US20170225234A1 - A preparation method of rare earth oxide dispersion strengthened fine grain tungsten materials - Google Patents
A preparation method of rare earth oxide dispersion strengthened fine grain tungsten materials Download PDFInfo
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- US20170225234A1 US20170225234A1 US14/901,780 US201414901780A US2017225234A1 US 20170225234 A1 US20170225234 A1 US 20170225234A1 US 201414901780 A US201414901780 A US 201414901780A US 2017225234 A1 US2017225234 A1 US 2017225234A1
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- Prior art keywords
- rare earth
- tungsten
- earth oxide
- dispersion strengthened
- preparation
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000010937 tungsten Substances 0.000 title claims abstract description 54
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 48
- 229910001404 rare earth metal oxide Inorganic materials 0.000 title claims abstract description 47
- 239000000463 material Substances 0.000 title claims abstract description 46
- 239000006185 dispersion Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 43
- 239000002245 particle Substances 0.000 claims abstract description 37
- 239000000843 powder Substances 0.000 claims abstract description 29
- -1 rare earth salt Chemical class 0.000 claims abstract description 24
- 239000012266 salt solution Substances 0.000 claims abstract description 24
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002270 dispersing agent Substances 0.000 claims abstract description 20
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 18
- 239000011248 coating agent Substances 0.000 claims abstract description 16
- 238000000576 coating method Methods 0.000 claims abstract description 16
- 238000005245 sintering Methods 0.000 claims abstract description 16
- 239000000084 colloidal system Substances 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims abstract description 12
- 238000000975 co-precipitation Methods 0.000 claims abstract description 11
- 239000003513 alkali Substances 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 229910001930 tungsten oxide Inorganic materials 0.000 claims abstract description 9
- 239000011859 microparticle Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- 239000004615 ingredient Substances 0.000 claims abstract description 4
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 18
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 14
- 238000003825 pressing Methods 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 11
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 10
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 claims description 10
- 238000001694 spray drying Methods 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 229910052727 yttrium Inorganic materials 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 7
- 238000005056 compaction Methods 0.000 claims description 7
- 230000006835 compression Effects 0.000 claims description 7
- 238000007906 compression Methods 0.000 claims description 7
- 238000007873 sieving Methods 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 238000009694 cold isostatic pressing Methods 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 claims description 2
- 239000003995 emulsifying agent Substances 0.000 claims description 2
- 239000007970 homogeneous dispersion Substances 0.000 claims description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims 1
- 239000004202 carbamide Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 230000009467 reduction Effects 0.000 abstract description 4
- 238000001354 calcination Methods 0.000 abstract 1
- 238000000748 compression moulding Methods 0.000 abstract 1
- 150000003657 tungsten Chemical class 0.000 description 12
- 230000009471 action Effects 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 229910020854 La(OH)3 Inorganic materials 0.000 description 9
- 229910009454 Y(OH)3 Inorganic materials 0.000 description 9
- 238000011068 loading method Methods 0.000 description 6
- 238000005551 mechanical alloying Methods 0.000 description 6
- 238000005728 strengthening Methods 0.000 description 6
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 5
- 230000004907 flux Effects 0.000 description 5
- 239000007863 gel particle Substances 0.000 description 5
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 5
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 4
- 229910001175 oxide dispersion-strengthened alloy Inorganic materials 0.000 description 4
- 238000002490 spark plasma sintering Methods 0.000 description 4
- 229910000420 cerium oxide Inorganic materials 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000009770 conventional sintering Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000012190 activator Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- KHZAMZAEBBFMFS-UHFFFAOYSA-H lanthanum(3+);oxalate;hydrate Chemical compound O.[La+3].[La+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O KHZAMZAEBBFMFS-UHFFFAOYSA-H 0.000 description 2
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 206010011469 Crying Diseases 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 229910000756 V alloy Inorganic materials 0.000 description 1
- 229910001080 W alloy Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000004992 fission Effects 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 238000001513 hot isostatic pressing Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/30—Making metallic powder or suspensions thereof using chemical processes with decomposition of metal compounds, e.g. by pyrolysis
-
- 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
- C22C27/04—Alloys based on tungsten or molybdenum
-
- 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
-
- B22F1/0003—
-
- 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
- B22F3/04—Compacting only by applying fluid pressure, e.g. by cold isostatic pressing [CIP]
-
- 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
- B22F3/12—Both compacting and sintering
- B22F3/16—Both compacting and sintering in successive or repeated steps
-
- 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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
- B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
-
- 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
-
- 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
- C22C1/05—Mixtures of metal powder with non-metallic powder
-
- 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
- C22C1/1026—Alloys containing non-metals starting from a solution or a suspension of (a) compound(s) of at least one of the alloy constituents
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
- C22C32/0015—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
- C22C32/0031—Matrix based on refractory metals, W, Mo, Nb, Hf, Ta, Zr, Ti, V or alloys thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2301/00—Metallic composition of the powder or its coating
- B22F2301/20—Refractory metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2302/00—Metal Compound, non-Metallic compound or non-metal composition of the powder or its coating
- B22F2302/25—Oxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- 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
- 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
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C2200/00—Crystalline structure
- C22C2200/04—Nanocrystalline
Definitions
- the invention relates to field of nanomaterials and powder metallurgy field, especially a preparation method of rare earth oxide dispersion strengthened fine grain tungsten materials by nano-composite technology.
