US3911194A - Method for forming pure metal or non-metal deposits - Google Patents
Method for forming pure metal or non-metal deposits Download PDFInfo
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- US3911194A US3911194A US41201673A US3911194A US 3911194 A US3911194 A US 3911194A US 41201673 A US41201673 A US 41201673A US 3911194 A US3911194 A US 3911194A
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- US
- United States
- Prior art keywords
- metal
- source
- substratum
- fluoride
- vapour
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- Expired - Lifetime
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 110
- 239000002184 metal Substances 0.000 title claims abstract description 110
- 238000000034 method Methods 0.000 title claims abstract description 65
- 229910052755 nonmetal Inorganic materials 0.000 title abstract description 18
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 29
- 239000011737 fluorine Substances 0.000 claims abstract description 12
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 17
- 239000010937 tungsten Substances 0.000 claims description 17
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims description 8
- 239000011733 molybdenum Substances 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- 229910001512 metal fluoride Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- WSWMGHRLUYADNA-UHFFFAOYSA-N 7-nitro-1,2,3,4-tetrahydroquinoline Chemical group C1CCNC2=CC([N+](=O)[O-])=CC=C21 WSWMGHRLUYADNA-UHFFFAOYSA-N 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052793 cadmium Inorganic materials 0.000 claims description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000012634 fragment Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910000792 Monel Inorganic materials 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910001026 inconel Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 229910052752 metalloid Inorganic materials 0.000 claims description 2
- 101100140581 Arabidopsis thaliana REF6 gene Proteins 0.000 claims 1
- 101000674742 Homo sapiens Transcription initiation factor TFIID subunit 5 Proteins 0.000 claims 1
- 101100528972 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) RPD3 gene Proteins 0.000 claims 1
- 102100021230 Transcription initiation factor TFIID subunit 5 Human genes 0.000 claims 1
- 150000002738 metalloids Chemical class 0.000 claims 1
- 238000000151 deposition Methods 0.000 description 25
- 150000002222 fluorine compounds Chemical class 0.000 description 13
- 239000007789 gas Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 230000008021 deposition Effects 0.000 description 11
- 150000002739 metals Chemical class 0.000 description 11
- 238000000576 coating method Methods 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 125000001153 fluoro group Chemical group F* 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 230000002542 deteriorative effect Effects 0.000 description 2
- -1 e.g. Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007792 gaseous phase Substances 0.000 description 2
- 238000005272 metallurgy Methods 0.000 description 2
- 150000002843 nonmetals Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000003870 refractory metal Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 229910015255 MoF6 Inorganic materials 0.000 description 1
- 229910019593 ReF6 Inorganic materials 0.000 description 1
- 229910004014 SiF4 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910010342 TiF4 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- WUUZKBJEUBFVMV-UHFFFAOYSA-N copper molybdenum Chemical compound [Cu].[Mo] WUUZKBJEUBFVMV-UHFFFAOYSA-N 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- RLCOZMCCEKDUPY-UHFFFAOYSA-H molybdenum hexafluoride Chemical compound F[Mo](F)(F)(F)(F)F RLCOZMCCEKDUPY-UHFFFAOYSA-H 0.000 description 1
- KFTNEILVDDUXGR-SECBINFHSA-N n-[(1r)-1-(4-bromophenyl)ethyl]-5-fluoro-2-hydroxybenzamide Chemical compound N([C@H](C)C=1C=CC(Br)=CC=1)C(=O)C1=CC(F)=CC=C1O KFTNEILVDDUXGR-SECBINFHSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- QHIRVZBLPRTQQO-UHFFFAOYSA-I pentafluorotungsten Chemical compound F[W](F)(F)(F)F QHIRVZBLPRTQQO-UHFFFAOYSA-I 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- YUCDNKHFHNORTO-UHFFFAOYSA-H rhenium hexafluoride Chemical compound F[Re](F)(F)(F)(F)F YUCDNKHFHNORTO-UHFFFAOYSA-H 0.000 description 1
- 239000010979 ruby Substances 0.000 description 1
- 229910001750 ruby Inorganic materials 0.000 description 1
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- NXHILIPIEUBEPD-UHFFFAOYSA-H tungsten hexafluoride Chemical compound F[W](F)(F)(F)(F)F NXHILIPIEUBEPD-UHFFFAOYSA-H 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
- C23C16/08—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metal halides
-
- 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
- Y10T428/30—Self-sustaining carbon mass or layer with impregnant or other layer
-
- 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
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
Definitions
- the present invention relates to a method for obtaining metal or metal-like coatings in the pure state from the high-valence corresponding fluorides.
- the positioning of the metal atom in the surface lattice of the receiver metal occurs very quickly.
- the adsorbed two fluorine atoms are capable of moving under the conditions of the experiment, and the desorption thereof, which proves to be one of the main factors governing the kinetics of the deposition, allows the metal surface to be permanently uncovered.
- Another method consists in reducing a fluoride by 1 means of hydrogen, and it also leads to good coatings,
- the excess hydrogen may alter the hydrogen/- gaseous fluoride ratio to the point of deteriorating the metal deposit, or even causing the vapour-deposition to stop.
- Too great a concentration of hydrofluoric gas in the vicinity of the substratum may, quite undesirably, lead to a reaction opposite to the desired one, viz. the recombination of the metal deposited in the fluoride state.
