WO2010058200A1 - Method for making an alloy - Google Patents
Method for making an alloy Download PDFInfo
- Publication number
- WO2010058200A1 WO2010058200A1 PCT/GB2009/051540 GB2009051540W WO2010058200A1 WO 2010058200 A1 WO2010058200 A1 WO 2010058200A1 GB 2009051540 W GB2009051540 W GB 2009051540W WO 2010058200 A1 WO2010058200 A1 WO 2010058200A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- particles
- alloy
- coated
- primary particles
- secondary particles
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 54
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 48
- 239000000956 alloy Substances 0.000 title claims abstract description 48
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 67
- 239000011164 primary particle Substances 0.000 claims abstract description 48
- 239000011163 secondary particle Substances 0.000 claims abstract description 43
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 34
- 239000002245 particle Substances 0.000 claims abstract description 32
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 24
- 239000010936 titanium Substances 0.000 claims abstract description 21
- 238000000498 ball milling Methods 0.000 claims abstract description 20
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 15
- 238000000576 coating method Methods 0.000 claims abstract description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011248 coating agent Substances 0.000 claims abstract description 10
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 8
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 6
- 239000010937 tungsten Substances 0.000 claims abstract description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000004411 aluminium Substances 0.000 claims abstract description 5
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052737 gold Inorganic materials 0.000 claims abstract description 5
- 239000010931 gold Substances 0.000 claims abstract description 5
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 5
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 5
- 239000011733 molybdenum Substances 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 229910052762 osmium Inorganic materials 0.000 claims abstract description 5
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 5
- 239000010948 rhodium Substances 0.000 claims abstract description 5
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052709 silver Inorganic materials 0.000 claims abstract description 5
- 239000004332 silver Substances 0.000 claims abstract description 5
- 238000003801 milling Methods 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 239000011230 binding agent Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- 150000002736 metal compounds Chemical class 0.000 claims description 8
- 150000002739 metals Chemical class 0.000 claims description 7
- 238000001746 injection moulding Methods 0.000 claims description 4
- 229910052987 metal hydride Inorganic materials 0.000 claims description 4
- 150000004681 metal hydrides Chemical class 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 4
- 239000011149 active material Substances 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 2
- 238000010894 electron beam technology Methods 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 229910001069 Ti alloy Inorganic materials 0.000 description 17
- 238000005260 corrosion Methods 0.000 description 14
- 230000007797 corrosion Effects 0.000 description 14
- 230000008569 process Effects 0.000 description 11
- 239000000843 powder Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910001252 Pd alloy Inorganic materials 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000005056 compaction Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- -1 for example Inorganic materials 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 238000011143 downstream manufacturing Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000001513 hot isostatic pressing Methods 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 1
- 235000020778 linoleic acid Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- HBEQXAKJSGXAIQ-UHFFFAOYSA-N oxopalladium Chemical compound [Pd]=O HBEQXAKJSGXAIQ-UHFFFAOYSA-N 0.000 description 1
- 229910003445 palladium oxide Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000012358 sourcing Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910000048 titanium hydride Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/045—Alloys based on refractory metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
Definitions
- the present invention relates to a method for making an alioy comprising compacting primary particles coated with secondary particles.
- metal alloys are used for different applications, each alloy offering a particular combination of properties, including strength, ductility, creep resistance, corrosion resistance, fatigue resistance and castability.
- pure titanium is highly resistant to corrosion, its corrosion resistance can be improved by forming an alloy with 0.15 wt% palladium.
- Ti-6AI-4V is a popular titanium alloy which displays high strength, creep resistance, fatigue resistance and castability. The corrosion resistance of Ti- 6AI-4V may also be similarly improved by the addition of palladium.
- titanium The global production of titanium is small in comparison with other metals or alloys and the majority of titanium currently produced is for use in the aerospace industries. Other industries, however, have encountered difficulties in sourcing the material they require and have additionally found it undesirable to maintain a large stock of a range of different titanium alloys as a result of the high price of titanium.
- a desired alloy composition comprising a primary metal, such as titanium, and at least one secondary metal would allow a manufacturer to store a reduced inventory while enabling the manufacture of a range of alloys, as well as the articles produced therefrom.
- a primary metal such as titanium
- at least one secondary metal would allow a manufacturer to store a reduced inventory while enabling the manufacture of a range of alloys, as well as the articles produced therefrom.
- the high price of titanium contributes to the problems associated with titanium alloy article manufacture, these problems are not unique to titanium alloys and the advantages associated with the rapid manufacture of specific alloy compositions on demand are equally applicable to a wide range of alloys.
