US2432657A - Process of evaporating metals - Google Patents
Process of evaporating metals Download PDFInfo
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- US2432657A US2432657A US690358A US69035846A US2432657A US 2432657 A US2432657 A US 2432657A US 690358 A US690358 A US 690358A US 69035846 A US69035846 A US 69035846A US 2432657 A US2432657 A US 2432657A
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- metals
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- silver
- wetting
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- 229910052751 metal Inorganic materials 0.000 title description 144
- 239000002184 metal Substances 0.000 title description 144
- 150000002739 metals Chemical class 0.000 title description 81
- 238000000034 method Methods 0.000 title description 35
- 238000001704 evaporation Methods 0.000 title description 23
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 46
- 239000004332 silver Substances 0.000 description 46
- 229910052709 silver Inorganic materials 0.000 description 44
- 238000009736 wetting Methods 0.000 description 40
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 39
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 38
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 37
- 229910045601 alloy Inorganic materials 0.000 description 33
- 239000000956 alloy Substances 0.000 description 33
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 32
- 229910052721 tungsten Inorganic materials 0.000 description 31
- 239000010937 tungsten Substances 0.000 description 31
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 29
- 239000010949 copper Substances 0.000 description 29
- 229910052802 copper Inorganic materials 0.000 description 27
- 229910052715 tantalum Inorganic materials 0.000 description 27
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 27
- 238000000576 coating method Methods 0.000 description 26
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 25
- 229910052750 molybdenum Inorganic materials 0.000 description 25
- 239000011733 molybdenum Substances 0.000 description 25
- 239000010955 niobium Substances 0.000 description 24
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 24
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 23
- 239000010931 gold Substances 0.000 description 23
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 22
- 239000011248 coating agent Substances 0.000 description 21
- 229910052737 gold Inorganic materials 0.000 description 21
- 229910052759 nickel Inorganic materials 0.000 description 19
- 229910052742 iron Inorganic materials 0.000 description 18
- 229910052697 platinum Inorganic materials 0.000 description 18
- 238000002207 thermal evaporation Methods 0.000 description 16
- 230000008018 melting Effects 0.000 description 15
- 238000002844 melting Methods 0.000 description 15
- 230000008020 evaporation Effects 0.000 description 13
- 229910052763 palladium Inorganic materials 0.000 description 11
- 238000005275 alloying Methods 0.000 description 10
- 238000000151 deposition Methods 0.000 description 10
- 230000008021 deposition Effects 0.000 description 10
- 229910017052 cobalt Inorganic materials 0.000 description 8
- 239000010941 cobalt Substances 0.000 description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 8
- 229910001260 Pt alloy Inorganic materials 0.000 description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- 229910052793 cadmium Inorganic materials 0.000 description 6
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- -1 platinum group metals Chemical class 0.000 description 6
- 229910052718 tin Inorganic materials 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- 229910052738 indium Inorganic materials 0.000 description 5
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 5
- 229910052787 antimony Inorganic materials 0.000 description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 4
- 229910052797 bismuth Inorganic materials 0.000 description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 4
- 229910052741 iridium Inorganic materials 0.000 description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 4
- 229910001092 metal group alloy Inorganic materials 0.000 description 4
- 230000000737 periodic effect Effects 0.000 description 4
- 229910052703 rhodium Inorganic materials 0.000 description 4
- 239000010948 rhodium Substances 0.000 description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 4
- 229910052716 thallium Inorganic materials 0.000 description 4
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 4
- 239000011135 tin Substances 0.000 description 4
- 229910001316 Ag alloy Inorganic materials 0.000 description 3
- 229910000881 Cu alloy Inorganic materials 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910001020 Au alloy Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000011505 plaster Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 238000002310 reflectometry Methods 0.000 description 2
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910001252 Pd alloy Inorganic materials 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 230000000135 prohibitive effect Effects 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Images
Classifications
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/26—Vacuum evaporation by resistance or inductive heating of the source
Definitions
- Our present invention relates to a novel process of evaporating metals. It has to do, more particularly. with the coating or wetting, by capillary attraction, of a filament which, for example may be formed "from a coil of ordinary tungsten wire, tantalum, molybdenum or columbium wire, by various metals in the form of an alloy or difierent alloys, which metal or metals it is desired to evaporate and which in pure form normally do not wet these metallic filaments, and the application of said metals or metal alloys by deposition resulting from thermal evaporation, to the face or surface or an article, such as a piece of glass, porcelain, plaster, metal, plastic, Cellophane, paper or the like, to provide a reflective or metallized surface coating for said article.
- the invention also has to do with securing wetting and with thermal evaporation oi such metals from pure tungsten, tantalum, molybdenum, o'r columbium filament
- the metals can be readily evaporated.
- aluminum, beryllium, magnesium, vanadium, barium, strontium, iron, nickel, cobalt, manganese, thorium, chromium and titanium when applied to filaments of tungsten, tantalum, molybdenum or columbium, will on heating in a vacuum, melt and spread over the filament by capillary attraction and satisfactory evaporation of these metals.
- tungsten, tantalum, molybdenum or columbium as filaments for the evaporation of metals which do not wet these filaments by causing them to wet such filaments by the application to such filaments, or the forming thereon, of alloys of these metals which we desire to evaporate with another metal which is characterized in that it will also form an alloy with tungsten, tantalum, molybdenum and columbium in the presence of the metal we desire to evaporate.
- -As metals which we have found which may be'used in a relatively small quantity which cause the normally non-wetting metals to wet the metallic filaments we may use iron, nickel, cobalt, platinum or palladium, or several of these together.