- the reduction method has therefore to be rejected whenever the geometry of the objects to be coated is complicated, or whenever it is desired to form deposits inside parts comprising many branches or, e.g., inside long and narrow tubes.
- the invention relates to a method for forming pure metal or non-metal deposits, said method consisting in introducing, in the vapour state, at least one metal or non-metal fluoride of higher valence into an enclosure containing at least one substratum to be coated and a source for providing the metal or non-metal to be deposited, heating said source in order that the higher valence fluoride is transformed, when contacting said source, into at least one sub-fluoride which evaporates, is condensed on the substratum and is transformed into fluorine and into the metal, or the non-metal, which constitutes the desired deposit.
- the fluorides of higher valence are fluoridizing and cannot be thermally decomposed until the metal is obtained. It is only by means of the reduction of these fluorides with hydrogen that a total chemical decomposition can be obtained.
- the sub-fluorides are not fluoridizing in general, and they can be thermally decomposed on a hot substratum in order to provide the metal directly.
- subfluorides and the thermal decomposition of same occur simultaneously.
- the formation of a sub-fluoride, having the general formula MF froma higher fluoride, having the general formula MF,,, and the metal M is carried out as follows:
- n and m being the valences of the elements and n being higher than m.
- the following compounds can be mentioned as fluorides of higher valence capable of providing a thermally decomposable sub-fluoride: wF6, MoF6, ReF6, PtF6, TaFS, NbFS, BFS, TiF4, CF4, SiF4
- the higher valence fluoride is caused to react on the corresponding metal or non-metal, heated to the appropriate temperature.
- the generating metal or non-metal can be very easily located in the vicinity of the part to be coated, which permits to form the subfluoride in the vicinity of the surface on which the de- MFm MFm- M mF- M F adsorbed adsorbed adsorbed solid desorbed gas metal
- a gaseous molecule of sub-fluoride MF inpinges on the substratum to be coated, heated to the appropriate temperature, the impact is efficient and the MF, molecule is activated to a sufficient extent to be quickly absorbed by the substratum.
- the chemical adsorption being of a dissociating nature, the sub-fluoride adsorbed decomposes into metal M and into fluorine atoms.
- the metal obtained is inserted into the surface cristalline lattice, and fluorine is desorbed, which permits further molecules of sub-fluorides to be introduced and the vapour deposition to proceed.
- the method according to the invention can be illustrated, for example, by the vapour deposition of tungsten (W). Hexafluoride WF reacts on tungsten metal W as follows:
- the tungsten hexafluoride used at the beginning of the reaction is re-generated at the end of that reaction; it thus acts as a catalyst. It is therefore possible to introduce the gas into the enclosure and to carry out the reaction under constant pressure.
- the metal fluoride MF or MP thus formed is then decomposed on the suitably heated part to be coated, thus freeing the metal which is deposited:
- the fluorine provided by the thermal decomposition of MP or MP recombines with Wlto give back fluoride WF i.e. the gaseous catalyst which is thus regenerated.
- a great many metal deposits can be obtained in this way.
- the copper deposits from CuF and CuF and the nickel deposits from NiF and NiF.
- the following metals are transfered and vapour-deposited according to that method: iron, cobalt, zinc, silver, gold, cadmium, and aluminum, to mention only the most frequently used metals.
- the above reaction has the advantage of permitting the vapour-deposition of metals such as, e.g., nickel, copper, aluminum, zinc, cadmium, zirconium, the fluorides of which, which are not volatile enough, cannot be validly used in the other vapour-metallurgy methods.
- metals such as, e.g., nickel, copper, aluminum, zinc, cadmium, zirconium, the fluorides of which, which are not volatile enough, cannot be validly used in the other vapour-metallurgy methods.
- the method according to the invention has many others advantages.
- the deposits obtained by means of the method according to the invention are compact, even, adhesive and epitaxic,:whenever allowed by the nature of the substratum and of the deposit. a
- a remarkable vapour-deposition technology can be developed, taking account of the fact that the fluoride (MF or MP useful to thevapour-deposition, can be generated in the. vicinity of the surface to be coated, whatever be the shape of the latter; one has only to put the metal source near the substratum.
- MF or MP useful to thevapour-deposition
- This is of considerable advantage for carrying out depositions inside parts of various shapes such as tubes, valves and containers.
- the shape of the part to be coated by no means impairs .the very good penetration power associated to the method.
- the metal generating member may be a wire or a bar, heated by Joule effect.
- the generatingsource may also be a rod, indirectly heated by means of a non-consumable thermal member, the shape of that rod being adapted to each particular instance.
- That rod may either be coated with the metal obtained by sin'tering, or consist in a tank containing fragments of the metal to be vapour-deposited.
- the part to be coated is preferably directly heated by the metal member which generates metal M, and in this case a heat insulating member must surround said part.
- the shape of the devices for carrying out the method according to the invention varies according to the shape, the nature and the number of the articles to be coated.
- FIG. 1 is a section through a device for coating the inside of a tube
- FIG. 2 is a section through a device for coating both the inner portion and the outer portion of a tube; as can be seen in FIG. 1, tube 1, made of any metal alloy, the inside portion of which is to be metal coated, is introduced into a heat insulated sleeve 2, with a view to avoiding as best as possible, heat-losses by radiation.