- required properties e.g. corrosion resistance
- the present invention provides a method for making an alloy comprising the steps of:
- the primary particles comprise at least one of titanium, molybdenum, tungsten, nickel or iron;
- the secondary particles comprise at least one of platinum, palladium, rhodium, ruthenium, iridium, osmium, silver, gold or aluminium;
- the primary particles are coated with secondary particles by low energy ball milling; and the coated particles are substantially spherical.
- the primary particles are preferably substantially spherical and maintain their substantially spherical shape during the coating process.
- the production of substantially spherical coated particles is advantageous because the flowability of the coated particles is improved, which assists in downstream metallurgical processing.
- the secondary particles may be coated onto the primary particles using simple physical methods, such as low energy ball milling or any other process that minimises the physical distortion of the primary particles.
- the secondary particles may be coated onto the primary particles using one of the chemical routines that would be known to those skilled in the art e.g. electroless plating or reductive chemical deposition.
- low energy ball milling is a gentle method which, while not wishing to be bound by theory, results in a physical change in the primary and secondary particles whereby the particles are physically cojoined.
- the milling process may be controlled by various parameters including the speed at which the milling takes place, the length of milling time and/or the level to which the milling container is filled. Additionally, improvement in the coating process can be made by controlling the milling media such as the particle ratio, the size of the milling media and other parameters as are familiar to the skilled person.
- the speed at which the milling takes place is from about 10 rpm to about
- the speed is from about 75 rpm to about 300 rpm. Even more preferably, the speed is from about 80 rpm to about 140 rpm.
- the length of milling time is preferably from about 3 hours to about 20 days, more preferably, about 6 hours to about 10 days and even more preferably, about 1 day to about 7 days.
- the milling container is charged to a level from about 10 vol% to about 50 vol%. More preferably, the level is from about 15 vol% to about 40 vol% and even more preferably, from about 20 vol% to about 30 vol%.
- Certain metals or metal alloys possessing a strong affinity for oxygen suffer from excessive surface oxide growth if the milling is carried out in the presence of oxygen.
- the final, compacted article is to conform to a recognised specification for oxygen content, it may be required that an oxygen-deficient atmosphere is to be used. Accordingly, the low energy ball milling of the present invention may be carried out under an inert atmosphere for at least a proportion of the milling time.
- an inert atmosphere is one which has limited or no ability to react with the primary and/or secondary particles.
- the inert atmosphere comprises argon, nitrogen or a mixture thereof.
- the low energy ball milling is carried out under an inert atmosphere for the same period of time as the milling process itself.
- the low energy ball milling may be carried out under a reactive atmosphere for at least a proportion of the milling time.
- a reactive atmosphere is one which may react with at least a proportion of the primary particles and/or secondary particles in order to reduce surface oxides on the particles or to convert a non-metallic source to a metallic one.
- the reactive atmosphere comprises hydrogen gas.
- the low energy ball milling process may be carried out in a wet or dry environment.
- at least one solvent may be added to the substances being milled, which solvent can act to minimise particle welding.
- the addition of a solvent is particularly helpful if the substances being milling has agglomerated prior to use, in which case the solvent can assist with breaking down the agglomerates.
- Solvents suitable for use within the claimed method include but are not limited to single solvents, e.g. tetrahydrofuran (THF) or hexane, or solvent mixtures, such as THF/hexane or alcohokwater mixtures, such as ethanokwater.
- THF tetrahydrofuran
- solvent mixtures such as THF/hexane
- alcohokwater mixtures such as ethanokwater.
- the ratio of the alcohokwater may be from about 3:1.
- the alcohokwater mixtures may be suitable, for example, where the oxygen affinity of the primary particles is low.
- the solvent may further comprise a soluble surface-active material, for example, a long-chain organic compound, such as stearic acid, linoleic acid and/or oleic acid.
- a soluble surface-active material for example, a long-chain organic compound, such as stearic acid, linoleic acid and/or oleic acid.
- the surface-active material may prevent particle agglomeration, as well as the presence of detrimental residues which can affect subsequent downstream processing, for example, in metal injection moulding (MIM).
- MIM metal injection moulding
- the primary particles preferably comprise a single metal, an admix of metals, an alloy or a combination thereof.
- titanium is preferred.
- the primary particles comprise an alloy, titanium alloys (e.g. Ti-6AI-4V) or iron alloys (e.g. steel and, in particular, stainless steel) are preferred.
- the secondary particles preferably comprise a single metal, an admix of metals, an alloy or a combination thereof.
- the metal is preferably palladium or ruthenium. In a particularly preferred embodiment, the metal is palladium.
- a preferred alloy is palladium and ruthenium.
- the primary particles preferably comprise titanium, e.g. commercially available titanium or titanium alloy, and the secondary particles preferably comprise palladium and/or ruthenium.