- One of the objects of our invention is to provide an improved and satisfactory method or process of evaporating metals which normally do not wet heater filament coils of tungsten, tantalum, molybdenum. or columbium, by alloying the metal so as to cause the metals to wet the coils of such filaments and to coat the coils by capillary attraction so that thermal evaporation can then be carried out.
- Another object oi our invention is to apply to a tungsten, tantalum, molybdenum or columbium filament a metal to be evaporated which does not wet such filament coils, alloyed with a suitable proportion of another metal of the iron or platinum groups which alloys with the filament and brings about a proper wetting or coating of the filament wires by capillary attraction under the influence of heat applied to the filament.
- the alloy element may also be alternatively used in the filament to secure the same objectives, as set forth in our copendlng application, Serial No. 537,676, filed May 27, 1944:.
- the said application hasynow matured into Patent No. 2,413,605 and is dated Dec. 31, 1946.
- a further object of our invention is to apply to a tungsten, tantalum, molybdenum or columbium filament, a metal such as copper, silver, gold, zinc, tin, antimony, cadmium, bismuth, lead, indium or thallium, alloyed with a suitable proportion of another metal which brings about a desirable wetting or coating or the filament metal by capillary attraction under the influence of heat applied to the filament and thus permits thermal I evaporation of the metals.
- a metal such as copper, silver, gold, zinc, tin, antimony, cadmium, bismuth, lead, indium or thallium
- the metal to be evaporated is applied alloyed with another suitable metal providing wetting characteristics to the coils of a filament which may be formed from tungsten, tantalum, molybdenum or columbium.
- a filament which may be formed from tungsten, tantalum, molybdenum or columbium.
- copper, zinc, gallium, or arsenic which are metals of the chemical periodic table arrangement found in series 5 or the metals silver, cadmium, indium, tin and antimony, which include metals of series 7, or the metals gold, thallium, lead and bismuth which in the periodic arrangement include series 11, all of which metals do not wet filaments made of tungsten, tantalum, molybdenum or columbium, we first bring about a satisfactory wetting and adhesion of these metals to the filaments by applying the metals to the filaments as an alloy with small amounts of another metal either selected from the iron group such as iron, nickel or cobalt, or selected from the platinum group metals such as
- the metals copper, silver, and gold constitute a family in the chemical periodic table arrangement.
- the applied metal alloys When the applied metal alloys are thus melted they apparently alloy to some degree with the metal comprising the heater filament wire and by reason of such tendency the molten metals wet the filament wires and by capillary attraction are drawn out over the surface of the coils.
- the molten metal which has thus covered considerable surface of the heated coil and is held thereto by capillary adhesion is thereafter evaporated uniformly from the heater coils to apply a surface coating of a metallic or reflective nature to an article such thermal evaporation of the metal from the diament.
- thermal evaporation may with some of the metals, be carried out at normal pressure but generally e preferably carried out in vacuum chambers Inc to the art and within a high vacuum. which may be of the order of one millimeterdown to to the minus 5 millimeters or better. It is very necessary that the metal to be evaporated wet and coat the coil surfaces in order that the metal will evaporate uniformly in all directions. By securing such wetting action the thermal deposition oi these metals, in addition to being made possible, has been found by our process to give uniform coatinss.
- pieces of the metal to be evaporated and which have been previously alloyed with the metal which brings about the alloying with and wetting of the filament maybe hung onto the loops or coils of the diament.
- Figure 1 is a perspective view, partly broken away, illustrating one suitable apparatus for carrying out our-improved method or process.
- Figure 2 is a perspective view of a fragment of an electric filament showing the application of a suitable metal alloy to several of the coils or convolutions thereof, and illustrating one phase of the method or process of wetting or coating the filament by said alloy;
- Figure 3 is a view similar to Figure 2 showing the filament after the completion of the wetting process by the alloy of Figure 2.
- a suitable work-piece support is for supporting a work piece, such as a plate or piece of glass, plastic, plaster, paper, porcelain, metal, or the like I 4, in upright position.
- an electric filament ll. 7 in the form of a coiled wire made of tungsten, molybdenum, columbium or tantalum whose opposite ends are attached to brackets il mounted upon the supporting posts II and adjustable thereon so as to vary the position or location of the iillzsment II with relation to the upporting base
- the chamber provided by the housing ll may, if desired, be completely evacuated of air through outlet pipe or conduit Illa and have a high vacuum createdtherein by means of suitable air evacuating and vacuum creating means, such as a pump (not shown).
- a metal alloy which may consist of silver, copper or sold or other normally non-wetting metal and approximately 5 to 15% or more of platinum. Pieces of this preformed silver and platinum alloy, or copper and platinum alloy, or gold and platinum alloy. several of which are shown at It, in Figures 1 and 2, are bent and hung on the loops or convolutions Ila of the illsment II in the manner shown.
- the chamber in the chamberof the housing ii the chamber, depending upon the metal being evaporated, may be at atmospheric pressure, or it may be evacuated of air and a vacuum created therein.
- a vacuum of 10 to the minus 3 millimeters or better is created and the filament i6 is then energized and therefore heated so as to melt the alloys and to start in motion the wetting action of the filament by capillary attraction, as explained above.
- the filament I6 is further energized to increase the heat therein, whereby silver, copper, or gold in the coating 20 of the alloy will be thermally evaporated and transferred by deposition to the face or surface of the work piece H which, as shown. is disposed in a position opposite the filament IS.