- a metal or non-metal rod 3 is held by the ends thereof inside the tube at the level of plugs 4 and 5.
- Plug 4 has an opening for conduct 6 through which a higher valence fluoride is introduced. For operating that device, the rod must be heated to a predetermined temperature before introducing, through conduct 6, the fluoride which, by contacting bar 3, generates a sub-fluoride that forms a deposit of the inner wall of tube 1.
- Tube 1 is held within an enclosure 7 by means of brackets (not shown).
- the arrangement as shown permits, as in the previous instance, to coat the innerportion of tube 1 with metal, and also permits to coat the outer portion of that tube, through the addition of bars 3 and 3" which are metal canon-metal generating sources like bar 3, and of conducts-5' and 5" for the introduction of fluorine.
- bars 3 and 3" which are metal canon-metal generating sources like bar 3, and of conducts-5' and 5" for the introduction of fluorine.
- the inner wall of enclosure 7 is of a material which is not likely to retain a metal deposit. 1 Y v r
- the method according to the invention permits to.
- the vapour-deposit is necessarily good. This is even the case with deposits carried out at temperatures which would prove much too low for the reduction method. It follows that the method according to the invention permits to coat materials likely to be definitively altered at higher temperatures,. O ine can mention, for instance, the case of deposits made on metals subjected to allotropic transformations at high temperatures and for which there is a risk of deteriorating the deposit-substratum interface, at the moment of passing the allotropic transformation point, during the cooling step.
- thedep osits obtained carrying out themethodaccording to,,th e invention are both adhesive, compact and even, and that their growth is carried out epitaxically, viz. the cristalline lattice 'develops atom per atom in agreement with the surface cristalline lattice, which permits to obtain as desired monocristals having agiven orientation.
- tungsten deposits were obtained, from WP on the following substrata, given merely as examples: tungsten, molybdenum copper, nickel, monel-metal, inconel, iron, graphite, silicon, alumina.
- vapour-deposits with alloys. It is indeed possible to carry out the co-deposition of two metals, by taking advantage of the respective chemical natures of the generating metal and of the gaseous fluoride of higher valence.
- a remarkable vapour-deposition technology can be developed taking into account the fact that sub-fluoride useful for the vapour-deposition can be generated in the vicinity of the surface to be coated whatever be the shape of the latter. It is only sufficient to put the metal or non-metal source near the substratum. This is of considerable advantage for making deposits e.g. inside tubes, even very long and narrow tubes, inside valve bodies, complicated tubing, containers, etc. The shape of the member to be coated by no means impairs the excellent penetrating power associated to the method.
- the metal or non-metal source can be a wire or a bar, heated by Joule effect. That source can also be a rod directly heated by means of a non-consumable thermal member. The shape of that rod may be adapted to each particular instance.
- the rod either can be coated with the metal obtained by sintering or according to any vapour-deposition method, or consists in a tank containing metal fragments to be vapour-deposited.
- the part to be coated is preferably heated directly by the generating metal member, said part being surrounded by a heat-insulating member.
- the invention may have quite a number of applications in the field of electronics, in particular for the manufacture of the transmitters of electronic-tungsten converters, and for the manufacture of X-ray tubes anticathodes and in particular, in the field of space research, for manufacturing titanium thermal shields.
- the following applications can also be mentioned:
- refractory metal e.g. of tungsten, tantalum, molybdenum
- refractory substrata such as ruby or corundum
- the deposition of refractory metals on various types of glass in view of the possibility of making the deposition at a low temperature
- the deposition of various metals on substrata sensitive to hydrogen in view of the possibility of making the deposition at a low temperature
- catalysts by depositing metals having a high specific area.
- a method for forming pure metal deposits consisting in introducing, in the vapour state, at least one metal or metalloid fluoride of higher valence selected from the group consisting of: WF MF ReF PtF TaF NbF BF TiF SiF CF, into an enclosure containing at least one substratum to be metal-coated and a source of the metal to be deposited selected from the group consisting of nickel, copper, aluminum, zinc, cadmium, molybdenum, tungsten and zirconium, heating said source in order that the higher valence fluoride is transformed, when contacting said source, into at least one sub-fluoride of the source metal which coats the substratum and is transformed into fluorine and into the metal, which constitutes the desired deposit.
- the substratum is a material selected from the group consisting of tungsten, molybdenum, copper, nickel, monel metal, inconel, iron, graphite, silicon and alumina.
- a method according to claim 1, wherein the source is selected from the group consisting of an electrically heated wire or a hollow rod.
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Vapour Deposition (AREA)
- Physical Vapour Deposition (AREA)
- Surface Treatment Of Glass (AREA)
Abstract
A method for forming pure metal or non-metal deposits, said method consisting in introducing, in the vapour state, at least one metal or non-metal fluoride of higher valence into an enclosure containing at least one substratum to be metal-coated and a source for providing the metal or non-metal to be deposited, heating said source in order that the higher-valence fluoride is transformed, when contacting said source, into at least one sub-fluoride which evaporates, is condensed on the substratum and is transformed into fluorine and into the metal, or the non-metal, which constitutes the desired deposit.
Description
ueu 5R lO--7-75 QR United States Patent [191 Dejachy et al.