- the primary particles comprise " T ⁇ -6AI-4V and the secondary particles comprise palladium.
- the inventors have found that the corrosion resistance of articles produced using a titanium/palladium alloy made according to this process is equal to the corrosion resistance of articles produced using commercial titanium/palladium alloys. This would enable a manufacturer of alloy articles to keep an inventory of titanium powder and palladium powder, and to coat the titanium powder with the required amount of palladium whenever the manufacturer needed to fabricate articles from a particular alloy composition. This is particularly advantageous for the manufacturer of small, intricate articles who does not manufacture in bulk and so cannot normally benefit from economies of scale.
- the primary particles may comprise tungsten and the secondary particles may comprise rhenium and/or copper.
- the coating of the secondary particles on the primary particles may be in the form of a film or in the form of discrete particles.
- the form may vary depending on the method used to apply the secondary particles to the primary particles.
- the degree of coverage will depend on the ductility of the secondary particles, the length of time allowed for the coating process and/or the quantity of secondary particles present e.g. palladium may be added to titanium alloys in a proportion of about 0.05 wt% to about 0.25 wt%, which is recognisable as the levels of additions in ASTM/ASME Ti grades, 7, 11 , 16, 17, 24 and 25.
- the quantity of secondary particles can also affect one or more properties of the desired alloy formed. In this respect, when the quantity of Pd is increased in a Pd/Ti alloy, the corrosion resistance of the alloy to chloride-containing solutions (such as salt water) improves.
- a binder may be used to assist the mixing or dispersion of the primary particles and/or secondary particles. Whether a binder is present during the mixing stage and/or during any other pre-compaction stages, the binder will not be present in the alloy formed by the claimed method nor will any degradation products of the binder be present. This is because the binders used are destroyed during compaction.
- the science of the use of binders and the processes by which binder removal occurs are well documented, for example, in "Injection Molding of Metals and Ceramics" by Randall M. German and Animesh Bose, MPIF Publishers, 1997 (ISBN No.
- the primary particles may be formed from at least one metal compound before being coated with the secondary particles, during the coating of the secondary particles, prior to compacting the coated primary particles or during the compacting of the coated primary particles. Even if metal compounds are used in the claimed method, the alloy thereby formed will not substantially contain any of the metal compounds.
- the primary particles are formed from at least one metal hydride, for example, titanium hydride.
- the secondary particles are formed from at least one metal compound prior to or during the compacting of the coated primary particles.
- the secondary particles are formed from at least one metal oxide (for example, palladium oxide or ruthenium oxide), metal hydride (such as palladium hydride or Pd/Ti mixed hydrides).
- the primary particles will have an average diameter of about ⁇ 1000 ⁇ m, more preferably about ⁇ 800 ⁇ m and even more preferably, about ⁇ 550 ⁇ m.
- the average diameter of the primary particles is dependent on the downstream processing envisaged for the coated particles. For example, when MIM is to take place, the average diameter of the primary particles is preferably ⁇ 45 ⁇ m and more preferably, ⁇ 10 ⁇ m.
- the secondary particles need not necessarily be substantially spherical in shape.
- the coated particles are compacted and an alloy formed therefrom.
- Suitable methods for compacting the coated particles include Hot lsostatic Pressing (HIP-ing), Cold lsostatic Pressing (CIP-ing), Metal Injection Moulding (MIM) and high energy beam fabrication methods, such as Direct Laser Fabrication (DLF), and Electron Beam Melting.
- HIP-ing Hot lsostatic Pressing
- CIP-ing Cold lsostatic Pressing
- MIM Metal Injection Moulding
- high energy beam fabrication methods such as Direct Laser Fabrication (DLF), and Electron Beam Melting.
- the present invention provides substantially spherical coated particles, wherein the primary particles are coated with secondary particles; and wherein, the primary particles comprise at least one of titanium, molybdenum, tungsten, nickel or iron; and the secondary particles comprise at least one of platinum, palladium, rhodium, ruthenium, iridium, osmium, silver, gold or aluminium.
- the present invention provides an alloy formed by the claimed method, and metal articles formed from such an alloy.
- Figure 1 is a backscattered electron image of a titanium alloy powder coated with 0.2 wt% Pd by a low energy ball milling process.
- Figure 2 is a backscattered electron image of titanium alloy powder compacted structure that has been formed by first coating a titanium alloy powder with 2.0 wt% Pd via a low energy ball milling process and then subjecting the coated powder to a standard hot isostatic pressing cycle process (93O 0 C, 4 hours, 100MPa).
