pushing down a former at a rate of 5 mm/min. The test was terminated either when the test piece was broken or when a displacement of the former reached 20 mm. - Element mapping in the surface of a molded article was conducted by using an X-ray microanalyzer “JXA-8500FS” from JEOL Ltd. An acceleration voltage and a sample irradiation current were set to 15 kV and 1×10−8 A, respectively for measurement.
- A chemical composition of a molded article was determined using an optical emission spectrometer “PDA-7000” from Shimadzu Corporation. A diameter of a measuring spot was 5 mm. However, a carbon content was measured as described below.
- A carbon content in a molded article was measured by using a carbon/sulfur analyzer “EMIA-920V” from HORIBA Ltd. Measurement was conducted in accordance with JIS Z2615 “General rules for determination of carbon in metallic materials” (infrared absorption spectrometry (integration)).
- A molded article was cut vertically to a flow direction of a molten metal. After the piece obtained was embedded in a resin, the cut surface was polished. The cross section after polishing was observed using a light microscope.
- An ingot made of AZ91D (specifications; Al: 8.5 to 9.5% by weight, Zn: 0.45 to 0.9% by weight, Mn: 0.17 to 0.4% by weight, Be: 0.0008 to 0.0012% by weight, Si: 0.05% by weight or less, Fe: 0.004% by weight or less, Cu: 0.025% by weight or less, Ni: 0.001% by weight or less, balance: Mg) was cut into cylindrical magnesium alloy chips with a radius of about 0.5 mm and a length of about 4 mm. 100 kg of the magnesium alloy chips obtained and 100 g of carbon black (furnace black “#30” from Mitsubishi Chemical Corporation, average primary particle diameter: 30 nm, DBP absorption: 113 mL/100 g) were separately introduced in a V-type mixer, and mixed at a rotation number of 30 r.p.m. for 20 min to give chips for injection molding in which the surfaces of the magnesium alloy chips were coated with carbon black. Here, the chips for injection molding obtained were visually observed, showing that the surfaces of the chips were substantially homogeneously coated with carbon black. The chips for injection molding obtained were introduced in an injection-molding machine for thixomolding (“JSW JLM220-MG” from The Japan Steel Works, Ltd.) and injection-molded. During injection-molding, a melting temperature and a mold temperature were set to 610° C. and 225° C., respectively. The mold used was a mold for producing a test piece for a tensile test. Thus, a plate-type molded article with a thickness of 2 mm which had a parallel portion with a width of 20 mm and a length of 60 mm in the center and grips at both ends was produced. The molded article obtained had an aluminum content of 8.9% by weight, a zinc content of 0.68% by weight, a manganese content of 0.26% by weight, a beryllium content of 0.0011% by weight, an iron content of 0.002% by weight, a copper content of 0.003% by weight, a nickel content of 0.001% by weight and a carbon content of 0.085% by weight.
FIG. 3 shows a microgram of a cross section of a molded article cut in a direction vertical to a flowing direction of a molten metal. As shown inFIG. 3 , there were no large cavities in the molded article. - A tensile test and a bending test were conducted for the molded article obtained. For each test, a plurality of samples were used.
FIG. 4 shows a relationship between a displacement and a load at break of the test piece as determined by the tensile test.FIG. 5 shows a relationship between a displacement and a load at break of the test piece as determined by the bending test. When a sample was not broken at the end of the bending test (a displacement is 20 mm), a load at the end of the test is given.FIG. 10 shows a 0.2% proof stress as determined by the tensile test. - Element mapping was conducted for the surface of the molded article obtained.
FIG. 6 shows an elemental map of an area containing a complex of aluminum and carbon. - Distribution of a content of each of aluminum and zinc in the surface of the molded article were determined.
FIG. 7 shows measurement points in determination of content distribution of each of aluminum and zinc in the molded article.FIG. 8 shows content distribution of aluminum in a molded article whileFIG. 9 shows content distribution of zinc. The number of sample was three for each. - A molded article was produced using chips for injection molding which was not coated with carbon black. A molded article was produced as described in Example 1, except that carbon black coating was not conducted. The molded article obtained had an aluminum content of 9.2% by weight, a zinc content of 0.78% by weight, a manganese content of 0.25% by weight, a beryllium content of 0.0010% by weight, an iron content of 0.002% by weight, a copper content of 0.004% by weight and a nickel content of 0.001% by weight. A carbon content was below a detection limit (0.0001% by weight).
FIG. 3 shows a microgram of a cross section of the molded article cut in a direction vertical to a flowing direction of the molten metal. As shown inFIG. 3 , relatively larger cavities were observed in the molded article. - A tensile test and a bending test for the molded article were conducted as described in Example 1.
FIG. 4 shows a relationship between a displacement and a load at break of the test piece as determined by the tensile test.FIG. 5 shows a relationship between a displacement and a load at break of the test piece as determined by the bending test.FIG. 10 shows a 0.2% proof stress as determined by the tensile test. Furthermore, distribution of a content of each of aluminum and zinc in the surface of the molded article was determined as described in Example 1.FIG. 8 shows relationship between a measurement point and an aluminum content, whileFIG. 9 shows a relationship between a measurement point and a zinc content. - As shown in
FIG. 4 , the molded article in Example 1 produced by the manufacturing process of the present invention had excellent tensile strength. Furthermore, variation of tensile strength between samples was small. In contrast, the molded article in Comparative Example 1 produced using the chips for injection molding which were not coated with carbon black exhibited large variation of tensile strength between samples. Furthermore, as shown inFIG. 5 , the molded article in Example 1 had excellent bending properties. In the test, any of the measured samples (four) was not broken at the maximum displacement (20 mm). In contrast, the molded article in Comparative Example 1 was broken even at a small displacement and variation of bending properties between samples was large. - Element mapping of the molded article in Example 1 was conducted, and a complex of aluminum and carbon as shown in
FIG. 6 was observed. Such a complex was substantially homogeneously dispersed in the surface of the molded article. - As shown in
FIGS. 8 and 9 , the molded article in Example 1 had lower level of segregation of aluminum (FIG. 8 ) and zinc (FIG. 9 ) than the molded article in Comparative Example 1. - A molded article was produced as described in Example 1, except that a different type of carbon black was used. In Example 2, carbon black “#45L” from Mitsubishi Chemical. Corporation (average primary particle diameter: 24 nm and DBP absorption: 53 mL/100 g) was used. In Example 3, carbon black “#3050B” from Mitsubishi Chemical Corporation (average primary particle diameter: 50 nm and DBP absorption 175 mL/100 g) was used. For the molded articles obtained, a tensile test was conducted as described in Example 1.