- the platinum does not evaporate at the temperatures required to evaporate the gold.
- silver or copper and the reflective deposits produced in such cases are of reflective values and otherwise similar to gold. silver and copper mirrors made by evaporating these metals alone from crucibles within a high vacuum.
- pieces of a preformed alloy of silver with to 15% or more of palladium may have been applied to the heater filament coils of tungsten, tantalum, molybdenum or columbium and on heating such coils the alloy melts. wets the filaments, and thereafter in a vacuum the silver evaporates oi! the filament onto the article to be coated and produces a silver mirror of 95 to 98% reflection thereon. The palladium all remains with the filament. Alloys of copper and 5 to 15% or more palladium are similarly useful in preparing copper mirrors and the copper 1 deposits in their reflectivity and color show that no palladium is carried over. Palladium alloys with the other non-wetting metals cause thee to wet the filaments desirably.
- the iron metals are particularly active in alloying with tungsten and tantalum and the alloys produced are of much lower melting point than is true of the pure tungsten or tantalum. Consequently, we have found that where we apply pieces of iron. cobalt, or nickel to such filaments along with the metals to be evaporated, or use these as fine wire winding around such metals, that upon heating the filaments. the iron metals cause rapid melting through the filaments and breakage of the same which stops or interrupts the attempt to carry out a thermal evaporation.
- our improved method or process as preferably being carried out in a vacuumized chamber in which the step of wetting the filament takes place, as does also the step oi thermal evaporation of the metal to eflect its deposition upon the work piece to provide a reflective ,volatile metals.
- a reflective ,volatile metals such as cadmium or zinc
- cadmium or zinc may be carried out under atmospheric conditions of pressure if desired, while employing a suitable inert atmosphere.
Description
Dec. 16, 1947. w. H. COLBERT ETAL PROCESS OF EVAPORATING METALS Original Filed May 27, 1944 I uvvmrons Patented DectlG, i947 2,432,657, PROCESS OF EVA I'QRATING METALS William n. Golbert in Arthur R. Weinrlch, Breckenridge, Pa., assignors to Libbey-Owens- Ford Glass Company, Toledo, Ohio, as corporation of Ohio Original application May 27, 1944, Serial No. I 537,675. Divided and this application August 14, 19%3, Scrial'No. 6390,?58
9 Claims. (Cl, 1117-10?) Our present invention relates to a novel process of evaporating metals. It has to do, more particularly. with the coating or wetting, by capillary attraction, of a filament which, for example may be formed "from a coil of ordinary tungsten wire, tantalum, molybdenum or columbium wire, by various metals in the form of an alloy or difierent alloys, which metal or metals it is desired to evaporate and which in pure form normally do not wet these metallic filaments, and the application of said metals or metal alloys by deposition resulting from thermal evaporation, to the face or surface or an article, such as a piece of glass, porcelain, plaster, metal, plastic, Cellophane, paper or the like, to provide a reflective or metallized surface coating for said article.- The invention also has to do with securing wetting and with thermal evaporation oi such metals from pure tungsten, tantalum, molybdenum, o'r columbium filaments by alloying such filaments by the application to the filaments of the metals desired to be evaporated alloyed with and carrying the elements which we have found it desirable that the filaments be alloyed with. This application is a division of our copending application Serial No. 537,675, filed May 27, 1944. The said application has inow matured into Patent No. 2,413,604 and is dated December 31, 1946.
Methods and apparatus have previously been employed to apply coatings of metals by thermal evaporation to the faces or surfaces of such articles to produce mirrors, reflectors or metallized materials for other purposes. it is desirable to effect the thermal evaporation of the metal, such as silver or aluminum, by applying the metal directly to an electrically enersized and thus heated tungsten or other metallic filament which is preferably located within a vacuumized chamber. The metals which may be used as filaments for such evaporations must obviously be of high melting point and also of low vapor pressure at the elevated temperatures at which the metals applied to the filaments evaporate. .Thus, tungsten. tantalum, molybdenum and columbium have represented the only practical materials for such use. Platinum also has been used to a small degree but its high cost is generally prohibitive. While iron and nickel are In these methods 2 of relatively low vapor pressure. they are of such relatively low melting point that filaments made from them rapidly burn out.
With these filaments many oi the metals can be readily evaporated. Thus, for example, aluminum, beryllium, magnesium, vanadium, barium, strontium, iron, nickel, cobalt, manganese, thorium, chromium and titanium, when applied to filaments of tungsten, tantalum, molybdenum or columbium, will on heating in a vacuum, melt and spread over the filament by capillary attraction and satisfactory evaporation of these metals.
then occurs from the large amount oi surface which the molten metal covers.
However, with a large number of metals which it is desirable to be able to thermally evaporate and which from their vapor pressure at elevated temperatures should readily evaporate, it has been-found dimcult, if not impossible, to carry out satisfactory deposition 0! such coatings by thermal evaporation. Thus, for example, silver while readily lending itself to thermal evaporation from a crucible, cannot be evaporated readily from a coil of tungsten, tantalum, molybdenum or columbium when applied to a filament 01 these metals and heated by electrical resistance. The silver on melting shows no afiinity for the metallic filaments and almost immediately after melting collects into a drop, and falls of! the filament. This lack of ability to wet tungsten, tantalum, molybdenum and columbium occurs also with the metals copper, gold, zinc, tin, antimony, cadmium, bismuth, lead, thallium and indium. with each of these metals the use of the four available coll filaments as a means of evaporating these metals has not been possible, and less desirable means of heating have been necessary where it became necessary to evaporate these under practical conditions repeatedly in the commercial production of mirrors and metallic coated articles. As, each of these metals, after melting, pulls together into droplets and falls oil? the filaments, there has resulted a wastage of the metal whenever it has been attempted to evaporate them from these filaments and there have been continuous tailures of the apparatus to function due to the loss of the metals from the heated wires; and where ny me al. has been evaporated the amounts so 33 evaporated have always been uncertain and without control.
