EP2193002A1 - Membranes perméables à l'hydrogène, en un matériau composite métallique - Google Patents
Membranes perméables à l'hydrogène, en un matériau composite métalliqueInfo
- Publication number
- EP2193002A1 EP2193002A1 EP08801921A EP08801921A EP2193002A1 EP 2193002 A1 EP2193002 A1 EP 2193002A1 EP 08801921 A EP08801921 A EP 08801921A EP 08801921 A EP08801921 A EP 08801921A EP 2193002 A1 EP2193002 A1 EP 2193002A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- metal
- matrix material
- coating
- hydrogen
- particles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 115
- 239000002905 metal composite material Substances 0.000 title 1
- 229910052751 metal Inorganic materials 0.000 claims abstract description 196
- 239000002184 metal Substances 0.000 claims abstract description 196
- 238000000576 coating method Methods 0.000 claims abstract description 87
- 239000011248 coating agent Substances 0.000 claims abstract description 81
- 238000000034 method Methods 0.000 claims abstract description 81
- 239000001257 hydrogen Substances 0.000 claims abstract description 46
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 46
- 239000011159 matrix material Substances 0.000 claims abstract description 42
- 239000000843 powder Substances 0.000 claims abstract description 37
- 239000007789 gas Substances 0.000 claims abstract description 22
- 239000002131 composite material Substances 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims description 123
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 100
- 239000010955 niobium Substances 0.000 claims description 58
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 45
- 229910052758 niobium Inorganic materials 0.000 claims description 42
- 229910052763 palladium Inorganic materials 0.000 claims description 35
- 230000008569 process Effects 0.000 claims description 22
- 238000010899 nucleation Methods 0.000 claims description 19
- 230000006911 nucleation Effects 0.000 claims description 19
- 238000005530 etching Methods 0.000 claims description 18
- 238000001513 hot isostatic pressing Methods 0.000 claims description 17
- 238000000151 deposition Methods 0.000 claims description 13
- 230000008021 deposition Effects 0.000 claims description 12
- 238000000465 moulding Methods 0.000 claims description 11
- 238000009736 wetting Methods 0.000 claims description 11
- 239000012266 salt solution Substances 0.000 claims description 9
- 238000005229 chemical vapour deposition Methods 0.000 claims description 8
- 238000007906 compression Methods 0.000 claims description 8
- 230000006835 compression Effects 0.000 claims description 8
- 238000005240 physical vapour deposition Methods 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 5
- 229910052715 tantalum Inorganic materials 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 239000000446 fuel Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 238000007747 plating Methods 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 238000007772 electroless plating Methods 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 35
- 239000000463 material Substances 0.000 abstract description 34
- 239000000203 mixture Substances 0.000 abstract description 14
- 238000009792 diffusion process Methods 0.000 abstract description 6
- 238000003825 pressing Methods 0.000 abstract description 6
- 230000008859 change Effects 0.000 abstract description 4
- 238000009826 distribution Methods 0.000 abstract description 3
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 230000035699 permeability Effects 0.000 description 27
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 22
- 239000000243 solution Substances 0.000 description 21
- 238000012360 testing method Methods 0.000 description 18
- 230000035882 stress Effects 0.000 description 16
- 239000000126 substance Substances 0.000 description 15
- 239000010410 layer Substances 0.000 description 13
- 238000001878 scanning electron micrograph Methods 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 229910045601 alloy Inorganic materials 0.000 description 11
- 239000000956 alloy Substances 0.000 description 11
- 229910052786 argon Inorganic materials 0.000 description 11
- 238000000227 grinding Methods 0.000 description 10
- 150000002431 hydrogen Chemical class 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 239000012071 phase Substances 0.000 description 9
- 239000012255 powdered metal Substances 0.000 description 9
- 239000002243 precursor Substances 0.000 description 9
- 239000012298 atmosphere Substances 0.000 description 8
- 150000002739 metals Chemical class 0.000 description 8
- 239000012466 permeate Substances 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000011261 inert gas Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 238000005245 sintering Methods 0.000 description 7
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 6
- 230000003628 erosive effect Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910021124 PdAg Inorganic materials 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 230000036961 partial effect Effects 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- 238000004544 sputter deposition Methods 0.000 description 5
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000002826 coolant Substances 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910001252 Pd alloy Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005275 alloying Methods 0.000 description 3
- 239000002775 capsule Substances 0.000 description 3
- 239000010432 diamond Substances 0.000 description 3
- 229910003460 diamond Inorganic materials 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 3
- 238000010310 metallurgical process Methods 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000003870 refractory metal Substances 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 101150003085 Pdcl gene Proteins 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000007771 core particle Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000010297 mechanical methods and process Methods 0.000 description 2
- 238000010606 normalization Methods 0.000 description 2
- 238000011022 operating instruction Methods 0.000 description 2
- 150000002940 palladium Chemical class 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000007788 roughening Methods 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000007669 thermal treatment Methods 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical class OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 229910001257 Nb alloy Inorganic materials 0.000 description 1
- 229910021120 PdC12 Inorganic materials 0.000 description 1
- 241000233805 Phoenix Species 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000002925 chemical effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000110 cooling liquid Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229910001090 inconels X-750 Inorganic materials 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000000462 isostatic pressing Methods 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000320 mechanical mixture Substances 0.000 description 1
- 230000005226 mechanical processes and functions Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 150000001457 metallic cations Chemical class 0.000 description 1
- 238000007431 microscopic evaluation Methods 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012465 retentate Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/022—Metals
- B01D71/0221—Group 4 or 5 metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0041—Inorganic membrane manufacture by agglomeration of particles in the dry state
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0041—Inorganic membrane manufacture by agglomeration of particles in the dry state
- B01D67/00411—Inorganic membrane manufacture by agglomeration of particles in the dry state by sintering
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0076—Pretreatment of inorganic membrane material prior to membrane formation, e.g. coating of metal powder
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/022—Metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/022—Metals
- B01D71/0223—Group 8, 9 or 10 metals
- B01D71/02231—Palladium
-
- 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
- B22F1/17—Metallic particles coated with metal
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/501—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/219—Specific solvent system
- B01D2323/225—Use of supercritical fluids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/30—Chemical resistance
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0405—Purification by membrane separation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12014—All metal or with adjacent metals having metal particles
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12181—Composite powder [e.g., coated, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12479—Porous [e.g., foamed, spongy, cracked, etc.]
Definitions
- the invention relates to hydrogen permeable membranes which separate hydrogen from gas mixtures by selective diffusion through a membrane while blocking the diffusion of other gas components through the membrane.