- Figure 3 is a graph showing the polarisation curves for titanium alloy samples produced from a) Ti alloy powder coated with 0.15 wt% Pd via a low energy ball milling process and then compacted using a hot isostatic pressing cycle as per Figure 2, and b) a melt and cast, followed by hot isostatically pressed alloy article containing 0.15 wt% Pd.
- Figure 4 is a graph comparing the corrosion potential (open circuit potential) vs. time for HIP-ed titanium alloy powders made by a) coating with 0.15 wt% Pd for 7 days and b) milling alone for 7 days.
- Ti-6AI-4V powder (20Og) with a particle size of 150-500 ⁇ m is low energy ball milled with 0.15 wt% of palladium particles (surface area 19-26 m 2 /g) for 7 days.
- a sample of the resulting palladium coated alloy particles (see Figure 1) are encapsulated in a mild steel container, which is evacuated and sealed prior to HlP-ing at 930 0 C for 4 hours at 100 MPa. This process results in a heterogeneous distribution of palladium in which palladium is located preferentially within the beta phase at the particle boundaries of the primary particles. Palladium concentrations within areas that would have formed the interior of the original primary Ti particles are below the limits of detection.
- Example 1 is fabricated into a solid article by direct laser fabrication using process parameters suitable for the manufacture of Ti-6AI-4V articles (laser power 750 W, laser scan speed 400 mm/min and step build height 0.3 mm). Melting of the particles during the DLF process results in a homogeneous distribution of palladium within the article formed.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Powder Metallurgy (AREA)
Abstract
A method for making an alloy comprising the steps of: (a) coating primary particles with secondary particles; (b) compacting the coated particles; and (c) forming an alloy therefrom; wherein, the primary particles comprise at least one of titanium, molybdenum, tungsten, nickel or iron; the secondary particles comprise at least one of platinum, palladium, rhodium, ruthenium, iridium, osmium, silver, gold or aluminium; the primary particles are coated with secondary particles by low energy ball milling; and the coated particles are substantially spherical. Alloys formed by this method and metal articles formed from such alloys are also described.
Description
METHOD FOR MAKING AN ALLOY
The present invention relates to a method for making an alioy comprising compacting primary particles coated with secondary particles.
A very wide range of metal alloys are used for different applications, each alloy offering a particular combination of properties, including strength, ductility, creep resistance, corrosion resistance, fatigue resistance and castability. For example, although pure titanium is highly resistant to corrosion, its corrosion resistance can be improved by forming an alloy with 0.15 wt% palladium. Likewise, Ti-6AI-4V is a popular titanium alloy which displays high strength, creep resistance, fatigue resistance and castability. The corrosion resistance of Ti- 6AI-4V may also be similarly improved by the addition of palladium.
The global production of titanium is small in comparison with other metals or alloys and the majority of titanium currently produced is for use in the aerospace industries. Other industries, however, have encountered difficulties in sourcing the material they require and have additionally found it undesirable to maintain a large stock of a range of different titanium alloys as a result of the high price of titanium.
The rapid manufacture of a desired alloy composition comprising a primary metal, such as titanium, and at least one secondary metal would allow a manufacturer to store a reduced inventory while enabling the manufacture of a range of alloys, as well as the articles produced therefrom. However, while the high price of titanium contributes to the problems associated with titanium alloy article manufacture, these problems are not unique to titanium alloys and the advantages associated with the rapid manufacture of specific alloy compositions on demand are equally applicable to a wide range of alloys.
The inventors believe that the ability to generate a tailored alloy composition with required properties (e.g. corrosion resistance) would encourage the use of those alloys and, in particular, the use of titanium alloys, in addition, the subsequent fabrication of articles from the alloys would accordingly be facilitated as the period of time within which the wrought alloy is purchased would be reduced or even eliminated.
Accordingly, the present invention provides a method for making an alloy comprising the steps of:
(a) coating primary particles with secondary particles;
(b) compacting the coated particles; and
(c) forming an alloy therefrom; wherein,
i
the primary particles comprise at least one of titanium, molybdenum, tungsten, nickel or iron; the secondary particles comprise at least one of platinum, palladium, rhodium, ruthenium, iridium, osmium, silver, gold or aluminium; the primary particles are coated with secondary particles by low energy ball milling; and the coated particles are substantially spherical.
The primary particles are preferably substantially spherical and maintain their substantially spherical shape during the coating process. The production of substantially spherical coated particles is advantageous because the flowability of the coated particles is improved, which assists in downstream metallurgical processing.
The secondary particles may be coated onto the primary particles using simple physical methods, such as low energy ball milling or any other process that minimises the physical distortion of the primary particles. Alternatively, the secondary particles may be coated onto the primary particles using one of the chemical routines that would be known to those skilled in the art e.g. electroless plating or reductive chemical deposition.
