JP5253738B2 - 硬化肉盛合金鉄材料 - Google Patents
硬化肉盛合金鉄材料 Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 67
- 238000005552 hardfacing Methods 0.000 title claims abstract description 43
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims description 152
- 239000000956 alloy Substances 0.000 title claims description 80
- 229910045601 alloy Inorganic materials 0.000 title claims description 76
- 229910052742 iron Inorganic materials 0.000 title claims description 69
- 239000011651 chromium Substances 0.000 claims abstract description 54
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 45
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 43
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 35
- 238000003466 welding Methods 0.000 claims abstract description 35
- 239000000155 melt Substances 0.000 claims abstract description 32
- 239000000758 substrate Substances 0.000 claims abstract description 19
- 229910001021 Ferroalloy Inorganic materials 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims description 31
- 239000007787 solid Substances 0.000 claims description 17
- UFGZSIPAQKLCGR-UHFFFAOYSA-N chromium carbide Chemical compound [Cr]#C[Cr]C#[Cr] UFGZSIPAQKLCGR-UHFFFAOYSA-N 0.000 claims description 12
- 229910003470 tongbaite Inorganic materials 0.000 claims description 12
- 229910001037 White iron Inorganic materials 0.000 claims description 8
- 229910000831 Steel Inorganic materials 0.000 claims description 7
- 239000010959 steel Substances 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 238000005266 casting Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000007872 degassing Methods 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims description 2
- 239000002893 slag Substances 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 238000007865 diluting Methods 0.000 claims 1
- 239000012768 molten material Substances 0.000 claims 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 abstract 1
- 239000000203 mixture Substances 0.000 description 49
- 239000000126 substance Substances 0.000 description 13
- 239000002994 raw material Substances 0.000 description 9
- 229910000640 Fe alloy Inorganic materials 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000010790 dilution Methods 0.000 description 5
- 239000012895 dilution Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- -1 C 3 carbides Chemical class 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- 229910001309 Ferromolybdenum Inorganic materials 0.000 description 3
- 229910001200 Ferrotitanium Inorganic materials 0.000 description 3
- 229910000628 Ferrovanadium Inorganic materials 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- PNXOJQQRXBVKEX-UHFFFAOYSA-N iron vanadium Chemical compound [V].[Fe] PNXOJQQRXBVKEX-UHFFFAOYSA-N 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- 239000010955 niobium Substances 0.000 description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 3
- 229910005438 FeTi Inorganic materials 0.000 description 2
- 229910000604 Ferrochrome Inorganic materials 0.000 description 2
- 229910000616 Ferromanganese Inorganic materials 0.000 description 2