- the invention relates to the possible use of the membrane according to the invention in membrane reactors for hydrogen separation.
- Hydrogen can be used as a clean fuel to drive numerous aggregates of different sizes from the gas turbine to power generation to the smallest fuel cell. It is also possible to use hydrogen to drive automobiles, ships and submarines. Furthermore, large quantities of hydrogen are used in the chemical and petrochemical industry. In particular, in the chemical industry can be carried out by the use of hydrogen-permeable membranes, the purification of hydrogen. Furthermore, such membranes may be e.g. be used to shift the equilibrium in Hyd ⁇ réelles- and Dehyd ⁇ réellesre hopeen. Highly pure hydrogen is also needed in the semi-alloy industry, so that hydrogen-permeable membranes can also be used here. In the nuclear industry, membranes are used to separate hydrogen isotopes, helium, and other components.
- Metal membranes are characterized by a significantly higher selectivity for the field of hydrogen separation compared to other membrane materials such as ceramic, glass or polymer. At the same time, the metal membranes also have increased thermal stability.
- the membranes used for hydrogen separation often consist of palladium, which has a high hydrogen storage capacity even at room temperature and low hydrogen pressures. Because of these advantages, the Pd based membranes have been extensively studied and the state of the art has been reviewed in various reviews (A. Dixon, Int. J. Chem. Reactor Eng., 1, 2003, R6). However, the initially developed Pd Fohenmembranen could be produced only up to a thickness of about 75 microns usually. At this thickness, however, the permeability is insufficient. For this reason, Pd layers were applied to ceramic bodies, as described, for example, by Zhao et al. (Catal. Today, 1995, 25, 237).
- Pd As an alternative to Pd offer the so-called refractory metals tantalum, vanadium or niobium, because they have a significantly higher hydrogen permeability and are cheaper than Pd or Pd alloys.
- a direct use of these metals as hydrogen-permeable membranes fails due to their lack of chemical resistance, especially by oxidative attack in an oxygen-containing atmosphere.
- the oxides formed on the metal surface act as a diffusion barrier and thus prevent hydrogen transport through the membrane.
- DE10057161C2 (Heraeus) describes the preparation of a metallic membrane for hydrogen separation, for example by coating a niobium sheet with palladium on both sides, wherein a 50 ⁇ m thick palladium foil is plated on a 2 mm thick niobium sheet.
- a high-temperature sintering at 1400 ° C. produces a targeted Pd / Nb alloy over the entire film thickness (85% Pd / 15% Nb). Before use, the film is heated in a hydrogen atmosphere to remove oxides.
- Such a membrane was also produced by means of a palladium sputtering layer and with an alloy of Nb and Zr.
- further publications on such membranes are known, which differ only in the method of application of the Pd protective layer.
- US Pat. No. 5,149,420 (Buxbaum and Hsu) describes methods for coating Group IVB and VB metals, such as niobium, vanadium, zirconium, titanium and tantalum, with palladium from aqueous solution.
- the solution was carried out by a material according to main claim 1, and by a method for its preparation according to the main claim. 7
- such a metal matrix Mate ⁇ al can prevent complete oxidation of the molding produced therefrom (eg a membrane) and that this at the same time compared to a conventionally coated Metallfohe a higher mechanical stability by a more homogeneous stress distribution in the change in volume of the metallic phases as a result of hydrogen uptake or thermal expansion.
- the hydrogen permeability of a metal is the value K 0 , calculated in relation to a membrane of the metal of an area A,
- Thickness 1 with a hydrogen flux in moles across the membrane of Q 11- , at a
- Membrane surface permeates p F and a hydrogen partial pressure on the side of the membrane from which the permeating hydrogen exits p P. This is preferably greater than
- Chemically stable in the context of the invention is a substance which does not undergo chemical bonding with other atoms or molecules under the conditions of use envisioned for the invention with another substance.
- Chemical bond in the context of this invention refers to a covalent and / or ionic bond.
- a special form of chemically stable referred to in the present invention the term oxidation resistant. This here denotes a chemically stable substance, which does not undergo any covalent bonding with oxygen, in particular under the uses conceivable according to the invention.
- metal 1 in the metal matrix material according to the invention is a metal, or an alloy, or an intermetallic phase or a mixture thereof, which can take up hydrogen and has a higher permeability with respect to hydrogen than metal 2.
- metal 1 is a metal from the group of refractory metals.
- it is one of the metals such as niobium, vanadium, tantalum or a mixture (alloys) of these. Very particular preference is given to niobium.
- average particle sizes of from 0.1 to 1000 ⁇ m are preferred. Particularly preferred are average particle sizes of 1 to 500 microns, particularly preferred are average particle sizes of 10 to 300 microns.
- Metal 2 in the metal matrix material according to the invention is preferably an oxidation-resistant metal.
- Particularly preferred metal 2 is one of the list: palladium, platinum, nickel, cobalt, gold, iron, rhodium, iridium, titanium, hafnium, zirconium or an alloy of said metals and / or an alloy with niobium, vanadium and tantalum.
- metal 2 Particularly preferred for metal 2 are palladium and its alloys, since they are resistant to the formation of hydrides and Oberfiumbleenoxidation and have a particularly high H 2 permeability.
- Palladium alloys can be used particularly preferably with alloying partners of at least one metal from groups IB, IVB, VB or VLB of the periodic table.
- metal 2 is also a non-hydrogen embrittling alloy such as "Nb 1% Zr, Nb 10 Hf 1 Ti”, Vanstar (Trademark) and V15Cr5Ti.
- a metal matrix material according to the invention or a molded article produced therefrom has a porosity of less than 1%.
- Another object of the present invention is a method by which the metal-matrix material according to the invention can be produced.
- the process according to the invention for producing a metal-matrix material according to the invention in this case comprises at least the following steps:
- FIG. 1 An exemplary, schematic production by means of the method is shown in FIG.
- metal 1 comprises the metals and / or alloys specified in the metal matrix material according to the invention as metal 1 and is preferably a powder.
- the selection of powders of metal 1 of the method according to the invention is usually carried out on the basis of the parameters particle size, purity and porosity and target properties of the metal matrix material with respect to the mass fraction of metal 1 to be achieved in the resulting metal matrix material.
- Porosity is in terms of the invention a value expressed in percent. Calculated by
- Density (total) is in this case that value which is obtained by dividing the weighted mass of the particle, or of the shaped body, or of the metal-matrix material according to the invention by the measured volume of particles or moldings, or of metal-matrix material according to the invention. For particles, this is an average over a set of particles in a powder.
- Measuring a volume is done by measuring the external dimensions and calculating them.