The inventors have surprisingly found that low energy ball milling is a gentle method which, while not wishing to be bound by theory, results in a physical change in the primary and secondary particles whereby the particles are physically cojoined. When low energy ball milling is used as the means to apply the coating to the primary particles, the milling process may be controlled by various parameters including the speed at which the milling takes place, the length of milling time and/or the level to which the milling container is filled. Additionally, improvement in the coating process can be made by controlling the milling media such as the particle ratio, the size of the milling media and other parameters as are familiar to the skilled person.
Preferably, the speed at which the milling takes place is from about 10 rpm to about
350 rpm. More preferably, the speed is from about 75 rpm to about 300 rpm. Even more preferably, the speed is from about 80 rpm to about 140 rpm.
The length of milling time is preferably from about 3 hours to about 20 days, more preferably, about 6 hours to about 10 days and even more preferably, about 1 day to about 7 days.
Preferably, the milling container is charged to a level from about 10 vol% to about 50 vol%. More preferably, the level is from about 15 vol% to about 40 vol% and even more preferably, from about 20 vol% to about 30 vol%.
Certain metals or metal alloys possessing a strong affinity for oxygen suffer from excessive surface oxide growth if the milling is carried out in the presence of oxygen. In particular, if the final, compacted article is to conform to a recognised specification for oxygen content, it may be required that an oxygen-deficient atmosphere is to be used. Accordingly, the low energy ball milling of the present invention may be carried out under an inert atmosphere for at least a proportion of the milling time. Within the context of the invention, an inert atmosphere is one which has limited or no ability to react with the primary and/or secondary particles. Preferably, the inert atmosphere comprises argon, nitrogen or a mixture thereof. Preferably, the low energy ball milling is carried out under an inert atmosphere for the same period of time as the milling process itself.
Alternatively, the low energy ball milling may be carried out under a reactive atmosphere for at least a proportion of the milling time. A reactive atmosphere is one which may react with at least a proportion of the primary particles and/or secondary particles in order to reduce surface oxides on the particles or to convert a non-metallic source to a metallic one. Preferably, the reactive atmosphere comprises hydrogen gas.
The low energy ball milling process may be carried out in a wet or dry environment. For example, at least one solvent may added to the substances being milled, which solvent can act to minimise particle welding. The addition of a solvent is particularly helpful if the substances being milling has agglomerated prior to use, in which case the solvent can assist with breaking down the agglomerates.
Solvents suitable for use within the claimed method include but are not limited to single solvents, e.g. tetrahydrofuran (THF) or hexane, or solvent mixtures, such as THF/hexane or alcohokwater mixtures, such as ethanokwater. The ratio of the alcohokwater may be from about 3:1. The alcohokwater mixtures may be suitable, for example, where the oxygen affinity of the primary particles is low.
The solvent may further comprise a soluble surface-active material, for example, a long-chain organic compound, such as stearic acid, linoleic acid and/or oleic acid. When utilised, the surface-active material may prevent particle agglomeration, as well as the presence of detrimental residues which can affect subsequent downstream processing, for example, in metal injection moulding (MIM).
The primary particles preferably comprise a single metal, an admix of metals, an alloy or a combination thereof. When the primary particles comprise a single metal, titanium is preferred. When the primary particles comprise an alloy, titanium alloys (e.g. Ti-6AI-4V) or iron alloys (e.g. steel and, in particular, stainless steel) are preferred.
The secondary particles preferably comprise a single metal, an admix of metals, an alloy or a combination thereof. When the secondary particles comprise a single metal, the metal is preferably palladium or ruthenium. In a particularly preferred embodiment, the metal is palladium. When the secondary particles comprise an alloy, a preferred alloy is palladium and ruthenium.
In one embodiment, the primary particles preferably comprise titanium, e.g. commercially available titanium or titanium alloy, and the secondary particles preferably comprise palladium and/or ruthenium. In a particularly preferred embodiment, the primary particles comprise "TΪ-6AI-4V and the secondary particles comprise palladium. The inventors have found that the corrosion resistance of articles produced using a titanium/palladium alloy made according to this process is equal to the corrosion resistance of articles produced using commercial titanium/palladium alloys. This would enable a manufacturer of alloy articles to keep an inventory of titanium powder and palladium powder, and to coat the titanium powder with the required amount of palladium whenever the manufacturer needed to fabricate articles from a particular alloy composition. This is particularly advantageous for the manufacturer of small, intricate articles who does not manufacture in bulk and so cannot normally benefit from economies of scale.