- Tungsten has characteristics such as high melting point, high hardness, good high temperature strength, thermal conductivity, electrical conductivity, low thermal expansion coefficient low sputtering and plasma effect, does not react with H, low H + retention, is a very important high temperature structural materials and functional materials and is widely used as a plasma facing material and divertor component material in the nuclear fusion field.
- pure tungsten material is a widely used, typical high temperature materials.
- tungsten grain size is about 100 microns
- the ductile to brittle transition temperature (DBTT) is about 300 ⁇ 350 ⁇
- the recrystallization temperature is of 1300 ⁇ 1350 ⁇
- room temperature tensile strength is more than 500 MPa
- high temperature tensile strength at 1000 ⁇ is about 400 MPa.
- this material exists defects such as coarse grain, fiber microstructure, high DBTT, low recrystallization temperature, high brittleness.
- the present invention adopts the heterogeneous precipitation—spray drying—calcining—thermal reduction—conventional sintering technology to prepare high performance rare-earth oxide dispersion strengthened fine grain tungsten materials, its density is close to full density (98.5% or higher), and the rare earth oxides particles evenly distribute in tungsten intracrystalline or grain boundary, its grain size is uniform and very fine (average in about 10 microns or less), with good room temperature and high temperature performance as well as high thermal loading shock resistance.
- a rare earth oxide dispersion strengthened fine grain tungsten material its character is that includes: rare earth oxides referred to any one or more of Y 2 O 3 , La 2 O 3 , or in CeO 2 , the mass percent of the rare earth oxide is of 0.1 ⁇ 2%, and the rest ingredient is W.
- The-mass percent of the rare earth oxide is of 0.1 ⁇ 2%, and the rest ingredient is W.
- the coprecipitation coating particle colloidal is spray-dried at 350 ⁇ 450 ⁇ forming tungsten and rare earth oxide compound precursor powder, which is then calcined at 300 ⁇ 600 ⁇ for 1 ⁇ 4 h. After deaggregation and sieving, the calcined powder is hydrogen reduced at 600 ⁇ 850° C. for 2 ⁇ 6 h, ultrafine or nanoscale tungsten powder with particle size of 50 ⁇ 500 nm is obtained.
- Rare earth oxides referred to any one or more of Y 2 O 2 , La 2 O 3 , or in CeO 2 ;
- the ultrafine/nanoscale tungsten powder containing trace rare earth oxide prepared in step (1) is compression molded under 150 ⁇ 300 MPa using mold pressing or cold isostatic pressing;
- the described tungstate is ammonium metatungstate, ammonium paratungstate or ammonium tungstate.
- the described rare earth salts are nitrate, oxalate, carbonate, chloride or sulfate of Y, La or Ce.
- the described stirring speed is 1000 ⁇ 5000 revolutions per minute.
- the described spray drying nozzle rotating speed is 20000 ⁇ 30000 revolutions per minute.
- reaction dispersant are stearic acid, polyethylene glycol (PEG), area, N, N-dimethyl formamide, OP emulsifier, twain-20 or sodium dodecyl sulfate, the mass fraction of reaction dispersant is of 0.1 ⁇ 1.5% of rare earth salt solution or tungstate solution.
- the described acid is hydrochloric acid (HCl), nitric acid (HNO 3 ) or oxalic acid (H 2 C 2 O 4 ), the described alkali is sodium hydroxide (NaOH), potassium hydroxide (KOH), or aqueous ammonia (NH 3 ⁇ H 2 O).
- heterogeneous precipitation—spray drying” adding rare earth oxide in tungsten matrix improves the compatibility of tungsten and rare earth oxides particles surface, spray drying achieves the uniformity of composition, microstructure in powder and alloy, so rare earth elements in tungsten matrix distribute more uniform, and do not introduce impurities.
- ultrafine tungsten composite powder containing trace rare earth oxides prepared by “heterogeneous precipitation—spray drying—calcining—hydrogen reduction” method has much higher sintering activity;
- the powder of this invention can reach more than 98.5% density sintered at 1800 ⁇ 2000 ⁇ by conventional sintering, grain size for sintered body is about 5 ⁇ 10 microns, and microstructure more evenly, excellent toughness at room temperature and high temperature.
- the invention adopts the conventional sintering method preparation of rare earth oxide dispersion strengthened fine grain tungsten materials, the technological process is simple and suitable for engineering preparation.