[451 v Oct. 7, 1975 METHOD FOR FORMING PURE METAL OR NON-METAL DEPOSITS [75] Inventors: Jacques Dejachy, Saint-Cloud;
Jacques Gillardeau, Longjumeau, both of France [73] Assignee: Commissariat a IEnergie Atomique,
Paris, France 22 Filed: Nov. 1,1973
21 Appl.No.:4l2,0l6
[30] Foreign Application Priority Data Nov. 7, I972 France 72.39334 ['52] U.S. Cl. 428/408; 427/237; 427/253;
427/255; 428/450; 428/457; 428/472 [51] Int. Cl. C23C 11/02 [58] Field of Search 117/106 R, 107.2 R
[56] References Cited UNITED STATES PATENTS 2,887,407 5/1959 Koch 1 ll7/107 3,658,577 4/1972 Wakefield 117/106 R Primary Examiner-Harris A. Pitlick Attorney, Agent, or FirmCameron, Kerkam, Sutton, Stowell & Stowell 57 ABSTRACT 14 Claims, 2 Drawvin' g Figures US. Patent Oct. 7,1975
METHOD FOR FORMING PURE METAL OR NON-METAL DEPOSITS The present invention relates to a method for obtaining metal or metal-like coatings in the pure state from the high-valence corresponding fluorides.
It has already been possible to obtain metal coatings from metal fluorides by decomposing the latter in the vapour state, under a given pressure and at a given temperature, on a substratum to be metallized, said substratum being itself of metal or of a material likely to decompose fluorides.
According to the above method, whenever a metal M is brought into contact with its fluoride MFn (n being the valence of said metal) in the vapour state and at an appropriate temperature, there is formed on the surface thereof a deposit of the fluoride metal, according to the following reaction:
nF (adsorbed) Whenever a gaseous MF molecule impinges on the metal surface, the impact is efficient: the metal atom is deposited and two fluorine atoms are chemically adsorbed.
The positioning of the metal atom in the surface lattice of the receiver metal occurs very quickly. The adsorbed two fluorine atoms are capable of moving under the conditions of the experiment, and the desorption thereof, which proves to be one of the main factors governing the kinetics of the deposition, allows the metal surface to be permanently uncovered.
When a fluoride MF,,, in the vapour state and at an appropriate temperature is in contact with a substratum that provides volatile fluorides, the fluorides obtained are eliminated and leave the metal in the pure state.
When a fluoride MP in the vapour state and at an appropriate temperature is in contact with a metal that does not provide volatile fluorides and the pure metal obtained is soluble in the metal forming the substratum, alloys are obtained, which occurs, e.g., when the two metals involved are platinum and copper. When a fluoride MF,,, in the vapour state and at an appropriate temperature, happens to be in the presence of a substratum that does not provide volatile fluorides, and the substratum and the metal obtained are not miscible, it is possible to decompose the fluoride in contact with said substratum and then eliminate same with a view to obtaining pure metal.
The thus formed coatings are good, but they require a highly careful and uneasy preparation of the fluorides as used, which have to be thermally decomposable in a direct way. It happens that some fluorides are hygroscopic to such an extent that their previous preparation apart from the vapour-deposition enclosure could not be resorted to, since their handling is, in fact, rendered impossible in view of their considerable instability with respect to the traces of water which are always to be found on the sites of experiments.
Another method consists in reducing a fluoride by 1 means of hydrogen, and it also leads to good coatings,
while however showing major drawbacks.
In certain instances, e.g. when the geometry of the substratum to be coated prevents the easy renewal or 2 reagents, the excess hydrogen may alter the hydrogen/- gaseous fluoride ratio to the point of deteriorating the metal deposit, or even causing the vapour-deposition to stop.
The presence of hydrogen leads to the production of hydrofluoric gas, and steps, generally considered as dangerous, have to be taken for draining and storing said gas.
Too great a concentration of hydrofluoric gas in the vicinity of the substratum may, quite undesirably, lead to a reaction opposite to the desired one, viz. the recombination of the metal deposited in the fluoride state.
The reduction method has therefore to be rejected whenever the geometry of the objects to be coated is complicated, or whenever it is desired to form deposits inside parts comprising many branches or, e.g., inside long and narrow tubes.
A new method, free of the above drawbacks, has been discovered and it is based on the thermal decomposition of a metal or non-metal sub-fluoride, obtained in situ by the reaction of the corresponding higher valence fluoride on the metal or the non-metal substance.
The invention relates to a method for forming pure metal or non-metal deposits, said method consisting in introducing, in the vapour state, at least one metal or non-metal fluoride of higher valence into an enclosure containing at least one substratum to be coated and a source for providing the metal or non-metal to be deposited, heating said source in order that the higher valence fluoride is transformed, when contacting said source, into at least one sub-fluoride which evaporates, is condensed on the substratum and is transformed into fluorine and into the metal, or the non-metal, which constitutes the desired deposit.
It is well known that the fluorides of higher valence are fluoridizing and cannot be thermally decomposed until the metal is obtained. It is only by means of the reduction of these fluorides with hydrogen that a total chemical decomposition can be obtained. On the other hand, the sub-fluorides are not fluoridizing in general, and they can be thermally decomposed on a hot substratum in order to provide the metal directly.
According to the invention, the formation of subfluorides and the thermal decomposition of same occur simultaneously. The formation of a sub-fluoride, having the general formula MF froma higher fluoride, having the general formula MF,,, and the metal M is carried out as follows:
In MF,
gas
n and m being the valences of the elements and n being higher than m.