The same inventory/convenience advantages would apply to a range of different alloy compositions. For example, in an alternative embodiment the primary particles may comprise tungsten and the secondary particles may comprise rhenium and/or copper.
The coating of the secondary particles on the primary particles may be in the form of a film or in the form of discrete particles. The form may vary depending on the method used to apply the secondary particles to the primary particles. The degree of coverage will depend on the ductility of the secondary particles, the length of time allowed for the coating process and/or the quantity of secondary particles present e.g. palladium may be added to titanium alloys in a proportion of about 0.05 wt% to about 0.25 wt%, which is recognisable as the levels of additions in ASTM/ASME Ti grades, 7, 11 , 16, 17, 24 and 25. The quantity of secondary particles can also affect one or more properties of the desired alloy formed. In this respect, when the quantity of Pd is increased in a Pd/Ti alloy, the corrosion resistance of the alloy to chloride-containing solutions (such as salt water) improves.
A binder may be used to assist the mixing or dispersion of the primary particles and/or secondary particles. Whether a binder is present during the mixing stage and/or during any other pre-compaction stages, the binder will not be present in the alloy formed by the claimed method nor will any degradation products of the binder be present. This is because the binders used are destroyed during compaction. The science of the use of
binders and the processes by which binder removal occurs are well documented, for example, in "Injection Molding of Metals and Ceramics" by Randall M. German and Animesh Bose, MPIF Publishers, 1997 (ISBN No. 1-878-954-61 -X) which is hereby incorporated by reference in its entirety for all purposes, and which will not be discussed further other than to say that the removal of the binder systems can generally be achieved cleanly and readily. Table 4.3 on page 91 of the above reference lists 24 example binder formulations, many employing components such as stearic acid, glycerine, polymethylmethacrylate, paraffin wax or carnauba wax.
The primary particles may be formed from at least one metal compound before being coated with the secondary particles, during the coating of the secondary particles, prior to compacting the coated primary particles or during the compacting of the coated primary particles. Even if metal compounds are used in the claimed method, the alloy thereby formed will not substantially contain any of the metal compounds. Preferably, the primary particles are formed from at least one metal hydride, for example, titanium hydride.
In another embodiment, the secondary particles are formed from at least one metal compound prior to or during the compacting of the coated primary particles. Preferably, the secondary particles are formed from at least one metal oxide (for example, palladium oxide or ruthenium oxide), metal hydride (such as palladium hydride or Pd/Ti mixed hydrides).
In one embodiment, the primary particles will have an average diameter of about ≤1000 μm, more preferably about ≤800 μm and even more preferably, about ≤550 μm. The average diameter of the primary particles is dependent on the downstream processing envisaged for the coated particles. For example, when MIM is to take place, the average diameter of the primary particles is preferably ≤45 μm and more preferably, ≤10 μm. However, the secondary particles need not necessarily be substantially spherical in shape.
The coated particles are compacted and an alloy formed therefrom. Suitable methods for compacting the coated particles include Hot lsostatic Pressing (HIP-ing), Cold lsostatic Pressing (CIP-ing), Metal Injection Moulding (MIM) and high energy beam fabrication methods, such as Direct Laser Fabrication (DLF), and Electron Beam Melting. Despite the fact that articles produced by HIP-ing have an inhomogeneous distribution of the metal from the secondary particles, the inventors have found that the corrosion resistance of the alloy formed by the claimed method is independent of the method used to compact the particles, therefore, whichever technique best suits the article to be made from the alloy may be used.
However, the mechanical properties of the alloy formed by the claimed method do depend on the method used to compact the particles, therefore, the compaction technique must be carefully selected depending on the required mechanical properties of the final article to be made from the alloy.
In a further aspect, the present invention provides substantially spherical coated particles, wherein the primary particles are coated with secondary particles; and wherein, the primary particles comprise at least one of titanium, molybdenum, tungsten, nickel or iron; and the secondary particles comprise at least one of platinum, palladium, rhodium, ruthenium, iridium, osmium, silver, gold or aluminium.
In yet another aspect, the present invention provides an alloy formed by the claimed method, and metal articles formed from such an alloy.
The invention will now be described by way of the following non-limiting examples and with reference to the following drawings in which:
Figure 1 is a backscattered electron image of a titanium alloy powder coated with 0.2 wt% Pd by a low energy ball milling process.
Figure 2 is a backscattered electron image of titanium alloy powder compacted structure that has been formed by first coating a titanium alloy powder with 2.0 wt% Pd via a low energy ball milling process and then subjecting the coated powder to a standard hot isostatic pressing cycle process (93O0C, 4 hours, 100MPa).