- the coprecipitated coating particle colloidal is spray-dried at 360 ⁇ , spray drying nozzle rotating speed is 20000 revolutions per minute, forming tungsten and rare earth oxide compound precursor powder,
- the precursor powder is then calcined at 350 ⁇ for 2 h. After desegregation and sieving, the calcined powder is hydrogen reduced at 780° C. for 4 h, ultrafine tungsten powder containing 0.1 wt % Y 2 O 3 is obtained.
- the ultrafine tungsten powder containing trace rare earth oxide is compression molded using mold pressing.
- the pressing molded compaction is subjected to pre-sintering and then high temperature sintered at 1950 ⁇ for 2 h and W-0.1 wt %Y 2 O 3 material is obtained, its density is above 99.2%, its microstructure is uniform and very fine, average grain size is less than 10 microns.
- This materials can bear 200 MW/m 2 high heat flux loading without surface crack appearing.
- the coprecipitated coating particle colloidal is spray-dried at 400 ⁇ , spray drying nozzle rotating speed is 20000 revolutions per minute, forming tungsten and rare earth lanthanum oxide compound precursor powder.
- the precursor powder is then calcined at 350 ⁇ for 2 h. After deaggregation and sieving, the calcined powder is hydrogen reduced at 780° C. for 4 h, ultrafine tungsten powder containing 0.3 wt % La 2 O 3 is obtained.
- the ultrafine tungsten powder containing trace rare earth lanthanum oxide is compression molded using mold pressing.
- the pressing molded compaction is subjected to pre-sintering and then high temperature sintered at 1950 ⁇ for 2 h and W-0.3 wt % La 2 O 3 material is obtained, its density is above 99.1%, its microstructure is uniform and very fine, average grain size is less than 8 microns.
- This materials can bear 200 MW/m 2 high heat flux loading without surface crack appearing.
- the coprecipitated coating particle colloidal is spray-dried at 400 ⁇ , spray drying nozzle rotating speed is 25000 revolutions per minute, forming tungsten and rare earth cerium oxide compound precursor powder.
- the precursor powder is then calcined at 400 ⁇ for 2 h. After deaggregation and sieving, the calcined powder is two-step hydrogen reduced at 600 ⁇ for 2 h subsequent with 800 ⁇ for 2 h, ultrafine tungsten powder containing 0.5 wt % CeO 2 is obtained.
- the ultrafine tungsten powder containing trace rare earth cerium oxide is compression molded using cold isostatic pressing.
- the pressing molded compaction is subjected to pre-sintering and then high temperature sintered at 1950 ⁇ for 4 h and W-0.5 wt % CeO 2 material is obtained, its density is above 99.3%, its microstructure is uniform and very fine, average grain size is less than 8 microns.
- This materials can bear 200 MW/m 2 high heat flux loading without surface crack appearing.
- the coprecipitated coating particle colloidal is spray-dried at 450 ⁇ , spray drying nozzle rotating speed is 25000 revolutions per minute, forming tungsten and rare earth yttrium and lanthanum oxide compound precursor powder.
- the precursor powder is then calcined at 400 ⁇ for 3 h. After disaggregation and sieving, the calcined powder is hydrogen reduced at 800 ⁇ for 3 h, ultrafine tungsten powder containing 0.3 wt % Y 2 O 3 +0.3 wt % La 2 O 3 is obtained.
- the ultrafine tungsten powder containing trace rare earth yttrium and lanthanum oxide is compression molded using mold pressing.
- the pressing molded compaction is subjected to pre-sintering at 1000 ⁇ for 2 h and then high temperature sintered at 1920 ⁇ for 3 h and W-0.3 wt % Y 2 +3.0 wt % La 2 O 3 material is obtained, its density is above 99.4%, its microstructure is uniform and very fine, average grain size is less than 6 microns. This materials can bear 300 MW/m 2 high heat flux loading without surface crack appearing.
- the coprecipitated coating particle colloidal is spray-dried at 450 ⁇ , spray drying nozzle rotating speed is 30000 revolutions per minute, forming tungsten and rare earth yttrium+lanthanum+cerium oxide compound precursor powder.
- the precursor powder is then calcined at 500 ⁇ for 3 h. After deaggregation and sieving, the calcined powder is two-step hydrogen reduced at 600 ⁇ for 2 h subsequent with 800 ⁇ for 4 h, ultrafine tungsten powder containing 0.3 wt % Y 2 O 3 -0.3 wt %La 2 O 3 0.3 wt %CeO 2 is obtained.
- the ultrafine tungsten powder containing trace rare earth yttrium and lanthanum oxide is compression molded using mold pressing.
- the pressing molded compaction is subjected to pre-sintering and then high temperature sintered at 1950 ⁇ for 4 h and W-0.3 wt %Y 2 O 3 -0.3 wt %La 2 O 3 -0.3 wt %CeO 2 material is obtained, its density is above 99.1%, its microstructure is uniform and very fine, average grain size is less than 5 microns.
- This materials can bear 300 MW/m 2 high heat flux loading without surface crack appearing.