By way of non limitating. examples, the following compounds can be mentioned as fluorides of higher valence capable of providing a thermally decomposable sub-fluoride: wF6, MoF6, ReF6, PtF6, TaFS, NbFS, BFS, TiF4, CF4, SiF4 In order to obtain the useful sub-fluoride, the higher valence fluoride is caused to react on the corresponding metal or non-metal, heated to the appropriate temperature. It is to be noted that the generating metal or non-metal can be very easily located in the vicinity of the part to be coated, which permits to form the subfluoride in the vicinity of the surface on which the de- MFm MFm- M mF- M F adsorbed adsorbed adsorbed solid desorbed gas metal When a gaseous molecule of sub-fluoride MF,, inpinges on the substratum to be coated, heated to the appropriate temperature, the impact is efficient and the MF, molecule is activated to a sufficient extent to be quickly absorbed by the substratum. The chemical adsorption being of a dissociating nature, the sub-fluoride adsorbed decomposes into metal M and into fluorine atoms. The metal obtained is inserted into the surface cristalline lattice, and fluorine is desorbed, which permits further molecules of sub-fluorides to be introduced and the vapour deposition to proceed. The method according to the invention can be illustrated, for example, by the vapour deposition of tungsten (W). Hexafluoride WF reacts on tungsten metal W as follows:
SWF W--) 6 WF,,
gas metal gas When those two metals are different, reactions of the following types will take place:
It can be noted that the tungsten hexafluoride used at the beginning of the reaction is re-generated at the end of that reaction; it thus acts as a catalyst. It is therefore possible to introduce the gas into the enclosure and to carry out the reaction under constant pressure.
The above reaction can be written as follows:
The metal fluoride MF or MP thus formed is then decomposed on the suitably heated part to be coated, thus freeing the metal which is deposited:
MF MF M F---) M F gas adsorbed adsorbed adsorbed metal desorbed deposited or MF MF M 2F) M F gas adsorbed adsorbed adsorbed metal desorbed deposited and the tungsten pentafluoride thus formed is thermally decomposed as follows:
5 WF5 WF5 W 5F -)W F gas adsorbed adsorbed adsorbed metal desorbed The formation of sub-fluoride and the decomposition of said fluoride occur simultaneously provided the substratum to be coated and the sub-fluoride generating metal are heated to carefully chosen different temperatures.
A careful selection of these temperatures will permit not only to carry out the method but also to act favorably on the kinetics of vapour-deposition and on the properties of the metal deposits obtained.
It can be noted that, in the particular instance of tungsten, very good coatings are achieved by raising the generating source to a temperature of about 750F (400C) and the substratum to a slightly lower temperature. It can also be noted that similar results can be obtained by carrying out the reduction method, but, in the latter case, the temperature must reach about 1290F (700C), leaving aside the already mentioned drawbacks of the method itself.
Two different cases can be contemplated, according as the source metal and the metal of the gazeous fluoride introduced into the reaction enclosure are the same or not.
When those two metals are identical, reactions of the following types will take place:
The fluorine provided by the thermal decomposition of MP or MP recombines with Wlto give back fluoride WF i.e. the gaseous catalyst which is thus regenerated.
A great many metal deposits can be obtained in this way. By way of example can be mentioned the copper deposits from CuF and CuF, and the nickel deposits from NiF and NiF. The following metals are transfered and vapour-deposited according to that method: iron, cobalt, zinc, silver, gold, cadmium, and aluminum, to mention only the most frequently used metals.
The above reaction has the advantage of permitting the vapour-deposition of metals such as, e.g., nickel, copper, aluminum, zinc, cadmium, zirconium, the fluorides of which, which are not volatile enough, cannot be validly used in the other vapour-metallurgy methods.
The operating conditions and the results of several tests are summed up in the following table 1.
The method according to the invention has many others advantages.
It permits to obtain deposits of metals the fluorides of which are very poorly volatile, and therefore can hardly be used, and even cannot be used at all, in the ordinary vapour metallurgy methods, in particular in the reduction methods.
Since the gaseous phase contains no hydrogen, no hydrofluoric acid is formed, which might impair the formation of good deposits.
The method which consists in adsorbing the sub-fluorides molecules and desorbing the fluorine atoms formed which ensure a self-regulation of the deposition speed, necessarily leads to good deposits, even when operating at temperatures which would beconsidered as too low, for instance in a reduction method. It is thus possible to make metal deposits on substrata which could no sustain high temperatures. The deposits obtained by means of the method according to the invention are compact, even, adhesive and epitaxic,:whenever allowed by the nature of the substratum and of the deposit. a
A remarkable vapour-deposition technology. can be developed, taking account of the fact that the fluoride (MF or MP useful to thevapour-deposition, can be generated in the. vicinity of the surface to be coated, whatever be the shape of the latter; one has only to put the metal source near the substratum. This is of considerable advantage for carrying out depositions inside parts of various shapes such as tubes, valves and containers. The shape of the part to be coated by no means impairs .the very good penetration power associated to the method.
With a view to carrying out said method properly, it is necessary that the metal generating source be hot enough for causing the useful fluoride (MF or MF to vaporize and to be transferred to the substratum to be coated. I I
The metal generating member may be a wire or a bar, heated by Joule effect. The generatingsource may also be a rod, indirectly heated by means of a non-consumable thermal member, the shape of that rod being adapted to each particular instance.