- Density material is the specific density of a substance as a property of matter; or, in the case of mixtures (alloys), the resulting density, determined by proportionate addition of the specific densities of the components of the mixture (alloy) contained in particles or moldings or metal-matrix materials.
- average particle sizes of 0.1 to 1000 ⁇ m are preferred. Particularly preferred are average particle sizes of 1 to 500 microns, particularly preferred are average particle sizes of 10 to 300 microns.
- the purity of metal 1 is usually from 98% to 99.99%, preferably from 99.8% to 99.99%.
- metal 1 relative to metal 2 on the resulting metal-matrix material it is preferred to use nonporous metal 1 having a high mean particle diameter, within the limits given above. Is a lower one
- porous metal 1 having a small mean particle diameter within the limits given above.
- a pretreatment according to step 1 of the method according to the invention is desirable, then this can preferably be effected by one or a combination of the methods etching, nucleation of metal 2 to metal 1, and mechanical rounding. Particularly preferred in this case is a pretreatment which uses the methods of etching, mechanical rounding and / or nucleation of metal 2 on metal 1.
- the method of etching is desirable as a pretreatment, this can preferably be done by using an etchant selected from the group of acids and / or alkalis. Particularly preferred for this purpose, for example, as acids HCl, H 2 SO 4 , HNO 3 , H 3 PO 4 , and as the alkali NaOH. Further preferably, the etching is carried out at elevated temperature. In this case, temperatures between 80 ° C. and 150 ° C. are particularly preferred.
- This process step is advantageous because an etching leads to a chemical attack on the material surface.
- a cleaning effect can also be a roughening of the
- Particle surface can be achieved, which can lead to an increase in the particle surface, which has the possibly desired higher mass fraction of metal 2 relative to metal 1 on the resulting metal-matrix material result. Furthermore, the roughening can lead to a better behavior of metal 1 and / or metal 2 in the subsequent, inventive process step 2, insofar as that more homogeneous coatings can be obtained. Furthermore, it may be desirable to smooth sharp edges and / or scaly ones
- SEM images (eg with the device SFEGSEM Sirion 100 T or ESEM Quanta 400 T from the company FEI according to manufacturer's operating instructions) allow a control of the effect of the etching.
- the method of nucleation of metal 2 on metal 1 is desirable as a pretreatment, this may be, for.
- Example by the embodiments chemical vapor deposition, physical vapor deposition or wetting with a metal-2-salt solution are made possible.
- both embodiments of the chemical vapor deposition include the use of a precursor of metal 2 and the use of a reactant.
- the precursor preferably comprises an organometallic or inorganic compound of the metal 2 which is vaporizable and thermally stable under evaporation conditions.
- Particularly preferred are compounds containing metal 2 from the series: Palladiumdichlo ⁇ d, Pdacac 2 , Pd (hfac) 2 , pad (allyl) 2 , Pd (Me allyl) 2 , Pd (Me allyl) 2 , CpPd (allyl), Pd (allyl ) (hfac), Pd (Me allyl) (hfac), PdMe 2 (PMe 3) ;,, PdMe 2 (PEt 3); ,, Pd (acetate) 2, Pd (C 2 H 4) 2 and PdMe 2 ( tMEDA).
- reducing or oxidizing gases e.g. Hydrogen as reducing, or oxygen used as oxidizing gas.
- the single-stage vapor deposition preferably comprises the steps:
- the two-stage chemical vapor deposition preferably comprises the steps:
- the conversion of the precursor of metal 2 is preferably carried out by elevated temperature, more preferably by temperatures of 0-1000 0 C, most preferably by temperatures of 10 to 900 0 C and particularly preferably by temperatures of 20 to 600 0 C.
- a plasma-assisted evaporation used under high vacuum conditions, so that in particular preferably atoms or molecules containing metal 2 by the action of physical mechanisms - such as the supply of thermal energy or impulse transfer by bombardment with high energy particles - are transferred to the gas phase and then condensed in solid form on the substrate ,
- the wetting according to step 1 is carried out so that the powdered metal 1 is completely immersed in a metal 2 - salt solution.
- This is particularly preferably carried out at elevated temperatures. Elevated temperatures preferably comprise 0-300 0 C, more preferably 10-250 0 C and particularly preferably 20-200 0 C.
- the aftertreatment preferably comprises the complete removal of the solvent under reduced pressure and, if appropriate, elevated temperature, with constant movement of the pulverulent metal 1 with metal 2 salt now present on it.
- Increased temperature here preferably comprises 200 ° C. to 700 ° C., particularly preferably 500 ° C.
- wetting / aftertreatment steps are repeated several times with the same or different salt solutions of metal 2.
- the reduction preferably comprises the treatment of the metal 2 wetted particles of metal 1 in an oven of 200 0 C to 700 0 C, preferably at about 500 0 C under reductive conditions.
- Reductive conditions include, for example, a hydrogen atmosphere.
- the reduction of the deposited metal 2 salt leads to the formation of metal 2 nuclei on the surface, which leads to an improvement of the coating according to step 2 of the method according to the invention.
- step 1 of the method according to the invention by mechanical rounding is desirable, then this is preferably carried out so that the preferably powdered metal 1 of the method according to the invention after mechanical rounding comprises a powder with particles having a sphericity near 1.
- a sphericity close to 1 is advantageous since, for reasons of symmetry, such particles can be coated more homogeneously in accordance with step 2 of the method according to the invention and a more homogeneous coating enables better delimitation of the metal 1 regions in the metal-matrix structure resulting from the method according to the invention.
- this preferably comprises a sphericity of 0.25-1, more preferably 0.5-1, more preferably 0.75-1.
- round off the particles are chemical (e.g., etching) or physical (e.g., erosion) methods or combinations thereof.
- suitable physico-mechanical methods systems can be considered in which the particles are either deformed to round off or in which the particles are rounded off by breaking off parts of the particles on the surface and the dust resulting from mechanical stress is properly dispersed and the rounded particles is separated.
- Methods for the physical-mechanical rounding of particles in the preferably powdered metal 1 of the method according to the invention include those which provide high stresses for metals and can be inertized to prevent the oxidation of emerging surfaces and usually operated cooled.
- LSM50 As an example of a e.g. suitable spiral jet mill is called LSM50, Bayer.
- the mill can usually be operated under argon atmosphere with argon as the grinding gas at 5 to 10 bar, preferably at 6 to 8 bar pre-pressure and 200 to 800 g / h, preferably 300 to 500 g / h throughput.
- the hybridizer type NHS-O from the company. Nara is called, in which the particles of metal 1 usually in a with Nitrogen inertized and cooled machine can be claimed at a speed of 8000 rev / min to 12000 rpm for 1 to 10 min.