We have found that we may use tungsten, tantalum, molybdenum or columbium as filaments for the evaporation of metals which do not wet these filaments by causing them to wet such filaments by the application to such filaments, or the forming thereon, of alloys of these metals which we desire to evaporate with another metal which is characterized in that it will also form an alloy with tungsten, tantalum, molybdenum and columbium in the presence of the metal we desire to evaporate. -As metals which we have found which may be'used in a relatively small quantity which cause the normally non-wetting metals to wet the metallic filaments we may use iron, nickel, cobalt, platinum or palladium, or several of these together. Thus, for example, we may add small amounts of nickel to silver and when such alloys are melted on a tungsten filament the silver will be found to wet the tungsten filament and to spread itself by capillary attraction over the surface of the tungsten wires. In the absence of the nickel the silver melts, draws itself into a droplet and falls oh the filament wire because it does not wet the same. Not all metals have been found to act in this manner. Alloying the normally non-wetting metals among themselves, such as adding lead to silver, does notseem to bring about any desirable improvement in the wetting characteristic. In each case it is found that the metals of the iron group,
namely, iron, nickel and cobalt. and the metals of the platinum group. namely palladium, platinum, rhodium and iridium readily form alloys with tungsten, tantalum, molybdenum and columbium and also form alloys with copper, silver,
gold, zinc, tin. antimony, cadmium, bismuth, lead, indium and thallium. Thus, the metals of the iron and platinum groups which we have enumerated readily bring about the desired wetting and it appears clearly that this is accomplished through the mutual alloying tendency which these metals possess.
One of the objects of our invention is to provide an improved and satisfactory method or process of evaporating metals which normally do not wet heater filament coils of tungsten, tantalum, molybdenum. or columbium, by alloying the metal so as to cause the metals to wet the coils of such filaments and to coat the coils by capillary attraction so that thermal evaporation can then be carried out.
Another object oi our invention is to apply to a tungsten, tantalum, molybdenum or columbium filament a metal to be evaporated which does not wet such filament coils, alloyed with a suitable proportion of another metal of the iron or platinum groups which alloys with the filament and brings about a proper wetting or coating of the filament wires by capillary attraction under the influence of heat applied to the filament.
As another object of our invention there is provided an improved method or process whereby a metal which is to be evaporated and which does not normally wet heater filaments of tungsten, tantalum, molybdenum and columbium is alloyed with anothermetal such as platinum, palladium, nickel, cobaltor iron, and applied to such a filament, or in which a suitable alloy consisting of one or more of these metals with the metal to be evaporated is applied to such filaments, and by securing a wetting and coating of the filament by capillary attraction of the metal desired to be evaporated may be deposited upon the face '91 provided an improved method or process whereby a metal desired to be evaporated to form a reflective surface coating is applied to a tungsten, tantalum, molybdenum or columhiiim filament as an alloy with another metal whose vaporizing temperature is higher and which metal brings about a wetting and coating of the filament by capil= lary attraction, thus permitting the deposition or" the desired metal upon the face or surface of an article by thermal evaporation without appra ciable evaporation of the added metal so as to give a reflective surface coating showing the characteristic properties of the desired metal only. The alloy element may also be alternatively used in the filament to secure the same objectives, as set forth in our copendlng application, Serial No. 537,676, filed May 27, 1944:. The said application hasynow matured into Patent No. 2,413,605 and is dated Dec. 31, 1946.
. which normally does not wet the heater filament A further object of our invention is to apply to a tungsten, tantalum, molybdenum or columbium filament, a metal such as copper, silver, gold, zinc, tin, antimony, cadmium, bismuth, lead, indium or thallium, alloyed with a suitable proportion of another metal which brings about a desirable wetting or coating or the filament metal by capillary attraction under the influence of heat applied to the filament and thus permits thermal I evaporation of the metals.
Generally speaking. and in accordance with our present invention, the metal to be evaporated is applied alloyed with another suitable metal providing wetting characteristics to the coils of a filament which may be formed from tungsten, tantalum, molybdenum or columbium. Thus, in order to thermally evaporate copper, zinc, gallium, or arsenic, which are metals of the chemical periodic table arrangement found in series 5 or the metals silver, cadmium, indium, tin and antimony, which include metals of series 7, or the metals gold, thallium, lead and bismuth which in the periodic arrangement include series 11, all of which metals do not wet filaments made of tungsten, tantalum, molybdenum or columbium, we first bring about a satisfactory wetting and adhesion of these metals to the filaments by applying the metals to the filaments as an alloy with small amounts of another metal either selected from the iron group such as iron, nickel or cobalt, or selected from the platinum group metals such as platinum, palladium, rhodium or iridium, and then by energizing the filament and thus heating it we cause a melting of the metals. It is, of course, well known that the metals copper, silver, and gold constitute a family in the chemical periodic table arrangement. When the applied metal alloys are thus melted they apparently alloy to some degree with the metal comprising the heater filament wire and by reason of such tendency the molten metals wet the filament wires and by capillary attraction are drawn out over the surface of the coils. The molten metal which has thus covered considerable surface of the heated coil and is held thereto by capillary adhesion is thereafter evaporated uniformly from the heater coils to apply a surface coating of a metallic or reflective nature to an article such thermal evaporation of the metal from the diament. The operations of thermal evaporation may with some of the metals, be carried out at normal pressure but generally e preferably carried out in vacuum chambers Inc to the art and within a high vacuum. which may be of the order of one millimeterdown to to the minus 5 millimeters or better. It is very necessary that the metal to be evaporated wet and coat the coil surfaces in order that the metal will evaporate uniformly in all directions. By securing such wetting action the thermal deposition oi these metals, in addition to being made possible, has been found by our process to give uniform coatinss.