That rod may either be coated with the metal obtained by sin'tering, or consist in a tank containing fragments of the metal to be vapour-deposited. I
In some devices for carrying out the above method, the part to be coated is preferably directly heated by the metal member which generates metal M, and in this case a heat insulating member must surround said part.
The shape of the devices for carrying out the method according to the invention varies according to the shape, the nature and the number of the articles to be coated.
The following description will provide two examples of the coating of tubes.
FIG. 1 is a section through a device for coating the inside of a tube, and
FIG. 2 is a section through a device for coating both the inner portion and the outer portion of a tube; as can be seen in FIG. 1, tube 1, made of any metal alloy, the inside portion of which is to be metal coated, is introduced into a heat insulated sleeve 2, with a view to avoiding as best as possible, heat-losses by radiation. A metal or non-metal rod 3 is held by the ends thereof inside the tube at the level of plugs 4 and 5. Plug 4 has an opening for conduct 6 through which a higher valence fluoride is introduced. For operating that device, the rod must be heated to a predetermined temperature before introducing, through conduct 6, the fluoride which, by contacting bar 3, generates a sub-fluoride that forms a deposit of the inner wall of tube 1.
In FIG. 2, the elements similar to those of FIG. 1 are given the same reference numerals. Tube 1 is held within an enclosure 7 by means of brackets (not shown). The arrangement as shown permits, as in the previous instance, to coat the innerportion of tube 1 with metal, and also permits to coat the outer portion of that tube, through the addition of bars 3 and 3" which are metal canon-metal generating sources like bar 3, and of conducts-5' and 5" for the introduction of fluorine. It is to be specified thatsthe inner wall of enclosure 7 is of a material which is not likely to retain a metal deposit. 1 Y v r In addition to the fact'that it is carried out as explained abovewith no. generation of hyrogen and hydrofluoric gas, the method according to the invention permits to. eliminate the fluorine generated during the dissociation of the sub-fluoride, by re-combining it with the source metal. The reaction interface, and more exactly the composition of the gaseous phase, are therefore perfectly constant for all the duration of the vapour-deposition, whatever be the shape of the part to be metal-coated. v
On account of the cristal growth whichfgoverns the deposition, viz. the adsorption of the sub-fluoride molecules and the desorption of the fluorine atoms generated through which .the deposition speed is selfregulated, the vapour-deposit is necessarily good. This is even the case with deposits carried out at temperatures which would prove much too low for the reduction method. It follows that the method according to the invention permits to coat materials likely to be definitively altered at higher temperatures,,. O ine can mention, for instance, the case of deposits made on metals subjected to allotropic transformations at high temperatures and for which there is a risk of deteriorating the deposit-substratum interface, at the moment of passing the allotropic transformation point, during the cooling step.
It must be pointed out that thedep osits obtained carrying out themethodaccording to,,th e invention are both adhesive, compact and even, and that their growth is carried out epitaxically, viz. the cristalline lattice 'develops atom per atom in agreement with the surface cristalline lattice, which permits to obtain as desired monocristals having agiven orientation.
Such deposits'can be made on many various substrata, all the more as, as already mentioned, the method accordingto the invention permits to obtain very good deposits at temperatures lower than those involved in known methods.
Excellent tungsten deposits were obtained, from WP on the following substrata, given merely as examples: tungsten, molybdenum copper, nickel, monel-metal, inconel, iron, graphite, silicon, alumina.
It is also to be noted that it is possible to make vapour-deposits with alloys. It is indeed possible to carry out the co-deposition of two metals, by taking advantage of the respective chemical natures of the generating metal and of the gaseous fluoride of higher valence. One can mention, by way of example, the excellent results acheived as regards the co-deposition of molybdenum and tungsten, starting with a generating source of tungsten and with molybdenum hexafluoride as the gas.
A remarkable vapour-deposition technology can be developed taking into account the fact that sub-fluoride useful for the vapour-deposition can be generated in the vicinity of the surface to be coated whatever be the shape of the latter. It is only sufficient to put the metal or non-metal source near the substratum. This is of considerable advantage for making deposits e.g. inside tubes, even very long and narrow tubes, inside valve bodies, complicated tubing, containers, etc The shape of the member to be coated by no means impairs the excellent penetrating power associated to the method.
The metal or non-metal source can be a wire or a bar, heated by Joule effect. That source can also be a rod directly heated by means of a non-consumable thermal member. The shape of that rod may be adapted to each particular instance. The rod either can be coated with the metal obtained by sintering or according to any vapour-deposition method, or consists in a tank containing metal fragments to be vapour-deposited.
In some devices for carrying out the method according to the invention, the part to be coated is preferably heated directly by the generating metal member, said part being surrounded by a heat-insulating member.
The invention may have quite a number of applications in the field of electronics, in particular for the manufacture of the transmitters of electronic-tungsten converters, and for the manufacture of X-ray tubes anticathodes and in particular, in the field of space research, for manufacturing titanium thermal shields. The following applications can also be mentioned:
- internal coating of tubular parts of small diameter;
- manufacture of metal tubes by making a deposit on the inner portion or on the outer portion of supporting tubes which are later on withdrawn either mechanically or chemically;
the deposition of reflecting or semi-reflecting metal layers of refractory metal, e.g. of tungsten, tantalum, molybdenum, on refractory substrata, such as ruby or corundum, permitting to use them at high temperatures; the deposition of refractory metals on various types of glass, in view of the possibility of making the deposition at a low temperature; the deposition of various metals on substrata sensitive to hydrogen; the production of catalysts, by depositing metals having a high specific area.