- the classifier speed of the mill for separating the ultrafine particles is usually 5,000 to 20,000 rpm, preferably 8,000 to 15,000 rpm.
- liquid media in which the physico-mechanical rounding takes place are, for example, liquid nitrogen or supercritical media (scCO 2 , etc.) which, on the one hand, largely avoid the contact of surfaces with oxygen and, on the other hand, optionally disperse any separated fines.
- the particles of the powdered metal 1 of the inventive method can also be processed in other conventional technical systems for the rounding of particles, preferably granules.
- Preferred systems are then rotating plates with static wall in batch or Konti operation (Shäronizer, Fa.- Fuji Paudal) or annular gap systems with rotating inner and / or outer ring (eg Nebulasizer, Fa. Nara), and systems containing the particles cutting stress, wherein a suitable hardness ratio between the particles and the Schneidtechnikzug and a suitable order of particle size of the powdered metal 1 is particularly preferred.
- step 2 of the method according to the invention for producing a metal matrix material according to the invention coating methods from the series of mechanical coating, electroless deposition, electrochemical coating, chemical vapor deposition (as described above) and physical vapor deposition (as already described) can be used.
- Preferred variants of step 2 of the inventive method are electroless deposition and mechanical coating.
- metal 2 preferably comprises a powder with high purity and a particle size matched to the particles of metal 1 present in the preferably pulverulent state.
- the purity of metal 2 is then preferably from 99.8% to 99.999%, more preferably from 99.85% to 99.999%, most preferably from 99.9% to 99.999%.
- the particle sizes of the preferably powdery particle of metal 2 are preferably in a size ratio in which they are finer than the particles in the preferably powdered metal 1. Especially a powder of metal 2 with particles that at least a factor of 10 smaller than the preferred particles of the powder of metal 1. Especially preferred are powders of the metal 2, which comprise particles in the sub- ⁇ m.
- the mechanical coating comprises a purely mechanical mixture of the above-mentioned preferred powders of metals 1 and 2 in order to achieve a suitable mixture or coating by adhesive forces.
- Preferred devices for such a mechanical coating are 1-D free-fall mixers (e.g., Röhnrad mixers, drum mixers, container mixers, twin-cone mixers, trouser mixers, etc.) or 2-D / 3-D tumble mixers (e.g., Turbula mixers).
- 1-D free-fall mixers e.g., Röhnrad mixers, drum mixers, container mixers, twin-cone mixers, trouser mixers, etc.
- 2-D / 3-D tumble mixers e.g., Turbula mixers
- Particularly useful devices are mixers with rotating internals and rigid mixing vessels (single shaft horizontal mixers (eg plowshare mixers) or two-shaft horizontal mixers (eg multi-flow centrifugal mixers) and single-shaft vertical mixers (eg intensive mixer for mixed granulation) or two-shaft vertical mixers (eg twin-shaft screw mixers) or rigid internals and rotary mixing vessels or combinations thereof (eg Eirich mixers) All such mixers may be equipped with additional fast rotating mixing tools in addition to the main mixer shaft.
- single shaft horizontal mixers eg plowshare mixers
- two-shaft horizontal mixers eg multi-flow centrifugal mixers
- single-shaft vertical mixers eg intensive mixer for mixed granulation
- two-shaft vertical mixers eg twin-shaft screw mixers
- rigid internals and rotary mixing vessels or combinations thereof eg Eirich mixers
- a powder mixture having a suitable particle size ratio is charged and the machine is operated at a suitable product fill level of suitable speed, stress duration and cooling so that the core and coating particles come into contact in the internal centrifugal-based cycle flow and the coating particles are mechanically fixed on the core particles by forces from particle-particle contacts or particle-wall contacts.
- An alternative embodiment of the coating of the particles, preferably of the metal powder 1, comprises the electroless deposition.
- this comprises the electroless deposition of metal 2 from the liquid phase onto the particles of the metal 1 preferably present as powder.
- the method preferably comprises at least the steps:
- the coating solution according to step 1 comprises a solvent and at least one precursor.
- the releasable form of metal 2 is preferably a metastable metal salt of metal 2 or a metal complex containing metal 2 or both.
- the solvent used for the coating solution is preferably water or methanol or a mixture of both.
- the coating solution according to step 1 comprises a hydrazine hydrate solution in solvent which preferably contains this in a concentration of 0.1-50% by weight and more preferably of 2-35% by weight.
- the execution of step 2 is preferably carried out by stirring particles of metal 1 in the coating solution.
- step 3 is preferably carried out for a long time under elevated temperature.
- the longer time preferably comprises a period of 1 minute to 24 hours, more preferably between 10 minutes and 6 hours.
- the elevated temperature preferably comprises between 10 0 C and 200 0 C, more preferably between 20 0 C and 150 0 C.
- the deposition is carried out by autocatalytic chemical reduction of the preferably releasable form of metal 2 without applying a voltage.
- This method is advantageous because hereby metal layers can be applied to almost any workpiece geometry. Furthermore, it is particularly cost-effective, since it dispenses with the use of additional energy and requires only a small amount of equipment.
- the effect of the method can be suitably controlled by SEM mounting (FEI, type ESEM Quanta 400 T according to the manufacturer's instructions) or by ESCA analyzes (Ametek, type EDAX Phoenix according to the operating instructions of the manufacturer).
- a composite metal powder whose particles have a mean diameter d50 of 1-10,000 .mu.m, preferably 10-1000 .mu.m, more preferably 30-300 microns and their layer thickness of the coating with metal 2 0.1-100 ⁇ m, preferably 0.1-10 ⁇ m, more preferably 0.2-5 ⁇ m.
- step 3 of the process according to the invention for producing a metal matrix material according to the invention the composite metal powder is pressed to form a so-called pressure.
- step 2 The processing of the composite metal powder obtained according to the invention in step 2 to form the metal matrix material according to the invention according to step 3 of the method according to the invention is carried out, for example. after one or more powder metallurgical processes. These include pressureless or pressurized compression and are performed at room temperature or higher temperature. After compaction, a heat treatment (sintering) may optionally follow in step 3.
- Pressure-less powder metallurgical processes include, for. As the pouring (eg filters), shaking or vibration and Schlickergie. Pressured powder metallurgical processes include, for. For example, densification by single or multi-sided static pressure in dies with upper and lower punches, sintering, (hot) isostatic pressing (HIP), extrusion and rolling.
- step 3 of the process according to the invention comprises pressurized pressing, which is particularly preferably carried out at elevated temperature. Especially preferred is hot isostatic pressing.