- As will be shown more fully later, pieces of the metal to be evaporated and which have been previously alloyed with the metal which brings about the alloying with and wetting of the filament, maybe hung onto the loops or coils of the diament.
The foregoing and other objects and advantages of the present invention will appear from the following description and appended claims when considered in connection with the accompanying drawings forming a part of this specification wherein similar reference characters designate corresponding parts in the several views.
In said drawings: a
Figure 1 is a perspective view, partly broken away, illustrating one suitable apparatus for carrying out our-improved method or process.
Figure 2 is a perspective view of a fragment of an electric filament showing the application of a suitable metal alloy to several of the coils or convolutions thereof, and illustrating one phase of the method or process of wetting or coating the filament by said alloy; and
Figure 3 is a view similar to Figure 2 showing the filament after the completion of the wetting process by the alloy of Figure 2.
Before explaining in detail the present invention it is to be understood that the invention is not limited in its application to the details of construction and arrangement of parts illustrated in the accompanying drawings, since the invention is capable of other embodiments and of being practiced or carried out in various ways. It is to be understood also that the phraseology or terminology employed herein is for the purpose of description and not of limitation, and it is not intended to limit the invention herein claimed beyond the requirements of the prior art.
Referring now to the drawings, we have shown -a suitable apparatus for carrying out our imsurrounding flange or projection I? which is' adapted to rest upon the top face or surface of the supporting base Iii.
Within the chamber provided by the housing ii, we have shown a suitable work-piece support is for supporting a work piece, such as a plate or piece of glass, plastic, plaster, paper, porcelain, metal, or the like I 4, in upright position.
Located within the chamber and mounted upon the supporting base II, is a pair of upright supporting posts I! between which is carried or supported, in substantially horizontal position, an electric filament ll. 7, in the form of a coiled wire made of tungsten, molybdenum, columbium or tantalum whose opposite ends are attached to brackets il mounted upon the supporting posts II and adjustable thereon so as to vary the position or location of the iillzsment II with relation to the upporting base The chamber provided by the housing ll may, if desired, be completely evacuated of air through outlet pipe or conduit Illa and have a high vacuum createdtherein by means of suitable air evacuating and vacuum creating means, such as a pump (not shown).
In accordance with one method embodying our invention which is to be performed or carried out within the chambered housing ii, we preferably provide a metal alloy which may consist of silver, copper or sold or other normally non-wetting metal and approximately 5 to 15% or more of platinum. Pieces of this preformed silver and platinum alloy, or copper and platinum alloy, or gold and platinum alloy. several of which are shown at It, in Figures 1 and 2, are bent and hung on the loops or convolutions Ila of the illsment II in the manner shown.
It is known that silver, copper and gold lend themselves admirably to thermal evaporation but they have no wetting affinity for tungsten, tantalum, molybdenum or columbium surfaces and therefore silver, copper or gold alone is unsatisfactory for coating the filament it formed from either of these metals by a wetting action effected by capillary attraction. Wetting of the filament wire is essential to secure a maximum of evaporating surfaces to provide evaporation uniformly in all directions, to the securing of uniform deposits, and also to avoid the dropping of the molten metal of! the heater wires. We have found that platinum. while having a higher melting point than gold, copper or silver, readily alloys with silver, gold and copper and the alloys have a wetting ailinity for the four above-mentioned metals, any one of which may be used for making the filament l6, and thus platinum lends itself particularly well to securing the wetting of the filament by capillary attraction. Therefore, by including a certain percentage of platinum, preferably 5% or more, with the silver, copper or gold to form the alloy it, the platinum will serve to bring about wetting or coating of said filament by the molten metal by capillary attraction when the filament is energized and thus heated and will act to cause the silver, copper or gold to also cling to or wet the filament. An early stage or phase of the wetting action of the filament I! by the alloy I8 is shown generally at l8, Figure 2. As the wetting action by capillary attraction continues, the two metals of the alloy will proceed to wet the coils of the filament it and in fact. will substantially wet or coat and cover the surfaces of the filament. In Figure 3, we have illustrated several of the coils or loops iia of the filament as being coated at 20 by the alloy from which the pieces it are formed.