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Abstract
This invention relates to a preparation method of rare earth oxide dispersion strengthened fee grain tungsten materials, the mass percent of the rare earth oxide is of 0.1-2%, and the rest ingredient is W. Weigh soluble rare earth salt and tungstate, dissolve into water to made into 50-100 g/L of rare earth salt solution and 150-300 g/L of tungstate solution, respectively. Firstly, add trace alkali in rare earth salt solution to control pH in 7-8, then add organic dispersant and stir to form evenly suspended R(OH)3 particle colloid (R refers to rare earth element). Secondly pour the tungstate solution into the R(OH)3colloid, add trace acid to control pH in 6-7, then add organic dispersant and stir to form tungstic acid micro particles, which wrap around the colloidal particles, forming coprecipitation coating particle colloid. Thirdly, the coprecipitation coating particle colloidal is spray-dried, forming tungsten and rare earth oxide compound precursor powder. Alter that, ultrafine or nanoscale tungsten powder with particle size of 50˜500 nm is obtained through a process of calcination subsequent with hydrogen thermal reduction. Finally, the tungsten powder is subjected to ordinary compression molding and then conventional high temperature sintering. The trace rare earth oxide dispersion strengthened high performance fine grain tungsten materials prepared by this invention, its density is close to full density (98.5% or higher), its grain size is uniform and very fine (average in 5˜10 microns), and the rare earth oxides particles evenly distribute in tungsten intracrystalline or grain, boundary with particle size of 100˜500 nm.
Description
- The present application claims priority to the PCT application Ser. No. PCT/CN2014/088882, filed on Oct. 20, 2014, the disclosure of which is expressly incorporated by reference herein in its entirety.
- The invention relates to field of nanomaterials and powder metallurgy field, especially a preparation method of rare earth oxide dispersion strengthened fine grain tungsten materials by nano-composite technology.
- Tungsten has characteristics such as high melting point, high hardness, good high temperature strength, thermal conductivity, electrical conductivity, low thermal expansion coefficient low sputtering and plasma effect, does not react with H, low H+ retention, is a very important high temperature structural materials and functional materials and is widely used as a plasma facing material and divertor component material in the nuclear fusion field.
- Among the tungsten materials which have been put into application, pure tungsten material is a widely used, typical high temperature materials. At present powder high purification and grain boundary purification method are used to produce sintered pure tungsten material, which is then strengthened through large deformation process, tungsten grain size is about 100 microns, the ductile to brittle transition temperature (DBTT) is about 300˜350□, the recrystallization temperature is of 1300˜1350□ and room temperature tensile strength is more than 500 MPa, high temperature tensile strength at 1000□ is about 400 MPa. However, this material exists defects such as coarse grain, fiber microstructure, high DBTT, low recrystallization temperature, high brittleness. Adding a second phase particle to refine tungsten grain and to dispersion strengthen pure tungsten is an important direction of the current development. According to this, in the 2010 Chinese patent “A kind of preparation method of nanometer oxide dispersion strengthened ultrafine grain tungsten-based composite” (Patent number: ZL201010250552.X), Zhou et al used tungsten powder, Y2O3 or Y, sintering additives Ti as raw materials, adopt mechanical alloying method to prepare superfine solid solution alloying powder,, and then using the method of spark plasma sintering (SPS) to prepare rare-earth yttrium oxide dispersion strengthened tungsten material its relative density is 96˜99%, tungsten grain size is about 3 μm or less, it has good mechanical properties and thermal shock resistance. In addition, Kim et al in the 2009 article “the Fabrication of high temperature oxides dispersion strengthened tungsten composites by spark plasma sintering process”, Munoz et al in 2011 article “La2O3-reinforced W and W-V alloys produced by hot isostatic pressing” has also used mechanical alloying method to prepare tungsten and rare earth oxide composite powder, and used SPS or hot pressing method to prepare oxide dispersion strengthened tungsten materials, the results show that adding trace rare earth tungsten oxide can refine grain and improve strength and heat load resistance. in the Chinese patent “A preparation method of nanometer yttrium oxide dispersion strengthened tungsten alloy” (Application number: 201310123415.3), Guo et al improved the earlier described preparation methods, yttrium nitrate was dissolved in alcohol and then mixed with ammonium tungstate (APT) by ball milling, hydrogen reduction after drying, and then mixed with 0.1˜1% Ni as sinter activator, finally tungsten material with oxide dispersion distribution can be produced from high temperature sintering, its density is 18.28˜19.2 g/cm3.