- Preferred compressive strengths of the preferred pressurized pressing method according to step 3 in this case include 1000 to 2500 N / mm 2 , more preferably 400 to 2000 N / mm 2 , most preferably from 500 to 1800 N / mm 2 .
- Preferred temperatures include temperatures of 10- 1000 0 C and more preferably temperatures of 20-750 ° C.
- a particularly preferred variant of step 3 of the process according to the invention is obtained by carrying out the preferred variants under an inert atmosphere such as. Argon.
- step 3 of the method according to the invention is obtained if the possibly still porous sintered body (often 10-15% porosity) is subsequently made free of pores by means of forming technology.
- a most preferred method is hot isostatic pressing (HIP) in an inert gas atmosphere such as argon.
- HIP hot isostatic pressing
- the components to be joined Under the influence of an isostatic pressure (the pressure medium is generally argon), the components to be joined are connected together at elevated temperature. The components maintain a solid state, it does not form a molten phase. Therefore, this so-called "hooking" is suitable for the cohesive joining of materials with different properties. Also, with this technique often multiple welds can be performed simultaneously.
- the high contact pressure ensures a plastic deformation of the surfaces and thus favors the running diffusion processes.
- the components are, for example, initially typically maintained at a starting pressure of 1 MPa and up to a set temperature of 500 0 C to 1200 0 C, preferably from 700 0 C to 1100 0 C, more preferably from 800 0 C to 1000 0 C heated with a temperature increase of 0.1 to 50 K / min, preferably 0.5 to 40 K / min, more preferably 5 to 15 K / min.
- the component is usually held at target pressure and set temperature for 1 to several hours.
- the erfmdungssiee metal matrix material in the form of a compact can be used according to step 4 of the inventive method for the production of moldings.
- these shaped bodies comprise sheets or membranes, particularly preferably gas-separating membranes. The use of these is also the subject of the present invention.
- step 4 of the process of the present invention may comprise different processes.
- known cutting or non-cutting shaping methods are applicable.
- Another possible method for producing sheets and membranes is rolling in all the technically known embodiments such as cold rolling and hot rolling. Also conceivable is a direct (hot) Verwalzung of metal powder at high temperature, optionally with temperature aftertreatment, to the target thickness of the membrane.
- Freewheeling, rolling and / or wire eroding are preferably used.
- the membrane surface is coated after step 4 in a further step with metal 2, to possibly exposed metal.
- Powder coating described methods such as electrochemical coating, electroplating, electroless deposition, chemical vapor deposition, physical vapor deposition, mechanical coating.
- the membranes according to the invention, obtained from step 4, usually have a membrane thickness of 0.01 ⁇ m to 10 mm, preferably 0.05 ⁇ m to 5 mm, particularly preferably 0.1 ⁇ m
- the hydrogen-permeable membrane layer is applied to a substrate, preferably to a porous substrate.
- Suitable substrates are, for example, porous oxides such as Al 2 O 3 , SiO 2 , ZrO 2 , TiO 2 or mixtures thereof.
- the membranes of the invention usually have a high permeability to hydrogen, which is significantly greater than the specific permeability of palladium.
- the membranes of the invention are characterized by a high stability. After 3 weeks of operation, no decrease in permeability was observed.
- FIG. 1 shows a schematic representation of the method according to the invention, wherein in step 1 a pretreatment, in step 2 a coating, in step 3 a pressing and in step 4 a forming is carried out.
- Example 2 shows in a) and b) each of the starting material used in Example 1 in scanning electron microscopic (SEM) recording, wherein in a) an 80-fold magnification and in b) a 300-fold magnification is shown.
- SEM scanning electron microscopic
- FIG. 3 shows an SEM image in which a nucleation according to Example 4 can be recognized.
- FIG. 4 shows an SEM image in which nucleation according to example 5 can be seen.
- Fig. 5 shows the result of a rounding in a fluidized bed counter-jet mill AFG100 according to Example 6 in transmitted light micrograph.
- Fig. 6 shows in a) and b) the result of a rounding in a spiral jet mill LSM50 according to Example 7, wherein in a) an SEM image and in b) a transmitted light micrograph is shown.
- FIG. 7 shows in a) and b) the result of a rounding by the Hosokawa Mechanofusion AM-Mini system according to Example 8, in each case in a transmitted-light micrograph at different light settings.
- Fig. 8 shows in a) and b) the result of a rounding by the system Nara Hybridizer according to Example 9 in SEM-recording, wherein in a) the system NHSO at 12000 U / min for 3 min. at 30 x g is shown and in b) the system NHSl at 8000 rpm for 3 min at 120 x g.
- FIG. 10 shows a SEM image of a coating of niobium particles with palladium by mechanical mixing according to Example 11.
- FIG. 11 shows a transmitted-light microscopic image of a coating of niobium particles with palladium by means of Hosokawa Mechanofusion AM Mini according to Example 12.
- FIG. 12 shows an SEM image of a coating of niobium particles with palladium by means of Nara Hybridizer NHS-O according to Example 13.
- FIG. 13 shows the result of a cold compression of Nb / Pd powder according to Example 14 in an SEM image.
- Fig. 14 shows the result of successive cold pressing and sintering of Nb / Pd powder according to Example 15 in an SEM photograph.
- FIG. 15 shows SEM images for producing a membrane by means of hot isostatic pressing (HIP) according to Example 16, in each case in 500 ⁇ magnification and recorded at 25 kV voltage;
- A Nb / Pd powder mixture, Pd unevenly distributed with residual pores;
- B Pd powder applied by Nara hybridizer, 10% Pd;
- C 5.4% Pd electroplated on rounded Nb particles;
- D 5.4% Pd electroplated on non-rounded Nb particles.
- Fig. 16 shows the structure of the test equipment for determining the hydrogen permeability using hydrogen (H2) and inert gases (IG) which can be combined to form the feed (F), the membrane (M), the actual test cell (T ), and a heater ( ⁇ T), so that a permeate (P) and a retentate (T) can be obtained.
- H2 hydrogen
- IG inert gases
- the measuring points shown in the circles show the type of measuring point in the upper line and their name in the lower line.
- the circle with the first row “TIC” and the second row “T2” indicate a temperature measuring point labeled T2, which indicates the measured temperature and which can control the temperature by means of its connection to the heating device ( ⁇ T).
- Examples 1 to 27 illustrate the present invention without being limited thereto.
- Example 1 educt selection
- Example 2 200 g of niobium powder according to Example 1, which was subjected to an etching step according to Example 2, was placed in a rotary evaporator, which was heated to 60 ° C by means of a water bath.