Thus, by including platinum with the silver. copper or gold, as an alloy, it is possible to quickly and effectively coat or wet the filament I 8 by capillary attraction. Since, therefore, the alloybuilds up onto the surfaces of the filament in substantially the manner illustrated in Figure 3, there will be a relatively uniform coating or wetting of The filament, as shown, is
the filament and a uniform dependable evaporation of the silver, copper or gold. I-Ieretofore, when attempts were made to wet the filament by the use of the silver, the copper or the gold alone, only small portions of the molten metal would cling to the filament as droplets hanging from the lower ends of the coils of the filament, with the major portion of the molten metal dropping or falling ofi the coils. This was particularly undesirable since it was practically impossible to produce, by thermal evaporation, an even surface coating by deposition, or to control the deposition to desired coating deposit thicknesses on the surface of an article, such as the article H, to which it was desired to apply a reflective surface coating. By virtue of the fact that the silver, copper or gold did not properly wet the tungsten or other metal filament but had a tendency to. drop oil said filament, the process of coating with these metals by deposition was unsatisfactory, slow and painstaking because only a small portion or percentage of the filament received the metal coating. Considerable shutting down and starting over again was required when most of the gold, silver or copper on first melting dropped off the coils and no evaporation was secured. Thus, great waste occurred, the process was considerably slowed down, and the coating produced by deposition, if any, was uneven or spotty and unsatisfactory because of such uneven character thereof on the surface of the article coated. Commercial production under such uncertain conditions was impossible.
It istobe understood that in carrying out our method or process as described above, in the chamberof the housing ii the chamber, depending upon the metal being evaporated, may be at atmospheric pressure, or it may be evacuated of air and a vacuum created therein. Thus, after the pieces ii of the silver and platinum alloy or copper and platinum alloy or gold and platinum alloy, as the case may be, have been applied to the coils of the filament l6 and the work piece I mounted upon its support I! within the chamber, a vacuum of 10 to the minus 3 millimeters or better, is created and the filament i6 is then energized and therefore heated so as to melt the alloys and to start in motion the wetting action of the filament by capillary attraction, as explained above. After the wetting action has been completed as illustrated generally at 20 in Figure 3, the filament I6 is further energized to increase the heat therein, whereby silver, copper, or gold in the coating 20 of the alloy will be thermally evaporated and transferred by deposition to the face or surface of the work piece H which, as shown. is disposed in a position opposite the filament IS. The platinum does not evaporate at the temperatures required to evaporate the gold. silver or copper and the reflective deposits produced in such cases are of reflective values and otherwise similar to gold. silver and copper mirrors made by evaporating these metals alone from crucibles within a high vacuum.
In a similar way pieces of a preformed alloy of silver with to 15% or more of palladium may have been applied to the heater filament coils of tungsten, tantalum, molybdenum or columbium and on heating such coils the alloy melts. wets the filaments, and thereafter in a vacuum the silver evaporates oi! the filament onto the article to be coated and produces a silver mirror of 95 to 98% reflection thereon. The palladium all remains with the filament. Alloys of copper and 5 to 15% or more palladium are similarly useful in preparing copper mirrors and the copper 1 deposits in their reflectivity and color show that no palladium is carried over. Palladium alloys with the other non-wetting metals cause thee to wet the filaments desirably.
We have found that using amixture of platinum and palladium, such as 5%to 10% of each in alloy with either silver, copper or gold, gives equally as good wetting action as is secured with either alone.
We have also found on the other hand. that if, for example, the loops No of an electric filament or coil i6. such as that shown in Fig. 2, were to have applied thereto pieces of pure silver, or of pure copper, and relatively smallerpieces of some suitable wetting and carrier metals, such as platinum or nickel, that when the coil or filament is energized and thus heated, whereby to cause a melting of the metals. the moltenmetals generally drop oi! the loops before sufllcient alloying of these, and alloying and a wetting of the surfaces of the filament occurs, and that the results are uncertain and losses of evaporations and materials and time occur. This is always the case with the low melting metals such as zinc, cadmium, tin, lead and indium, which nonwettlng metals melt quickly at low temperatures and fall ofi the heater wires or filaments before any appreciable solution or alloying with the higher melting iron or platinum metals occurs. Consequently, with all of the metals we find it necessary and desirable to start with a preformed alloy.
The iron metals are particularly active in alloying with tungsten and tantalum and the alloys produced are of much lower melting point than is true of the pure tungsten or tantalum. Consequently, we have found that where we apply pieces of iron. cobalt, or nickel to such filaments along with the metals to be evaporated, or use these as fine wire winding around such metals, that upon heating the filaments. the iron metals cause rapid melting through the filaments and breakage of the same which stops or interrupts the attempt to carry out a thermal evaporation.
Thus we find it necessary to utilize preformed alloys and with iron, cobalt or nickel, we use preferably 5% or less, by weight, in the alloys with the metal to be evaporated as, for example, silver, and a weight of such metals as low as 0.5% may often effectively be used to bring about satisfactory wetting of the filaments. Thus, in evaporating silver orcopper by the use of an alloy of either with either nickel or iron, we have used alloys very satisfactorily which wet the filaments uniformly in which there was 1% to 2%, by weight, of iron or nickel present on the. weight of the silver or copper. I
The use of our metals such as platinum, palladium, iridium or rhodium to bring about a satisfactory wetting and evaporation has been particularly attractive in that when used with the metals which it has been desired to evaporate. these metals, platinum, palladium, iridium and rhodium have not appreciably evaporated so that the deposits of silver, copper, tin; lead '-or other metals have been secured essentially pure and as mirrors they have shown the full normal reflectivity and colors characteristic of pure mirror deposits of these metals. Thus. with silver From the following table of temperatures at which the vapor pressure of the different metals is 0.01
assaesr millimeters, it is apparent that, as these are also I the boiling or evaporating temperatures in a deposits secured.
Temperatures at which metal boils Melting Metal At 0.01 mm. At 100 mm. normal Pressure atmospheric pressure 2, 200 l, Gill A further advantage of very practical importance in the thermal evaporation of the various metals has been secured through our securing good wetting of the filaments in that the metals being evaporated show very little explosive boiling or spitting which by reason of small chunks of metal blown over onto the article being coated has caused spoilages. This appears to have been accomplished by the decrease of surface tension forces accompanying the wetting and also in the elimination of conditions leading to super-heating by getting the metal to spread out in a thin coating over most of the filament surfaces.