- The above research fully shows that the advantages of rare earth oxides addition in refining tungsten grain and improve the mechanical properties and thermal shock performance. But there exist some problems in the preparation of above: using high-energy ball milling or mechanical alloying preparation powder is easy to produce heterogeneous component distribution and impurities, and SPS, hot-pressing sintering method is not suitable for the engineering of large scale preparation. And although Guo's method improve the oxide dispersion distribution uniformity in tungsten matrix, but Ni must be added as sinter activator, and Ni element in many fields, such as nuclear fusion, nuclear fission is forbidden to use, this will be greatly limit the application scope. This patent inventor in the former stage has applied for and received a Chinese invention patent “one kind of method of preparing ultrafine activated tungsten, powder (patent number: ZL201010049432.3)”, in this invention, the “sol spray crying—thermal reduction” technology was used to prepare ultrafine or nanometer activated tungsten powder, in which, any one or more trace activation elements such as Ni, Co, Fe was added. Compared with high-energy ball mill or mechanical alloying, powder composition produced by this invention distributes uniformly, and does not introduce impurity elements. But due to poor compatibility of tungsten and rare earth oxide on the surface of the particles, if sol spray drying method is directly used to prepare tungsten materials containing trace rare earth oxide, rare earth oxide particle dispersion strengthening effect for tungsten is very limited, leading to poor performance, so it is difficult to meet the application requirement of nuclear fusion.
- Invention contest:
- In order to solve the problems in the above method in the preparing high performance rare-earth oxide dispersion strengthened fine grain tungsten materials, the present invention adopts the heterogeneous precipitation—spray drying—calcining—thermal reduction—conventional sintering technology to prepare high performance rare-earth oxide dispersion strengthened fine grain tungsten materials, its density is close to full density (98.5% or higher), and the rare earth oxides particles evenly distribute in tungsten intracrystalline or grain boundary, its grain size is uniform and very fine (average in about 10 microns or less), with good room temperature and high temperature performance as well as high thermal loading shock resistance.
- A rare earth oxide dispersion strengthened fine grain tungsten material its character is that includes: rare earth oxides referred to any one or more of Y2O3, La2O3, or in CeO2, the mass percent of the rare earth oxide is of 0.1˜2%, and the rest ingredient is W.
- The above mentioned rare earth oxide dispersion strengthened fine grain tungsten material its character is that includes the following steps:
- (1) The-mass percent of the rare earth oxide is of 0.1˜2%, and the rest ingredient is W. Weigh soluble rare earth salt and tungstate, dissolve into water to made into 50˜100 g/L of rare earth salt solution and 150˜300 g/L of tungstate solution, respectively. Firstly, add trace alkali in rare earth salt solution to control pH in 7˜8, then add organic dispersant and stir to form evenly suspended R(OH)3 particle colloid (R refers to rare earth element). Secondly, pour the tungstate solution into the R(OH)3 colloid, add trace acid to control pH in 6˜7, then add organic dispersant and stir to form tungstic acid micro particles, which wrap around the colloidal particles, forming coprecipitation coating particle colloid. Thirdly, the coprecipitation coating particle colloidal is spray-dried at 350˜450□ forming tungsten and rare earth oxide compound precursor powder, which is then calcined at 300˜600□ for 1˜4 h. After deaggregation and sieving, the calcined powder is hydrogen reduced at 600˜850° C. for 2˜6 h, ultrafine or nanoscale tungsten powder with particle size of 50˜500 nm is obtained. Rare earth oxides referred to any one or more of Y2O2, La2O3, or in CeO2;
- (2) The ultrafine/nanoscale tungsten powder containing trace rare earth oxide prepared in step (1) is compression molded under 150˜300 MPa using mold pressing or cold isostatic pressing;
- (3) The pressing molded compaction is subjected to regular high temperature sintering in high temperature sintering furnace, sintering temperature is 1800˜2000□, holding time 1˜5 h, then dense high-performance rare earth oxide homogeneous dispersion strengthened fine grain tungsten materials are obtained.
- The described tungstate is ammonium metatungstate, ammonium paratungstate or ammonium tungstate.
- The described rare earth salts are nitrate, oxalate, carbonate, chloride or sulfate of Y, La or Ce.
- The described stirring speed is 1000˜5000 revolutions per minute.
- The described spray drying nozzle rotating speed is 20000˜30000 revolutions per minute.
- The described reaction dispersant are stearic acid, polyethylene glycol (PEG), area, N, N-dimethyl formamide, OP emulsifier, twain-20 or sodium dodecyl sulfate, the mass fraction of reaction dispersant is of 0.1˜1.5% of rare earth salt solution or tungstate solution.
- The described acid is hydrochloric acid (HCl), nitric acid (HNO3) or oxalic acid (H2C2O4), the described alkali is sodium hydroxide (NaOH), potassium hydroxide (KOH), or aqueous ammonia (NH3·H2O).
- The Invention compared with the existing methods of the preparation of tungsten oxide dispersion strengthened materials, its advantages are as follows:
- 1. Compared with the conventional high energy ball mill and mechanical alloying, adopt “heterogeneous precipitation—spray drying” adding rare earth oxide in tungsten matrix, heterogeneous precipitation improves the compatibility of tungsten and rare earth oxides particles surface, spray drying achieves the uniformity of composition, microstructure in powder and alloy, so rare earth elements in tungsten matrix distribute more uniform, and do not introduce impurities.