Figure 3 is a graph showing the polarisation curves for titanium alloy samples produced from a) Ti alloy powder coated with 0.15 wt% Pd via a low energy ball milling process and then compacted using a hot isostatic pressing cycle as per Figure 2, and b) a melt and cast, followed by hot isostatically pressed alloy article containing 0.15 wt% Pd.
Figure 4 is a graph comparing the corrosion potential (open circuit potential) vs. time for HIP-ed titanium alloy powders made by a) coating with 0.15 wt% Pd for 7 days and b) milling alone for 7 days.
EXAMPLE 1 HlP-ing of TJ-6AI-4V with Pd
Ti-6AI-4V powder (20Og) with a particle size of 150-500 μm is low energy ball milled with 0.15 wt% of palladium particles (surface area 19-26 m2/g) for 7 days. A sample of the resulting palladium coated alloy particles (see Figure 1) are encapsulated in a mild steel container, which is evacuated and sealed prior to HlP-ing at 930 0C for 4 hours at 100 MPa. This process results in a heterogeneous distribution of palladium in which palladium is located preferentially within the beta phase at the particle boundaries of the primary particles.
Palladium concentrations within areas that would have formed the interior of the original primary Ti particles are below the limits of detection.
An image of an alloy powder HIP-ed as described above but which contains 2.0 wt% palladium can be seen in Figure 2.
EXAMPLE 2 DLF of TJ-6A1-4V with Pd
A sample of the palladium coated particles produced by low energy ball milling in
Example 1 is fabricated into a solid article by direct laser fabrication using process parameters suitable for the manufacture of Ti-6AI-4V articles (laser power 750 W, laser scan speed 400 mm/min and step build height 0.3 mm). Melting of the particles during the DLF process results in a homogeneous distribution of palladium within the article formed.
EXAMPLE 3 Assessment of Corrosion Resistance
For corrosion experiments samples are mounted in cold setting resin and all of the tests were carried out in naturally aerated 2 M HCI at 37 0C using a 3-electrode cell (with the sample acting as the working electrode, a platinum counter electrode and a saturated calomel electrode (SCE) as reference). 2 M HCI was selected as the electrolyte to simulate aggressive environmental conditions that might exist within a crevice on the surface of an alloy particle.
Polarisation curve tests: Samples were prepared by grinding a) Ti powder compacts which had been low energy ball-milled with 0.15 wt% palladium then HIP-ed, and b) a cast alloy article containing 0.15 wt% palladium which had also been HIP-ed. Each sample was prepared by grinding to 1200 grit SiC, then washed in de-ionised water, rinsed in ethanol and dried and then tested immediately once dry. Figure 3 shows that the palladium still provides equivalent corrosion protection whether it is homogeneously distributed or inhomogeneously distributed within a titanium article.
Open circuit potential tests: Samples of HIP-ed Ti-6AI-4V powders a) low energy ball-milled with 0.15% Pd for 7 days and b) low energy ball-milled alone for 7 days, were polished using colloidal silica immediately prior to testing, then washed in de-ionised water, rinsed in ethanol and tested immediately once dry. Figure 4 shows that the sample containing palladium has a higher corrosion potential than the one not containing palladium.
Claims
1. A method for making an alloy comprising the steps of:
(a) coating primary particles with secondary particles;
(b) compacting the coated particles; and
(c) forming an alloy therefrom; wherein, the primary particles comprise at least one of titanium, molybdenum, tungsten, nickel or iron; the secondary particles comprise at least one of platinum, palladium, rhodium, ruthenium, iridium, osmium, silver, gold or aluminium; the primary particles are coated with secondary particles by low energy ball milling; and the coated particles are substantially spherical.
2. A method according to claim 1, wherein the primary particles are substantially spherical.
3. A method according to claim 1, wherein the low energy ball milling is carried out a speed of from 10 rpm to 350 rpm.
4. A method according to any one of the preceding claims, wherein the low energy ball milling is carried out from about 3 hours to about 20 days.
5. A method according to any one of the preceding claims, wherein a container for the low energy ball milling is charged to a level from about 10 vol% to about 50 vol%.
6. A method according to any one of the preceding claims, wherein the low energy ball milling is carried out under an inert atmosphere for at least a proportion of the milling time.
7. A method according to any one of the preceding claims, wherein the low energy ball milling is carried out under a reactive atmosphere for at least a proportion of the milling time.
8. A method according to any of the preceding claims, wherein the low energy ball milling is carried out in the presence of at least one solvent.
9. A method according to claim 8, wherein the solvent further comprises a soluble surface-active material.
10. A method according to any one of the preceding claims, wherein the primary particles comprise a single metal, an admix of metals, an alloy or a combination thereof.