- Example 4 Wetting of niobium particles with thermal aftertreatment
- Example 5 Wetting of niobium particles with thermal aftertreatment and reduction
- 900 g of a niobium powder (as in Example 1, but with a particle size distribution of d 50 about 100 ⁇ m, d 90 about 200 ⁇ m, d ] 0 about 50 ⁇ m) were in a fluidized bed counter-jet mill (AFG100, Fa. Alpine). 2 h with 6 bar pre-pressure of the two side jets and 2 bar pre-pressure of the floor nozzle with nitrogen as grinding gas to avoid O 2 contact with the existing and emerging surfaces claimed. The classifier speed of the mill to remove the fines was 11,000 rpm.
- Figure 5 shows the rounding success of the stress in the fluidized bed counter-jet mill.
- Example 1 Rounding off the product from Example 1 (product amount 200 g) was achieved by the stress in a spiral jet mill (LSM50, Fa Bayer). The mill was operated in an argon-purged glove box with argon as the mill gas at 7.5 bar inlet pressure and 400 g / hr throughput.
- FIG. 6 shows the rounding result of the stress in the spiral jet mill.
- Mechanofusion AM-Mini, Fa. Alpine Hosokawa were 90 g of niobium particles according to Example 1, which were previously sieved to 100 microns by air jet sieving (type ALS 200, Fa. Hosokawa
- the product was cooled down before opening the machine.
- the rounded powder was sieved to 32 ⁇ m after the stress (type ALS 200, Hosokawa Alpine,
- FIG. 7 shows the
- the rounding of 100 g of niobium particles according to Example 1 was carried out in the Hybridizer system from Nara. The particles were cooled and stressed under inert gas at a speed of 8000 or 12000 rpm for 3 min. The rounding of the niobium particles in the scale-up of the hybridizer system are shown in FIG.
- Example 10 Coating of pretreated Nb particles by electroless deposition
- An acidic receiver solution was prepared by adding 20 ml of concentrated HCl solution (37%) to about 900 ml of deionized water. To this solution was added 10 g of PdCl 2 . Then, to 1 liter of the acidic PdCl 2 -solubilizing solution was added 120 ml of deionized water and 715 ml of ammonia solution (28% by weight). After 3 days of aging, 1.75 g of Na 2 EDTA salt were added to 25 ml of the solution thus prepared. The coating solution thus prepared and 15 g of niobium according to Example 1, which had been pretreated in accordance with Example 2 and Example 4, were added to a 250 ml stirred glass apparatus with glass stirrer.
- the stirred tank was heated to 30 0 C by means of a water bath. Subsequently, 10 ml of a 25 wt .-% hydrazine hydrate solution were added at a metering rate of 5 ml / h over a period of 2 h and then stirred for one hour at the same temperature.
- the coated niobium particles were washed, filtered and dried at 60 ° C. in a drying oven. The particles showed almost complete coverage.
- FIG. 9 shows the result of coating experiments according to this coating specification.
- Example 11 Intensive mixing as the simplest case for mechanical coating
- Example 1 The simplest case of a coating moderately rounded niobium polver according to Example 1 (LSM50, argon, 8.5 bar, 400 g / h) with ultrafine disperse palladium powder (manufacturer Ferro, type 3101, particle size 0.6-1.8 microns) in a laboratory vibration mill (type MM200, Retsch) for 1 hour at 30 Hz oscillation frequency in a 10 ml zirconia cup intensively mixed. For the mixture, 18 g of niobium powder and 2 g of palladium powder were used.
- FIG. 10 shows the purely mechanical coating of niobium particles with very finely dispersed palladium powder.
- Example 12 Mechanical Coating by Hosokawa Mechanofusion
- niobium particles rounded off in Example 8 in the Mechanofusion AM-Mini system were subsequently coated with very finely dispersed palladium in this system.
- about 95.5 g of rounded niobium particles were mixed with about 10.6 g ultrafine palladium powder and stressed in the cooled, inactivated system Mechanofusion AM-Mini at a speed of 3820 U / min for ten minutes.
- FIG. 11 shows the mechanical coating of niobium particles with very finely dispersed palladium powder in the Mechanofusion System.
- Example 9 The particles rounded off in Example 9 in the system Hybridizer NHS-O were subsequently coated with ultrafine disperse palladium in this system.
- about 27 g of rounded niobium particles were mixed with about 3 g of very finely divided palladium powder and subjected to stress in the cooled inerted system Hybridizer NHS-O at a speed of 12000 rpm for one minute.
- FIG. 12 shows the mechanical coating of niobium particles with very finely dispersed palladium powder in the hybridizer system.
- Example 14 Cold compression of metal powder by means of tablet press
- niobium powder was pressed in accordance with Example 1 in a tablet press.
- a porosity of approx. 5% by rearranging and deforming the particles with a pressure of up to approx. 1500 N / mm 2 .
- the gas tightness of these compacts could be increased by sintering.
- FIG. 13 shows an SEM image of the surface of the cold-pressed material.
- Example 15 Successive pressing with tablet press / sintering under argon:
- FIG. 14 shows an SEM image of the surface of the successively cold-pressed and sintered material.
- Example 16 HIPing a single membrane:
- Coatings were for this purpose in a steel capsule (diameter 25 mm) with a Tantalum foil filled as a separating layer between powder and steel and vacuum-sealed.
- the nominal temperature was first set at 10 K / min at 1 MPa pressure and held for 1 h.
- the pressure was then superimposed and the setpoint pressure was set at 4 MPa / min to 200 MPa (200 N / mm 2 ) and held for 2 h under simultaneous temperature action.
- pressure and temperature were run at the same rates as during heating or increasing the pressure.
- metallic moldings with a diameter of about 20 mm and a thickness of about 3 mm were removed without coolant.
- a metallic bond with a porosity of ⁇ 1% was achieved with the stated experimental setting.
- Nb material according to example 1 • Pd coating (including etching according to Example 2, nucleation according to Example 4) according to Example 10
- Figure 15 shows the matrix structure of the coated and then hot isostatically pressed products.
- niobium and palladium To produce a larger amount of the desired matrix material from niobium and palladium, approximately 250 g of a rounded and coated niobium powder were hot isostatically pressed. As in the previous example, the amount of material was filled into a 25 mm diameter capsule, then vacuum sealed and subjected to the same pressure and temperature process. After cooling, metallic moldings with a diameter of about 20 mm and a thickness of about 60 mm were removed without coolant. In the HIP process, a metallic bond with a porosity of ⁇ 1% was achieved with the stated experimental setting.