What is claimed is:
1. A method for forming pure metal deposits, said method consisting in introducing, in the vapour state, at least one metal or metalloid fluoride of higher valence selected from the group consisting of: WF MF ReF PtF TaF NbF BF TiF SiF CF, into an enclosure containing at least one substratum to be metal-coated and a source of the metal to be deposited selected from the group consisting of nickel, copper, aluminum, zinc, cadmium, molybdenum, tungsten and zirconium, heating said source in order that the higher valence fluoride is transformed, when contacting said source, into at least one sub-fluoride of the source metal which coats the substratum and is transformed into fluorine and into the metal, which constitutes the desired deposit.
2. A method according to claim 1, wherein the metal of the metal fluoride introduced in the vapour state is the same as the metal of the source.
3. A method according to claim 1, wherein the metal of the metal fluoride introduced in the vapour state is different from the metal of the source.
4. A method according to claim 2, wherein the fluoride introduced in the vapour state is molybdenum hexafluoride, and wherein the source is molybdenum.
5. A method according to claim 3, wherein the fluoride introduced in the vapour state is molybdenum hexafluoride and wherein the source is tungsten.
6. A method according to claim 1, wherein the substratum is a material selected from the group consisting of tungsten, molybdenum, copper, nickel, monel metal, inconel, iron, graphite, silicon and alumina.
7. A method according to claim 1, wherein the source is heated to a temperature above the substratum temperature.
8. A method according to claim 1, wherein the source of tungsten is heated to about 750F (400C).
9. A method according to claim 1, wherein the source is selected from the group consisting of an electrically heated wire or a hollow rod.
10. A method according to claim 9, wherein said rod is coated with a metal obtained by sintering or by vapour-deposition.
1 l. A method according to claim 9, wherein said hollow rod forms a tank containing fragments of the metal to be vapour-deposited.
12. A method according to claim 1, wherein said substratum is the inner wall of a tube, and the source and the fluorine inlet conduit are located within said tube.
13. A method according to claim 1, wherein said substratum is the outer wall of a tube, said source and fluorine inlet conduits being located, outside said tube, within an enclosure which does not retain the metal deposit.
14. A product coated with metal deposits by the method of claim 1.
Claims (14)
1. A METHOD FOR FORMING PURE METAL DEPOSITS, SAID METHOD CONSISTING IN INTRODUCING, IN THE VAPOUR STATE, AT LEAST ONE METAL OR METALLOID FLUROIDE OF HIGHER VALENCE SELECTED FROM THE GROUP CONSISTING OF: WF6, MOF6, REF6, PTF6, TAF5, NBF5, BF5, TIF4, SIF4, CF4 INTO AN ENCLOSURE CONTAINING AT LEAST ONE SUBSTRATUM TO BE METAL-COATED AND A SOURCE OF THE METAL TO BE DEPOSITED SELECTED FROM THE GROUP CONSISTING OF NICKEL, COPPER, ALUMINUM, ZINC, CADMIUM, MOLYBDENUM, TUNGSTEN AND ZIRCONIUM, HEATING SAID SOURCE IN ORDER THAT THE HIGHER VALENCE FLUROIDE IS TRANSFORMED, WHEN CONTACTING SAID SOURCE, INTO AT LEAST ONE SUB-FLUORIDE OF THE SOURCE METAL WHICH COATS THE SUBSTRATUM AND IS TRANSFORMED INTO FLUORINE AND INTO THE METAL, WHICH CONSTITUTES THE DESIRED DEPOSIT.
2. A method according to claim 1, wherein the metal of the metal fluoride introduced in the vapour state is the same as the metal of the source.
3. A method according to claim 1, wherein the metal of the metal fluoride introduced in the vapour state is different from the metal of the source.
4. A method according to claim 2, wherein the fluoride introduced in the vapour state is molybdenum hexafluoride, and wherein the source is molybdenum.
5. A method according to claim 3, wherein the fluoride introduCed in the vapour state is molybdenum hexafluoride and wherein the source is tungsten.
6. A method according to claim 1, wherein the substratum is a material selected from the group consisting of tungsten, molybdenum, copper, nickel, monel metal, inconel, iron, graphite, silicon and alumina.
7. A method according to claim 1, wherein the source is heated to a temperature above the substratum temperature.
8. A method according to claim 1, wherein the source of tungsten is heated to about 750*F (400*C).
9. A method according to claim 1, wherein the source is selected from the group consisting of an electrically heated wire or a hollow rod.
10. A method according to claim 9, wherein said rod is coated with a metal obtained by sintering or by vapour-deposition.
11. A method according to claim 9, wherein said hollow rod forms a tank containing fragments of the metal to be vapour-deposited.
12. A method according to claim 1, wherein said substratum is the inner wall of a tube, and the source and the fluorine inlet conduit are located within said tube.