- 2. Compared with high energy ball mill and mechanical alloying, ultrafine tungsten composite powder containing trace rare earth oxides prepared by “heterogeneous precipitation—spray drying—calcining—hydrogen reduction” method has much higher sintering activity; The powder of this invention can reach more than 98.5% density sintered at 1800˜2000□ by conventional sintering, grain size for sintered body is about 5˜10 microns, and microstructure more evenly, excellent toughness at room temperature and high temperature.
- 3. The invention adopts the conventional sintering method preparation of rare earth oxide dispersion strengthened fine grain tungsten materials, the technological process is simple and suitable for engineering preparation.
- Concrete implementation way:
- The following examples further explains the invention, instead of limiting the invention.
- In the preparation of W-0.1 wt %Y2O3 of Y2O3 dispersion strengthening fine grain tungsten materials, for example.
- (1) First of all, according to the mass fraction of rare earth oxides, weigh and soluble rare earth salt and tungstate by quality proportion, namely take 1.02 g yttrium, nitrate, 411.27 g ammonium tungstate, respectively made into 50 g/L of rare earth salt solution and 150 g/L of tungsten salt solution.
- (2) Slowly drop ammonia with 10wt % concentration into yttrium nitrate solution, adjusting the pH to 7.2, and add 0.2 g PEG400 as dispersant, under the action of ultrasonic vibration and electric blender mixing, the rare earth salt and alkali reaction to form homogeneous suspension Y(OH)3 particle colloid; Then adding tungsten salt solution into the Y(OH)3 gel slowly drop oxalic acid with 10 wt % concentration, adjusting the pH to 6.5, and add 2 g PEG400 as dispersant, under the action of ultrasonic vibration and electric blender mixing to form tungstate micro particles, which precipitate and coat around the Y(OH)3 gel particles, eventually form colloidal coprecipitation coating particles.
- (3) Thirdly, the coprecipitated coating particle colloidal is spray-dried at 360□, spray drying nozzle rotating speed is 20000 revolutions per minute, forming tungsten and rare earth oxide compound precursor powder,
- (4) The precursor powder is then calcined at 350□ for 2 h. After desegregation and sieving, the calcined powder is hydrogen reduced at 780° C. for 4 h, ultrafine tungsten powder containing 0.1 wt % Y2O3 is obtained.
- (5) The ultrafine tungsten powder containing trace rare earth oxide is compression molded using mold pressing. The pressing molded compaction is subjected to pre-sintering and then high temperature sintered at 1950□ for 2 h and W-0.1 wt %Y2O3 material is obtained, its density is above 99.2%, its microstructure is uniform and very fine, average grain size is less than 10 microns. This materials can bear 200 MW/m2 high heat flux loading without surface crack appearing.
- In the preparation of W-0.3 wt % La2O3 of La2O3 dispersion strengthening fine grain tungsten materials, for example.
- (1) First of all, according to the mass fraction of rare earth oxides, weigh and soluble rare earth salt and tungstate by quality proportion, namely take 1.53 g lanthanum oxalate hydrate, 411.27 g ammonium tungstate, respectively made into 60 g/L of rare earth salt solution and 200 g/L of tungsten salt solution.
- (2) Slowly drop NaOH with 10 wt % concentration into lanthanum oxalate hydrate solution, adjusting the pH to 7.3, and add 0.3 g N,N-dimethyl formamide as dispersant, under the action of ultrasonic vibration and electric blender mixing, the rare earth salt and alkali reaction to form homogeneous suspension La(OH)3 particle colloid; Then adding tungsten salt solution into the La(OH)3 gel slowly drop HCl with 10 wt % concentration, adjusting the pH to 6.8, and add 1.5 g PEG400 as dispersant, under the action of ultrasonic vibration and electric blender mixing to form tungstate micro particles, which precipitate and coat around the La(OH)3 gel particles, eventually form colloidal coprecipitation coating particles.
- (3) Thirdly, the coprecipitated coating particle colloidal is spray-dried at 400□, spray drying nozzle rotating speed is 20000 revolutions per minute, forming tungsten and rare earth lanthanum oxide compound precursor powder.
- (4) The precursor powder is then calcined at 350□ for 2 h. After deaggregation and sieving, the calcined powder is hydrogen reduced at 780° C. for 4 h, ultrafine tungsten powder containing 0.3 wt % La2O3 is obtained.
- (5) The ultrafine tungsten powder containing trace rare earth lanthanum oxide is compression molded using mold pressing. The pressing molded compaction is subjected to pre-sintering and then high temperature sintered at 1950□ for 2 h and W-0.3 wt % La2O3 material is obtained, its density is above 99.1%, its microstructure is uniform and very fine, average grain size is less than 8 microns. This materials can bear 200 MW/m2 high heat flux loading without surface crack appearing.
- In the preparation of W-0.5 wt % CeO2 of CeO2 dispersion strengthening fine grain tungsten-materials, for example.
- (1) First of all according to the mass fraction of rare earth oxides, weigh and soluble rare earth salt and tungstate by quality proportion, namely take 2.1 g cerium carbonate, 409.6 g ammonium tungstate, respectively made into 70 g/L of rare earth salt solution and 220 g/L of tungsten salt solution.