- the membranes prepared in Example 17 were uncoated on a standard lathe without the use of cooling liquid to avoid chemical effects on the surface and in particular in deeper layers of the membrane. During free rotation of the capsule material of the HIP process, a membrane thickness of about 1 mm and a diameter of about 20 mm was achieved. The membranes obtained were used for the determination of theoretical porosities and for gas-tightness tests.
- Example 19 sawing thin slices of the composite material by means of a diamond disk
- membranes were prepared from the composite material according to the invention by diamond saw (Labcut 1010 type, Agar Scientific Ltd., diamond disc 0.5 mm) of the bars produced in Example 20 by hot isostatic pressing separated from about 0.3 to 1.0 mm.
- Example 20 Wire eroding to achieve minimum material slice thickness without forming
- a membrane with a thickness of 1 mm and a diameter of 20 mm was placed in a 250 ml stirring apparatus of glass with glass stirrer. 50 ml of a coating solution according to Example 10 was added. The stirred tank was heated to 30 0 C by means of a water bath. 2 ml of a 25% strength by weight hydrazine hydrate solution were added at a metering rate of 5 ml / h. After Hydrazinhydratzugabe one hour at the same temperature was stirred. The coated niobium particles were washed, filtered and dried at 60 ° C. in a drying oven.
- Example 23 Coating by Sputtering / Physical Vapor Deposition
- the outer surface on which metallic niobium exuded without coating was coated with palladium prior to testing.
- the coating was carried out after grinding and polishing of the surface and a cleaning in an acetonic ultrasonic bath by means of sputtering with a sputter Ceater 208HV the company. Cressington.
- a current of 80 mA was set at a sputtering time of 100-200 s with the aim of a 100 nm thick layer thickness. Thickness measurement is done using quartz crystals calibrated on the sputtering material.
- Permeation experiments were performed in a test cell at up to 575 ° C.
- the test cell had a receptacle for flat, round membranes with a diameter of 20 mm.
- the Additional sealing was carried out by metallic O-rings made of Inconel X-750, the active membrane area is 2,0i + IO "4 m 2.
- the heating and temperature control was carried out via an electric heating jacket.
- the membrane temperature was in the core of the test cell with a thermocouple of the type Feed gas was supplied from compressed gas cylinders and was regulated by flow regulators type Brooks 5850.
- the flow diagram of the test apparatus is shown in Figure 16.
- the permeability was determined using a PdAg 25 membrane (palladium-silver alloy Pd: Ag 75: 25wt%; manufacturer: Alfa Aesar, membrane thickness: 0.25 mm, membrane area: l, 77 * 10 '4 m 2 , permeate pressure: 1 bar abs) sealed in the test cell and under inert gas argon flushing at 1 bar abs
- the inert gas (argon) was slowly replaced by hydrogen and kept under hydrogen atmosphere for a few hours
- an H 2 charge or an H 2 permeate flow was generated.
- the hydrogen flux m 3 / m 2 h
- the membrane permeability K 0 was obtained in mol * m / (m 2 * s * Pa 0 ' 5 ) according to the following formula:
- K 0 membrane permeability [mol-m / m 2 -s-Pa 0 ' 5 ]
- P P hydrogen partial pressure permeate side [Pa 0 ' 5 ]
- the membrane was run in the reverse approach sequence, ie the steps pressure release, inert gas (argon) conversion and cooling to room temperature followed
- Nb material according to example 1 particle size 80-150 ⁇ m
- Nb material analogous to Example 1 Particle size 80-150 ⁇ m
- Nb material according to Example 1 particle size 80-150 microns
- Pd coating according to example 10 (including etching according to example 2, nucleation according to example 4)
- the membrane permeability of the own new membranes is well above the membrane permeability of the commercial PdAg 2s membrane.
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Organic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Powder Metallurgy (AREA)
Abstract
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102007044918A DE102007044918A1 (de) | 2007-09-19 | 2007-09-19 | Wasserstoffpermeable Membranen aus metallischem Verbundwerkstoff |
PCT/EP2008/007345 WO2009036905A1 (fr) | 2007-09-19 | 2008-09-09 | Membranes perméables à l'hydrogène, en un matériau composite métallique |
Publications (1)
Publication Number | Publication Date |
---|---|
EP2193002A1 true EP2193002A1 (fr) | 2010-06-09 |
Family
ID=40121788
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP08801921A Withdrawn EP2193002A1 (fr) | 2007-09-19 | 2008-09-09 | Membranes perméables à l'hydrogène, en un matériau composite métallique |
Country Status (5)
Country | Link |
---|---|
US (1) | US20100247944A1 (fr) |
EP (1) | EP2193002A1 (fr) |
CN (1) | CN101861221B (fr) |
DE (1) | DE102007044918A1 (fr) |
WO (1) | WO2009036905A1 (fr) |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI549347B (zh) * | 2011-11-18 | 2016-09-11 | 博隆能源股份有限公司 | 使用粉末冶金術製造燃料電池之互連體之方法 |
EP2596851B1 (fr) | 2011-11-24 | 2017-08-16 | Samsung Electronics Co., Ltd | Membrane de séparation et appareil comprenant la membrane de séparation |
US9073007B2 (en) | 2012-02-15 | 2015-07-07 | Samsung Electronics Co., Ltd. | Separation membrane, hydrogen separation membrane including the separation membrane, and hydrogen purifier including the hydrogen separation membrane |
US8900345B2 (en) | 2012-03-19 | 2014-12-02 | Samsung Electronics Co., Ltd. | Separation membrane, hydrogen separation membrane including the separation membrane, and device including the hydrogen separation membrane |
DE102012109154B4 (de) * | 2012-09-27 | 2016-01-07 | Mahnken & Partner GmbH | Verfahren zur Gewinnung von Wasserstoff |
US9555376B2 (en) * | 2013-01-26 | 2017-01-31 | Adma Products, Inc. | Multilayer, micro- and nanoporous membranes with controlled pore sizes for water separation and method of manufacturing thereof |