From the foregoing it will be seen that we have provided an improved method or process for applying certain metals to a filament of tungsten, tantalum, molybdenum or columbium by causing a wetting resulting from capillary attraction through the application of other metals and applying heat from the filament, and have thereby been able to carry out evaporation of such metals after the wetting action has been completed by thermally evaporating the metals and have caused their deposition upon the face or surface or a work piece to provide metallized or reflective surface therefor. It will also be seen that while we secure the desirable requisite of wetting of the filaments of tungsten, tantalum, molybdenum or columbium. by metals which normally do not wet these, by the use of a platinum group or iron group metal this may be accomplished in several ways. Thus, we may apply separate pieces of a preformed alloy of such metals with one of our platinum or iron group metals and these will wet the pure metallic filaments.
While we have reierred to the use oi tungsten. tantalum, molybdenum, or columbium as suitable metals from which the coiled filament or element it may be formed, other suitable metals may be used for this purpose. We have mentioned these metals particularly since their high melting points and low vapor pressures at the boiling temperatures of other metals as shown in the above table make these the practically desirable metals for use as such filaments.
We have described our improved method or process as preferably being carried out in a vacuumized chamber in which the step of wetting the filament takes place, as does also the step oi thermal evaporation of the metal to eflect its deposition upon the work piece to provide a reflective ,volatile metals. such as cadmium or zinc, may be carried out under atmospheric conditions of pressure if desired, while employing a suitable inert atmosphere.
Having thus described our invention, what we claim is:
1. The method of producing coatings by evaporation of silver from a filament selected from the group consisting of tungsten, tantalum, molybdenum and columbium, wherein the silver is alloyed with a metal selected from the group consisting of iron, cobalt and nickel, and is heated on said filament and wherein said metal causes the silver to wet, to adhere to, and to'spread out over the filament surfaces and by the continued application of heat, to evaporate and to deposit upon an article to be coated.
2. The method of producing coatings by evaporation of a metal of the silver chemical periodic table family from a filament selected from the group consisting of tungsten, tantalum, molybdenum, and columbium, wherein the metal to be evaporated is alloyed with a metal selected from the group consisting of iron, cobalt and nickel and is heated on said filament, and wherein said selected alloying metal causes the metal desired to be evaporated to wet, to adhere to, and to spread out over the filament surfaces and by the continued application of heat, to evaporate and to deposit upon an article to be coated.
3. The method of producing coatings on articles by evaporationof silver from a filament selected from the group consisting of tungsten, tantalum, molybdenum and columbium, wherein the silver is alloyed with nickel and is heated on said filament and wherein said nickel causes the silver to wet, to adhere to, and to spread out over the filament surfaces and by the continued application of heat, to evaporate and to deposit upon the article to be coated.
4. A method according to claim 3 wherein copper is substituted for the silver.
5. A method according to claim 3 wherein gold is substituted for the silver.
6. A method according to claim 3 wherein the nickel is present in amounts less than 5% b weight.
7. A method according to claim 1 wherein said metal is present in amounts ranging approximately from 0.5% to 5% by weight.
8. A method according to claim 3 wherein the nickel is present in amounts of approximately 1% to 2% by weight.
9. A method according to claim 2 wherein the 11 12 alloyin metal is iron and is present in amounts of approximately 1% w 2% by wemm- STATES WILLIAM H. COLBERT. Number Name Date ARTHUR R. WEINRICH. 2, 1 04 Colbert m. a1, 1948 REFERENCES 0mm 5 01m ems The mom game an of record in th Caldwell. article in Journal or Applied Physics,
' m, of t 9mm v m. 12. N0v.1941,pp.779-7a1,
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US690358A US2432657A (en) | 1944-05-27 | 1946-08-14 | Process of evaporating metals |
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US537675A US2413604A (en) | 1944-05-27 | 1944-05-27 | Method or process of evaporating metals |
US690358A US2432657A (en) | 1944-05-27 | 1946-08-14 | Process of evaporating metals |
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US2432657A true US2432657A (en) | 1947-12-16 |
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Cited By (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2586752A (en) * | 1946-09-26 | 1952-02-19 | Polytechnic Inst Brooklyn | Alloy resistance element and method for manufacturing same |
US2636916A (en) * | 1948-09-14 | 1953-04-28 | Internat Company For Ind Expl | Electrode for galvanic cells |
US2685531A (en) * | 1948-06-28 | 1954-08-03 | Gen Electric | Light-sensitive electron-emissive electrode |