- (3) Slowly drop KOH with 10 wt % concentration into cerium carbonate solution, adjusting the pH to 7.5, and add 0.3 g PEG400 as dispersant, under the action of ultrasonic vibration and electric blender mixing, the rare earth salt and alkali reaction to form homogeneous suspension Ce(OH)3 particle colloid: Then adding tungsten salt solution into the Ce(OH)3 gel, slowly drop HNO3 with 10 wt % concentration, adjusting the pH to 6.5, and add 2.3 g PEG400 as dispersant, under the action of ultrasonic vibration and electric blender mixing to form tungstate micro particles, which precipitate and coat around the Ce(OH)3 gel particles, eventually form colloidal coprecipitation coating particles.
- (3) Thirdly, the coprecipitated coating particle colloidal is spray-dried at 400□, spray drying nozzle rotating speed is 25000 revolutions per minute, forming tungsten and rare earth cerium oxide compound precursor powder.
- (4) The precursor powder is then calcined at 400□ for 2 h. After deaggregation and sieving, the calcined powder is two-step hydrogen reduced at 600□ for 2 h subsequent with 800□ for 2 h, ultrafine tungsten powder containing 0.5 wt % CeO2 is obtained.
- (5) The ultrafine tungsten powder containing trace rare earth cerium oxide is compression molded using cold isostatic pressing. The pressing molded compaction is subjected to pre-sintering and then high temperature sintered at 1950□ for 4 h and W-0.5 wt % CeO2 material is obtained, its density is above 99.3%, its microstructure is uniform and very fine, average grain size is less than 8 microns. This materials can bear 200 MW/m2 high heat flux loading without surface crack appearing.
- In the preparation of W-0.3 wt %Y2O3-0.3 wt % La2O3 dispersion strengthening fine grain tungsten materials, for example.
- (1) First of all, according to the mass fraction of rare earth oxides, weigh, and soluble rare earth salt and tungstate by quality proportion, namely take 1.52 g yttrium nitrate, 2.18 g lanthanum chloride, 409.2 g ammonium tungstate, respectively made into 80 g/L of mixed rare earth salt solution and 250 g/L of tungsten salt solution.
- (2) Slowly drop ammonia with 10 wt % concentration into yttrium nitrate and lanthanum chloride solution, adjusting the pH to 7.8, and add 0.4 g sodium dodecyl sulfate as dispersant, under the action of ultrasonic vibration and electric blender mixing, the rare earth salt, and alkali reaction to form homogeneous suspension Y(OH)3+ La(OH)3particle colloid: Then adding tungsten salt solution into the Y(OH)3+ La(OH)3 gel, slowly drop oxalic acid with 10 wt % concentration, adjusting the pH to 6.2, and add 3.0 g sodium dodecyl sulfate as dispersant, under the action of ultrasonic vibration and electric blender mixing to form tungstate micro particles, which precipitate and coat around the Y(OH)3+ La(OH)3 gel particles, eventually form colloidal coprecipitation coating particles.
- (3) Thirdly, the coprecipitated coating particle colloidal is spray-dried at 450□, spray drying nozzle rotating speed is 25000 revolutions per minute, forming tungsten and rare earth yttrium and lanthanum oxide compound precursor powder.
- (4) The precursor powder is then calcined at 400□ for 3 h. After disaggregation and sieving, the calcined powder is hydrogen reduced at 800□ for 3 h, ultrafine tungsten powder containing 0.3 wt % Y2O3+0.3 wt % La2O3 is obtained.
- (5) The ultrafine tungsten powder containing trace rare earth yttrium and lanthanum oxide is compression molded using mold pressing. The pressing molded compaction is subjected to pre-sintering at 1000□ for 2 h and then high temperature sintered at 1920□ for 3 h and W-0.3 wt % Y2 +3.0 wt % La2O3 material is obtained, its density is above 99.4%, its microstructure is uniform and very fine, average grain size is less than 6 microns. This materials can bear 300 MW/m2 high heat flux loading without surface crack appearing.
- In the preparation of W-0.3 wt %Y2O3-0.3 wt % La2O3-0.3 wt % CeO2 dispersion strengthening fine grain tungsten materials, for example.
- (1) First of all, according to the mass fraction of rare earth oxides, weigh and soluble rare earth salt and tungstate by quality proportion, namely take 1.85 g sulfuric acid yttrium, 0.8 g lanthanum nitrate, and 0.8 g cerium nitrate, 409 g ammonium tungstate, respectively made into 100 g/L of mixed rare earth salt solution and 300 g/L of tungsten salt solution.