- 229910000592 Ferroniobium Inorganic materials 0.000 description 2
- 238000007429 general method Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 2
- ZFGFKQDDQUAJQP-UHFFFAOYSA-N iron niobium Chemical compound [Fe].[Fe].[Nb] ZFGFKQDDQUAJQP-UHFFFAOYSA-N 0.000 description 2
- 150000001247 metal acetylides Chemical class 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- 238000005275 alloying Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 235000000396 iron Nutrition 0.000 description 1
- 229910001338 liquidmetal Inorganic materials 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000003923 scrap metal Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/04—Making ferrous alloys by melting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
- B23K35/3053—Fe as the principal constituent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/32—Selection of soldering or welding materials proper with the principal constituent melting at more than 1550 degrees C
- B23K35/327—Selection of soldering or welding materials proper with the principal constituent melting at more than 1550 degrees C comprising refractory compounds, e.g. carbides
-
- 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
- C22C1/10—Alloys containing non-metals
- C22C1/1036—Alloys containing non-metals starting from a melt
- C22C1/1068—Making hard metals based on borides, carbides, nitrides, oxides or silicides
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
- C22C27/06—Alloys based on chromium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/02—Making ferrous alloys by powder metallurgy
- C22C33/0207—Using a mixture of prealloyed powders or a master alloy
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/38—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of manganese
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
- C23C26/02—Coating not provided for in groups C23C2/00 - C23C24/00 applying molten material to the substrate
-
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
- B23K35/3053—Fe as the principal constituent
- B23K35/308—Fe as the principal constituent with Cr as next major constituent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K9/00—Arc welding or cutting
- B23K9/04—Welding for other purposes than joining, e.g. built-up welding
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nonmetallic Welding Materials (AREA)
- Arc Welding In General (AREA)
- Powder Metallurgy (AREA)
Description
本発明は、主として炭化クロムおよび他の強力な炭化物形成元素、例えばモリブデン、チタン、タングステン、バナジウム、ニオブおよびホウ素から形成された炭化物を含む硬化肉盛合金鉄材料に関する。
炭化物を含む合金鉄材料は、過酷な浸食および摩耗に対する耐性が必要とされる用途において、基材上の硬化肉盛溶着物(weld deposit)を得るための消耗材として広範囲に、長年にわたって使用されている。
炭化クロム合金鉄材料硬化肉盛の製造に溶接消耗材として使用される、高炭素フェロクロム(HCFeCr)と高炭素フェロマンガン(HCFeMn)粉末との典型的なブレンドを表1に示す。
上記のブレンドされた合金鉄粉末を含む溶接プールから軟鋼基材上に溶着する硬化肉盛の化学組成を例として表2に示す。硬化肉盛は、表中および以下、「硬化肉盛溶着物」と呼ぶ。
硬化肉盛溶着物を製造するための合金鉄粉末の製造および使用に関し、上記の先行技術や他の先行技術の制約は、本出願者の知る限り、以下の通りである。
(a)炭化クロム含有合金鉄溶接消耗材料における基本元素、例えば炭素、クロム、およびマンガンを規定濃度含有する均質な溶融物を形成し、
(b)前記溶融物から、固体の炭化物含有合金鉄溶接消耗材料を形成する、
ことを含む方法を提供する。
本発明により、HCFeCrおよびHCFeMn粉末およびグラファイトの形態にある遊離炭素から均質な溶融物を形成し、その後、溶融物を鋳型に流し込むことにより、合金鉄溶接消耗材料(以下、「ブレンドされた合金鉄材料」と呼ぶ)を製造した。その後、鋳造した材料を微粉末に粉砕した。