FIG. 10 shows a 0.2% proof stress as determined by the tensile test. - An ingot was produced using a scrap formed during injection-molding chips introduced in an injection-molding machine as described in Example 1. After the injection molding, 100 kg of an alloy (carbon content: 0.16% by weight) solidified in a sprue in the Injection-molding machine was placed in a pre-heated melting furnace. A temperature was regulated to make a temperature of the molten metal 650 to 700° C. After the alloy introduced was completely molten, 2 kg of a flux (Dow 310: MgCl2 50 parts by weight,
KCl 2 20 parts by weight,CaF 2 15 parts by weight andMgO 15 parts by weight.) was added to the molten metal. After stirring for 30 min, the molten metal was allowed to stand for 30 min. A clean part in the upper layer in the molten metal was cast in a mold and then cooled to give an ingot. A carbon content in the ingot was 0.003% by weight. The molded article produced from chips obtained by cutting the ingot had comparable corrosion resistance and mechanical properties to those in the molded article in Comparative Example 1.
Claims (9)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011-085941 | 2011-04-08 | ||
| JP2011085941 | 2011-04-08 | ||
| PCT/JP2012/059480 WO2012137907A1 (en) | 2011-04-08 | 2012-04-06 | Magnesium alloy chips and method for manufacturing molded article in which same are used |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US20140023547A1 true US20140023547A1 (en) | 2014-01-23 |
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| US14/009,861 Abandoned US20140023547A1 (en) | 2011-04-08 | 2012-04-06 | Magnesium alloy chips and process for manufacturing molded article using same |
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| Country | Link |
|---|---|
| US (1) | US20140023547A1 (en) |
| JP (1) | JP5137049B2 (en) |
| KR (1) | KR101310622B1 (en) |
| CN (1) | CN103079725B (en) |
| DE (1) | DE112012001625B4 (en) |
| WO (1) | WO2012137907A1 (en) |
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| US11148197B2 (en) | 2017-08-31 | 2021-10-19 | Seiko Epson Corporation | Raw material for thixomolding, method for producing raw material for thixomolding, and molded body |
| US11865609B2 (en) | 2020-03-23 | 2024-01-09 | Seiko Epson Corporation | Method for manufacturing powder-modified magnesium alloy chip |
| US11866808B2 (en) | 2020-03-23 | 2024-01-09 | Seiko Epson Corporation | Method for manufacturing thixomolding material |
| US12311437B2 (en) | 2021-03-30 | 2025-05-27 | Seiko Epson Corporation | Thixomolding material |
| US12479021B2 (en) | 2021-12-28 | 2025-11-25 | Seiko Epson Corporation | Thixomolding material and method of manufacturing thixomolding material |
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| JP2016204678A (en) * | 2015-04-15 | 2016-12-08 | 株式会社日本製鋼所 | Magnesium-zinc alloy member and manufacturing method thereof |
| CN107904430B (en) * | 2017-11-22 | 2020-01-17 | 上海紫燕合金应用科技有限公司 | Preparation method of single-walled carbon nanotube-doped magnesium alloy structural parts |
| CN107893165B (en) * | 2017-11-22 | 2020-01-21 | 上海紫燕合金应用科技有限公司 | Preparation method of graphene-doped magnesium alloy structural member |
| JP7718086B2 (en) * | 2021-03-30 | 2025-08-05 | セイコーエプソン株式会社 | Molded products and method for manufacturing Mg-based composite chips for thixomolding |
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| US11148197B2 (en) | 2017-08-31 | 2021-10-19 | Seiko Epson Corporation | Raw material for thixomolding, method for producing raw material for thixomolding, and molded body |
| US11865609B2 (en) | 2020-03-23 | 2024-01-09 | Seiko Epson Corporation | Method for manufacturing powder-modified magnesium alloy chip |
| US11866808B2 (en) | 2020-03-23 | 2024-01-09 | Seiko Epson Corporation | Method for manufacturing thixomolding material |
| US12311437B2 (en) | 2021-03-30 | 2025-05-27 | Seiko Epson Corporation | Thixomolding material |
| US12479021B2 (en) | 2021-12-28 | 2025-11-25 | Seiko Epson Corporation | Thixomolding material and method of manufacturing thixomolding material |
Also Published As
| Publication number | Publication date |
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| CN103079725A (en) | 2013-05-01 |
| KR101310622B1 (en) | 2013-09-24 |
| KR20130041354A (en) | 2013-04-24 |
| DE112012001625B4 (en) | 2019-06-13 |
| DE112012001625T5 (en) | 2014-04-17 |
| WO2012137907A1 (en) | 2012-10-11 |
| CN103079725B (en) | 2014-04-02 |
| JPWO2012137907A1 (en) | 2014-07-28 |
| JP5137049B2 (en) | 2013-02-06 |
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