- (2) Slowly drop NaOH with 10 wt % concentration into mixed rare earth salt solution, adjusting the pH to 8.0, and add 0.5 g twain-20 as dispersant under the action of ultrasonic vibration and: electric blender mixing, the rare earth salt and alkali reaction to form homogeneous suspension Y(OH)3+ La(OH)3+Ce(OH)3 particle colloid; Then adding tungsten salt solution into the Y(OH)3+La(OH)3+Ce(OH)3 gel, slowly drop HCl with 10 wt % concentration, adjusting the pH to 6.0, and add 4.0 g twain-20 as dispersant, under the action of ultrasonic vibration and electric blender mixing to form tungstate micro particles, which precipitate and coat around the Y(OH)3+ La(OH)3+ Ce(OH)3 gel particles, eventually form colloidal coprecipitation coating particles.
- (3) Thirdly, the coprecipitated coating particle colloidal is spray-dried at 450□, spray drying nozzle rotating speed is 30000 revolutions per minute, forming tungsten and rare earth yttrium+lanthanum+cerium oxide compound precursor powder.
- (4) The precursor powder is then calcined at 500□ for 3 h. After deaggregation and sieving, the calcined powder is two-step hydrogen reduced at 600□ for 2 h subsequent with 800□ for 4 h, ultrafine tungsten powder containing 0.3 wt % Y2O3-0.3 wt %La2O30.3 wt %CeO2 is obtained.
- (5) The ultrafine tungsten powder containing trace rare earth yttrium and lanthanum oxide is compression molded using mold pressing. The pressing molded compaction is subjected to pre-sintering and then high temperature sintered at 1950□ for 4 h and W-0.3 wt %Y2O3-0.3 wt %La2O3-0.3 wt %CeO2 material is obtained, its density is above 99.1%, its microstructure is uniform and very fine, average grain size is less than 5 microns. This materials can bear 300 MW/m2 high heat flux loading without surface crack appearing.
Claims (7)
1. A preparation method for rare earth oxide dispersion strengthened fine grain tungsten material, its character is that includes the following steps:
(1) The mass percent of the rare earth oxide is of 0.1˜2%, and the rest ingredient is W. Weigh soluble rare earth salt and tungstate, dissolve into water to made into 50˜100 g/L of rare earth salt solution and 150˜300 g/L of tungstate solution, respectively. Firstly, add trace alkali in rare earth salt solution to control pH in 7˜8, then add organic dispersant and stir to form evenly suspended R(OH)3 particle colloid (R refers to rare earth element). Secondly, pour the tungstate solution into the R(OH)3 colloid, add trace acid to control pH in 6˜7, then add organic dispersant and stir to form tungstic acid micro particles, which wrap around the colloidal particles, forming coprecipitation coating particle colloid. Thirdly, the coprecipitation coating particle colloidal is spray-dried at 350˜450□, forming tungsten and rare earth oxide compound precursor powder, which is then calcined at 300˜600□ for 1˜4 h. After deaggregatlon and sieving, the calcined powder is hydrogen reduced at 600˜850° C. for 2˜6 h, ultrafine or nanoscale tungsten powder with particle size of 50˜500 nm is obtained. Rare earth oxides referred to any one or more of Y2O3, La2O3, or in CeO2;
(2) The ultrafine/nanoscale tungsten powder containing trace rare earth oxide prepared in step (1) is compression molded under 150˜300 MPa using mold pressing or cold isostatic pressing;
(3) The pressing molded compaction is subjected to regular high temperature sintering in high temperature sintering furnace, sintering temperature is 1800˜2000□, holding time 1˜5 h, then dense high-performance rare earth oxide homogeneous dispersion strengthened fine grain tungsten materials are obtained.
2. According to the preparation method of rare earth oxide dispersion strengthened fine grain tungsten materials in claim 1 , its character is: the described tungstate is ammonium metatungstate, ammonium paratungstate or ammonium tungstate.
3. According to the preparation method of rare earth oxide dispersion strengthened fine grain tungsten materials in claim 1 , its character is: the described rare earth salts are nitrate, oxalate, carbonate, chloride or sulfate of Y, La or Ce.
4. According to the. preparation method of rare earth oxide dispersion strengthened fine grain tungsten materials in claim 1 , its character is: the described stirring speed is 10001˜5000 revolutions per minute.
5. According to the preparation method of rare earth oxide dispersion strengthened fine grain tungsten materials in claim 1 , its character is: the described spray drying nozzle rotating speed is 20000˜30000 revolutions per minute.
6. According to the preparation method of rare earth oxide dispersion strengthened tine grain tungsten materials in claim 1 , its character is: the described reaction dispersant are stearic acid, polyethylene glycol (PEG), urea, N,N-dimethyl formamide, OP emulsifier, twain-20 or sodium dodecyl sulfate, the mass fraction of reaction dispersant is of 0.1˜1.5% of rare earth salt solution or tungstate solution.
7. According to the preparation method of rare earth oxide dispersion strengthened fine grain tungsten materials in claim 1 , its character is: to control pH in step (1), the described acid is hydrochloric acid (HCl), nitric acid (HNO3) or oxalic acid (H2C2O4), the described alkali is sodium hydroxide (NaOH), potassium hydroxide (KOH) or aqueous ammonia (NH3·H2O).
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