液体金属中に溶解した3重量%の炭素は、合金鉄粉末の最終ブレンド中の化学結合した炭素の含有量を5.6%Cから8.4%Cに増加させた。
表1に示す公知の合金鉄粉末ブレンドで使用されている、炭素含有量が高い(例えば8.5%C)、より高価なHCFeCr原料ではなく、炭素含有量が比較的低い(例えば5.5%C)HCFeCr原料を使用できる。
表1に示す公知の合金鉄粉末ブレンドで使用されている、クロム含有量が高い(例えば67%Cr)、より高価なHCFeCr原料ではなく、クロム含有量が比較的低い(例えば63重量%C)HCFeCr原料を使用できる。
最終合金鉄ブレンドの化学的組成は、Fe−57.3Cr−8.4C−4.5Mnであった。この材料は、脆く、粉末にし易く、一般的な方法によって粉砕することにより、容易に微粉に加工することができる。
硬化肉盛溶着物のクロム含有量は、炭素含有量を低減することなく、先行技術(表2)における34.7%Crから本発明における31.5%Crに減少した。
最終溶着物の微小構造は、約50体積%のM7C3炭化物を含有する。
溶接消耗材の割合および希釈の量は表2と同様である、すなわち先行技術で使用される硬化肉盛溶接手順を変更する必要はなかった。
例1に関する上記と同様の本発明の方法により、ブレンドされた合金鉄材料を製造した。
スクラップ鋼(20重量%)により、最終ブレンドのクロム含有量が低減した。
合金鉄ブレンドのクロム含有量が、先行技術における63.0%から本発明における44.1%に減少した。
・最終合金鉄ブレンドの化学的組成は、Fe−44.1Cr−8.3C−4.7Mnであった。この材料は、脆く、粉末にし易く、一般的な方法によって粉砕することにより、容易に微粉に加工することができる。
例1に関する上記と同様の本発明の方法により、ブレンドされた合金鉄材料を製造した。
Claims (10)
- 好適な基材上に硬化肉盛溶着物を製造するのに使用する炭化クロム含有合金鉄溶接消耗材料を製造する方法であって、
(a)クロム含有合金鉄材料および遊離炭素の供給源から均質な溶融物を形成し、
(b)前記溶融物から、クロム/炭素比が7.0未満であり且つクロム含有量が30〜65重量%である、固体の炭化物含有合金鉄溶接消耗材料を形成する、
ことを含んでなり、
前記工程(a)が、前記溶融物の温度を比較的長い時間(公称30〜60分間)保持して炭素を前記溶融物中に溶解させ、前記工程(b)において前記溶融物から前記固体合金鉄溶接消耗材料中に規定濃度の化学結合した炭素を形成することを含む、方法。 - 前記工程(a)は、固体原料から前記均質な溶融物を形成する、ことを含む、請求項1に記載の方法。
- 前記工程(a)は、グラファイトを前記溶融物に添加して、前記溶融物を炭素で過飽和にする、ことを含む、請求項1または2に記載の方法。
- 前記工程(a)は、スクラップ鋼または高クロム白鋳鉄等の鉄含有材料(クロム含有合金鉄以外である)を前記クロム含有合金鉄材料および遊離炭素の供給源に添加して均質な溶融物を形成し、前記溶融物中のクロム濃度を希釈する、ことを含む、請求項1〜3のいずれか一項に記載の方法。
- 前記工程(b)において形成された前記固体合金鉄溶接消耗材料が、その後に続く硬化肉盛操作で安定した溶接アークを形成し、それによって、得られる硬化肉盛溶着物中の多孔度を最少に抑え、溶接プールから合金鉄粉末が放出されるのを阻止するように、前記工程(a)で形成された前記溶融物を脱気する、ことを含む、請求項1〜4のいずれか一項に記載の方法。
- 前記工程(b)において形成された前記固体合金鉄溶接消耗材料が、その後に続く硬化肉盛操作で得られる前記硬化肉盛溶着物中に存在する非金属性不純物量を最少に抑えるように、前記工程(a)において形成された前記溶融物からスラグを除去する、ことを含む、請求項1〜5のいずれか一項に記載の方法。
- 化学結合した炭素の含有量が7.5重量%を超える合金鉄溶接消耗材料を製造する、ことを含む、請求項1〜6のいずれか一項に記載の方法。
- 前記工程(b)は、前記溶融物を好適な鋳型または他の鋳造手段の中にキャスティングし、その後、前記鋳造製品を、粉末形態等の好適な形態に粉砕する、ことを含む、請求項1〜7のいずれか一項に記載の方法。
- 前記工程(b)は、前記溶融物をアルゴン等の好適なガスで噴霧し、前記溶融物から固体粉末を形成する、ことを含む、請求項1〜7のいずれか一項に記載の方法。
- 好適な基材上に硬化肉盛溶着物を製造する方法であって、
a)i)請求項1〜9のいずれか一項に記載の方法により製造された炭化クロム含有合金鉄溶接消耗材料であって、溶融物中のクロム/炭素比が7.0未満であり且つクロム含有量が30〜65重量%である炭化クロム含有合金鉄溶接消耗材料、およびii)溶接ワイヤ材料の溶接プールを基材上に形成し、
b)その後、前記基材上の溶接プールから材料の硬化肉盛溶着物を堆積させる、
ことを含む、方法。
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AU2004900769A AU2004900769A0 (en) | 2004-02-16 | Hardfacing ferroalloy materials | |
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EA009434B1 (ru) | 2007-12-28 |
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AU2005212384A1 (en) | 2005-08-25 |
JP2007524513A (ja) | 2007-08-30 |
EP1716271B1 (en) | 2013-09-04 |
KR101279840B1 (ko) | 2013-06-28 |
WO2005078156A1 (en) | 2005-08-25 |
EP1716271A1 (en) | 2006-11-02 |
ES2440192T3 (es) | 2014-01-28 |
AU2005212384B2 (en) | 2009-10-29 |
CN1946876A (zh) | 2007-04-11 |
NZ549758A (en) | 2009-10-30 |
BRPI0507749A (pt) | 2007-07-10 |
US8941032B2 (en) | 2015-01-27 |
US20080251507A1 (en) | 2008-10-16 |
CA2556621C (en) | 2014-08-12 |
CN1946876B (zh) | 2011-07-27 |
BRPI0507749B1 (pt) | 2017-07-18 |
KR20070027516A (ko) | 2007-03-09 |
ZA200606970B (en) | 2008-01-08 |
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