11. A method according to any one of the preceding claims, wherein the secondary particles comprise a single metal, an admix of metals, an alloy or a combination thereof.
12. A method according to any one of the preceding claims, wherein the coating of the secondary particles on the primary particles is in the form of a film or in the form of discrete particles.
13. A method according to any one of the preceding claims, wherein a binder assists the mixing or dispersion of the primary particles and/or the secondary particles.
14. A method according to any one of the preceding claims, wherein the primary particles are formed from at least one metal compound before being coated with the secondary particles, during the coating of the secondary particles, prior to the compacting of the coated particles or during the compacting of the coated particles.
15. A method according to claim 14, wherein the at least one metal compound is a metal hydride.
16. A method according to any one of the preceding claims, wherein the secondary particles are formed from at least one metal compound prior to or during the compacting of the coated primary particles.
17. A method according to claim 16, wherein the at least one metal compound is a metal oxide or metal hydride.
18. A method according to any one of the preceding claims, wherein the primary particles have an average diameter of about ≤1000 μm.
19. A method according to any one of the preceding claims, in which the compacting is carried out by Hot lsostatic Pressing, Cold lsostatic Pressing, Metal Injection Moulding, Electron Beam Melting or a high energy beam fabrication method.
20. A method according to claim 19, wherein the high energy beam fabrication method is Direct Laser Fabrication.
21. An alloy formed by a method according to any of claims 1 to 20.
22. A metal article formed from an alloy according to claim 21.
23. Substantially spherical coated particles, wherein the primary particles are coated with secondary particles; and wherein, the primary particles comprise at least one of titanium, molybdenum, tungsten, nickel or iron; and the secondary particles comprise at least one of platinum, palladium, rhodium, ruthenium, iridium, osmium, silver, gold or aluminium.
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Cited By (6)
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CN104404508A (en) * | 2014-11-24 | 2015-03-11 | 桂林电子科技大学 | Laser additive manufacturing method for aluminium alloy structural part |
AT14301U1 (en) * | 2014-07-09 | 2015-07-15 | Plansee Se | Method for producing a component |
US9334550B2 (en) | 2009-10-14 | 2016-05-10 | Anglo Platinum Marketing Limited | Method of controlling the carbon or oxygen content of a powder injection |
EP3096904A4 (en) * | 2014-01-24 | 2017-10-25 | United Technologies Corporation | Powder improvement for additive manufacturing |
CN109014198A (en) * | 2018-08-16 | 2018-12-18 | 北京科技大学 | A method of preparing the pure molybdenum part of high-performance |
US20220344096A1 (en) * | 2021-04-22 | 2022-10-27 | China Jiliang University | Method for preparing high-performance anisotropic rare-earth-free permanent magnets |
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WO2008034043A2 (en) * | 2006-09-14 | 2008-03-20 | Iap Research, Inc. | Method of producing uniform blends of nano and micron powders |
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Patent Citations (1)
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WO2008034043A2 (en) * | 2006-09-14 | 2008-03-20 | Iap Research, Inc. | Method of producing uniform blends of nano and micron powders |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
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US9334550B2 (en) | 2009-10-14 | 2016-05-10 | Anglo Platinum Marketing Limited | Method of controlling the carbon or oxygen content of a powder injection |
JP2016135913A (en) * | 2009-10-14 | 2016-07-28 | アングロ プラチナム マーケティング リミテッド | Method |
EP3096904A4 (en) * | 2014-01-24 | 2017-10-25 | United Technologies Corporation | Powder improvement for additive manufacturing |
US10005127B2 (en) | 2014-01-24 | 2018-06-26 | United Technologies Corporation | Powder improvement for additive manufacturing |
AT14301U1 (en) * | 2014-07-09 | 2015-07-15 | Plansee Se | Method for producing a component |
KR20170031688A (en) * | 2014-07-09 | 2017-03-21 | 플란제 에스이 | Method for producing a component |
KR102359523B1 (en) * | 2014-07-09 | 2022-02-07 | 플란제 에스이 | Method for producing a component |
CN104404508A (en) * | 2014-11-24 | 2015-03-11 | 桂林电子科技大学 | Laser additive manufacturing method for aluminium alloy structural part |
CN104404508B (en) * | 2014-11-24 | 2017-04-05 | 桂林电子科技大学 | A kind of laser gain material manufacture method of aluminum alloy junction component |
CN109014198A (en) * | 2018-08-16 | 2018-12-18 | 北京科技大学 | A method of preparing the pure molybdenum part of high-performance |
US20220344096A1 (en) * | 2021-04-22 | 2022-10-27 | China Jiliang University | Method for preparing high-performance anisotropic rare-earth-free permanent magnets |
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