13. A method according to claim 1, wherein said substratum is the outer wall of a tube, said source and fluorine inlet conduits being located, outside said tube, within an enclosure which does not retain the metal deposit.
14. A product coated with metal deposits by the method of claim
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US4196230A (en) * | 1978-09-15 | 1980-04-01 | Gibson James O | Production of carbon fiber-tantalum carbide composites |
EP0040092A1 (en) * | 1980-05-14 | 1981-11-18 | Permelec Electrode Ltd | Method for forming an anticorrosive coating on a metal substrate |
US4343963A (en) * | 1979-03-02 | 1982-08-10 | Westinghouse Electric Corp. | Substrate for silicon solar cells |
US4386137A (en) * | 1981-09-10 | 1983-05-31 | Nobuatsu Watanabe | Process for producing a graphite fluoride type film on the surface of an aluminum substrate |
US4387962A (en) * | 1981-10-06 | 1983-06-14 | The United States Of America As Represented By The Secretary Of The Air Force | Corrosion resistant laser mirror heat exchanger |
US4402771A (en) * | 1979-03-02 | 1983-09-06 | Westinghouse Electric Corp. | Substrate for silicon solar cells |
US4411861A (en) * | 1977-08-19 | 1983-10-25 | Kraftwerk Union Aktiengesellschaft | Method for protecting the casing tubes of nuclear reactor fuel rods |
US4540607A (en) * | 1983-08-08 | 1985-09-10 | Gould, Inc. | Selective LPCVD tungsten deposition by the silicon reduction method |
US4681652A (en) * | 1980-06-05 | 1987-07-21 | Rogers Leo C | Manufacture of polycrystalline silicon |
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US4842891A (en) * | 1987-02-20 | 1989-06-27 | Hitachi, Ltd. | Method of forming a copper film by chemical vapor deposition |
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JPS55134170A (en) * | 1979-04-04 | 1980-10-18 | Oyo Kagaku Kenkyusho | Manufacture of deformed tungusten structure |
DE3025680A1 (en) * | 1980-07-07 | 1982-02-04 | Siemens AG, 1000 Berlin und 8000 München | High-temp. furnace heating element - is graphite cylinder heated by high-frequency induction and platinum or iridium coated |
FR2527226B1 (en) * | 1982-05-19 | 1986-02-21 | Creusot Loire | METHOD FOR COATING IN THE GASEOUS PHASE OF SMALL HOLE HOUSINGS IN STEEL PARTS |
DE3300449A1 (en) * | 1983-01-08 | 1984-07-12 | Philips Patentverwaltung Gmbh, 2000 Hamburg | METHOD FOR PRODUCING AN ELECTRODE FOR A HIGH PRESSURE GAS DISCHARGE LAMP |
FR2629839B1 (en) * | 1988-04-07 | 1991-03-22 | Pauleau Yves | PROCESS FOR DEPOSITING REFRACTORY METALS |
GB9203394D0 (en) * | 1992-02-18 | 1992-04-01 | Johnson Matthey Plc | Coated article |
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- 1973-11-07 DE DE19732355531 patent/DE2355531A1/en active Pending
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US4411861A (en) * | 1977-08-19 | 1983-10-25 | Kraftwerk Union Aktiengesellschaft | Method for protecting the casing tubes of nuclear reactor fuel rods |
US4196230A (en) * | 1978-09-15 | 1980-04-01 | Gibson James O | Production of carbon fiber-tantalum carbide composites |
US4343963A (en) * | 1979-03-02 | 1982-08-10 | Westinghouse Electric Corp. | Substrate for silicon solar cells |
US4402771A (en) * | 1979-03-02 | 1983-09-06 | Westinghouse Electric Corp. | Substrate for silicon solar cells |
EP0040092A1 (en) * | 1980-05-14 | 1981-11-18 | Permelec Electrode Ltd | Method for forming an anticorrosive coating on a metal substrate |
US4681652A (en) * | 1980-06-05 | 1987-07-21 | Rogers Leo C | Manufacture of polycrystalline silicon |
US4386137A (en) * | 1981-09-10 | 1983-05-31 | Nobuatsu Watanabe | Process for producing a graphite fluoride type film on the surface of an aluminum substrate |
US4387962A (en) * | 1981-10-06 | 1983-06-14 | The United States Of America As Represented By The Secretary Of The Air Force | Corrosion resistant laser mirror heat exchanger |
US4540607A (en) * | 1983-08-08 | 1985-09-10 | Gould, Inc. | Selective LPCVD tungsten deposition by the silicon reduction method |
US4751044A (en) * | 1985-08-15 | 1988-06-14 | Westinghouse Electric Corp. | Composite nuclear fuel cladding tubing and other core internal structures with improved corrosion resistance |
US4741928A (en) * | 1985-12-27 | 1988-05-03 | General Electric Company | Method for selective deposition of tungsten by chemical vapor deposition onto metal and semiconductor surfaces |
US4842891A (en) * | 1987-02-20 | 1989-06-27 | Hitachi, Ltd. | Method of forming a copper film by chemical vapor deposition |
Also Published As
Publication number | Publication date |
---|---|
FR2205583A1 (en) | 1974-05-31 |
GB1406394A (en) | 1975-09-17 |
DE2355531A1 (en) | 1974-05-09 |
JPS4995832A (en) | 1974-09-11 |
FR2205583B1 (en) | 1975-09-12 |
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