CA3116407C (fr) * | 2013-03-15 | 2023-02-07 | President And Fellows Of Harvard College | Methode de mouillage de surface |
US10471511B2 (en) | 2013-11-25 | 2019-11-12 | United Technologies Corporation | Method of manufacturing a hybrid cylindrical structure |
CN103752821B (zh) * | 2014-01-24 | 2016-01-20 | 云南大学 | 一种制备金属微粉覆盖表面的导电复合微球材料方法 |
US10465295B2 (en) * | 2014-05-20 | 2019-11-05 | Alpha Assembly Solutions Inc. | Jettable inks for solar cell and semiconductor fabrication |
WO2015192166A1 (fr) | 2014-06-16 | 2015-12-23 | Commonwealth Scientific And Industrial Research Organisation | Procédé de production d'un produit en poudre |
KR102244851B1 (ko) * | 2014-06-24 | 2021-04-27 | 커먼웰쓰 사이언티픽 앤 인더스트리알 리서치 오거니제이션 | 촉매 멤브레인 반응기용 합금 |
US10590516B2 (en) * | 2014-06-24 | 2020-03-17 | Commonwealth Scientific And Industrial Research Organisation | Alloy for catalytic membrane reactors |
CN107008749A (zh) * | 2017-05-23 | 2017-08-04 | 常州大学 | 一种多相V‑Ti‑Ni氢分离合金膜片的制造方法 |
CN110257814A (zh) * | 2019-06-04 | 2019-09-20 | 中国船舶重工集团公司第七二五研究所 | 一种基于机械球磨涂覆技术的金属氧化物阳极制备方法 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2038556B (en) * | 1978-11-25 | 1983-02-16 | Matsushita Electric Ind Co Ltd | Porous tantalum anode for electrolytic capacitor |
US4450188A (en) * | 1980-04-18 | 1984-05-22 | Shinroku Kawasumi | Process for the preparation of precious metal-coated particles |
US5149420A (en) | 1990-07-16 | 1992-09-22 | Board Of Trustees, Operating Michigan State University | Method for plating palladium |
DE10057161C2 (de) | 2000-11-16 | 2003-08-21 | Heraeus Gmbh W C | Niob-Legierung und eine daraus hergestellte Wasserstoffpermeationsmembran |
DE10135390A1 (de) | 2001-07-25 | 2003-02-20 | Fraunhofer Ges Forschung | Metallische Lösungs-Diffusions-Membran sowie Verfahren zur Herstellung |
US7125440B2 (en) * | 2003-06-04 | 2006-10-24 | Bossard Peter R | Composite structure for high efficiency hydrogen separation and its associated methods of manufacture and use |
CN1628898B (zh) * | 2003-12-19 | 2012-08-29 | 雷敏宏 | 用于高纯度氢气纯化的支撑式钯膜的制备方法 |
US7771520B1 (en) * | 2006-09-06 | 2010-08-10 | Bossard Peter R | System and method for forming a membrane that is super-permeable to hydrogen |
-
2007
- 2007-09-19 DE DE102007044918A patent/DE102007044918A1/de not_active Withdrawn
-
2008
- 2008-09-09 US US12/679,038 patent/US20100247944A1/en not_active Abandoned
- 2008-09-09 WO PCT/EP2008/007345 patent/WO2009036905A1/fr active Application Filing
- 2008-09-09 CN CN2008801166505A patent/CN101861221B/zh not_active Expired - Fee Related
- 2008-09-09 EP EP08801921A patent/EP2193002A1/fr not_active Withdrawn
Non-Patent Citations (1)
Title |
---|
See references of WO2009036905A1 * |
Also Published As
Publication number | Publication date |
---|---|
WO2009036905A1 (fr) | 2009-03-26 |
US20100247944A1 (en) | 2010-09-30 |
CN101861221A (zh) | 2010-10-13 |
CN101861221B (zh) | 2013-03-27 |
DE102007044918A1 (de) | 2009-04-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2193002A1 (fr) | Membranes perméables à l'hydrogène, en un matériau composite métallique | |
DE10003982B4 (de) | Oxidbeschichtete feine Metallteilchen und Verfahren zu deren Herstellung | |
EP0326861B1 (fr) | Poudre métallique composite agglomérée, son procédé de préparation et son utilisation | |
CN1068264C (zh) | 制备金属复合粉末的方法 | |
EP3042727A1 (fr) | Composition contenant de fines particules d'argent, son procédé de production, procédé de production de fines particules d'argent et pâte contenant de fines particules d'argent | |
EP3598526A1 (fr) | Réseau de fibres métalliques, procédé de production d'un réseau de fibres métalliques électrode et batterie | |
CN111940750B (zh) | 一种合金粉体材料的制备方法 | |
EP1646465A2 (fr) | Procede de production de poudres fines metalliques, d'alliage et composees | |
WO2021058719A1 (fr) | Élément en mousse métallique contenant du cobalt et son procédé de production | |
CN106077695A (zh) | 一种高铜钨铜纳米复合粉末的制备方法 | |
US20160220933A1 (en) | Sintered fe-al based porous alloy material with high-temperature oxidization resistance and filtering elements | |
JP2008237945A (ja) | 水素分離膜 | |
EP0431165A1 (fr) | Materiau composite ceramique et son procede d'obtention | |
US11377358B2 (en) | Method for producing porous carbon material | |
DE10011104B4 (de) | Verwendung einer Amorphen Ni-Legierungsmembran zur Abtrennung/Dissoziation von Wasserstoff | |
EP3541552A1 (fr) | Procédé de fabrication d'un corps moulé poreux et corps moulé poreux | |
DE102007047874B4 (de) | Poröser Formkörper aus Metalloxiden und Verfahren zu seiner Herstellung | |
EP1379708B1 (fr) | Poudre de revetement a base de sous-oxydes de titane chimiquement modifies | |
DE102006005225B3 (de) | Titanwerkstoff und Verfahren zu seiner Herstellung | |
CN114875266A (zh) | 一种多孔FeCoNiCr均质固溶高熵合金及其制备方法 | |
JP2008212812A (ja) | 水素分離膜 | |
EP0443683B1 (fr) | Poudre d'alliage à base de nickel pour une anode poreuse pour une pile à combustible, méthode de préparation de la poudre et de l'anode, ainsi que l'anode obtenue et la pile à combustible | |
KR100707855B1 (ko) | 분말사출성형용 금속 미세입자 피드스톡의 제조방법 | |
WO2015042622A1 (fr) | Cible de pulvérisation cathodique cuivre-gallium | |
WO2019020214A1 (fr) | Procédé pour la préparation d'une couche à phase unique en composés intermétalliques |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20100419 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR |
|
AX | Request for extension of the european patent |
Extension state: AL BA MK RS |
|
RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: WOLF, AUREL Inventor name: WARSITZ, RAFAEL Inventor name: DAMMANN, ANDRE Inventor name: WEBER, RALPH Inventor name: KINTRUP, JUERGEN Inventor name: MLECZKO, LESLAW |
|
DAX | Request for extension of the european patent (deleted) | ||
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: BAYER INTELLECTUAL PROPERTY GMBH |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
|
18D | Application deemed to be withdrawn |
Effective date: 20150401 |