US2719097A (en) * | 1949-05-07 | 1955-09-27 | Alois Vogt | Method for the production of thin continuous surface layers of precious metals |
US2724663A (en) * | 1952-10-23 | 1955-11-22 | Bell Telephone Labor Inc | Plural metal vapor coating |
US2729880A (en) * | 1948-09-23 | 1956-01-10 | Rca Corp | Aluminum oxide semi-conductors |
US2756166A (en) * | 1951-01-27 | 1956-07-24 | Continental Can Co | Vacuum metallizing and apparatus therefor |
US2758510A (en) * | 1949-04-28 | 1956-08-14 | Alois Vogt | Interference filter for sunglasses |
US2787688A (en) * | 1951-07-10 | 1957-04-02 | North Electric Co | Contact material |
US2822301A (en) * | 1952-06-03 | 1958-02-04 | Continental Can Co | Vacuum metallizing and apparatus therefor |
US2839378A (en) * | 1955-04-15 | 1958-06-17 | American Marietta Co | Method of making metal flakes |
US2846650A (en) * | 1952-06-26 | 1958-08-05 | Gen Electric | Light reflecting transducer device |
US2856491A (en) * | 1952-09-27 | 1958-10-14 | North Electric Co | Electrical contact alloy of platinum group metal and zinc and method of making same |
US2859415A (en) * | 1952-09-03 | 1958-11-04 | Bell Telephone Labor Inc | Ultrasonic acoustic wave transmission delay lines |
US2900282A (en) * | 1956-07-20 | 1959-08-18 | Sperry Rand Corp | Method of treating magnetic material and resulting articles |
US2907626A (en) * | 1958-01-15 | 1959-10-06 | Bjorksten Res Lab Inc | Metal coating of glass fibers at high speeds |
US2913813A (en) * | 1955-06-22 | 1959-11-24 | Ohio Commw Eng Co | Composite metal product |
US2975075A (en) * | 1956-02-17 | 1961-03-14 | Norman C Beese | Method of evaporating metals |
US3055089A (en) * | 1958-08-06 | 1962-09-25 | Union Carbide Corp | Gaseous metal product and processes |
US3066042A (en) * | 1959-11-27 | 1962-11-27 | Engelhard Ind Inc | Method of coating metal |
US3217405A (en) * | 1962-06-27 | 1965-11-16 | Nat Res Corp | Plating process |
US3252832A (en) * | 1962-07-10 | 1966-05-24 | Bbc Brown Boveri & Cie | Method of making magnetically hard superconducting wires |
US3392055A (en) * | 1963-02-01 | 1968-07-09 | Gen Electric | Method of making superconducting wire |
US3637421A (en) * | 1969-08-27 | 1972-01-25 | Joseph Paul Gimigliano | Vacuum vapor coating with metals of high vapor pressure |
US4357368A (en) * | 1978-12-26 | 1982-11-02 | Rca Corporation | Method of making a photosensitive electrode and a photosensitive electrode made thereby |
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US2413604A (en) * | 1944-05-27 | 1946-12-31 | Libbey Owens Ford Glass Co | Method or process of evaporating metals |
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US2413604A (en) * | 1944-05-27 | 1946-12-31 | Libbey Owens Ford Glass Co | Method or process of evaporating metals |
Cited By (25)
Publication number | Priority date | Publication date | Assignee | Title |
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US2586752A (en) * | 1946-09-26 | 1952-02-19 | Polytechnic Inst Brooklyn | Alloy resistance element and method for manufacturing same |
US2685531A (en) * | 1948-06-28 | 1954-08-03 | Gen Electric | Light-sensitive electron-emissive electrode |
US2636916A (en) * | 1948-09-14 | 1953-04-28 | Internat Company For Ind Expl | Electrode for galvanic cells |
US2729880A (en) * | 1948-09-23 | 1956-01-10 | Rca Corp | Aluminum oxide semi-conductors |
US2758510A (en) * | 1949-04-28 | 1956-08-14 | Alois Vogt | Interference filter for sunglasses |
US2719097A (en) * | 1949-05-07 | 1955-09-27 | Alois Vogt | Method for the production of thin continuous surface layers of precious metals |
US2756166A (en) * | 1951-01-27 | 1956-07-24 | Continental Can Co | Vacuum metallizing and apparatus therefor |
US2787688A (en) * | 1951-07-10 | 1957-04-02 | North Electric Co | Contact material |
US2822301A (en) * | 1952-06-03 | 1958-02-04 | Continental Can Co | Vacuum metallizing and apparatus therefor |
US2846650A (en) * | 1952-06-26 | 1958-08-05 | Gen Electric | Light reflecting transducer device |
US2859415A (en) * | 1952-09-03 | 1958-11-04 | Bell Telephone Labor Inc | Ultrasonic acoustic wave transmission delay lines |
US2856491A (en) * | 1952-09-27 | 1958-10-14 | North Electric Co | Electrical contact alloy of platinum group metal and zinc and method of making same |
US2724663A (en) * | 1952-10-23 | 1955-11-22 | Bell Telephone Labor Inc | Plural metal vapor coating |
US2839378A (en) * | 1955-04-15 | 1958-06-17 | American Marietta Co | Method of making metal flakes |
US2913813A (en) * | 1955-06-22 | 1959-11-24 | Ohio Commw Eng Co | Composite metal product |
US2975075A (en) * | 1956-02-17 | 1961-03-14 | Norman C Beese | Method of evaporating metals |
US2900282A (en) * | 1956-07-20 | 1959-08-18 | Sperry Rand Corp | Method of treating magnetic material and resulting articles |
US2907626A (en) * | 1958-01-15 | 1959-10-06 | Bjorksten Res Lab Inc | Metal coating of glass fibers at high speeds |
US3055089A (en) * | 1958-08-06 | 1962-09-25 | Union Carbide Corp | Gaseous metal product and processes |
US3066042A (en) * | 1959-11-27 | 1962-11-27 | Engelhard Ind Inc | Method of coating metal |
US3217405A (en) * | 1962-06-27 | 1965-11-16 | Nat Res Corp | Plating process |
US3252832A (en) * | 1962-07-10 | 1966-05-24 | Bbc Brown Boveri & Cie | Method of making magnetically hard superconducting wires |
US3392055A (en) * | 1963-02-01 | 1968-07-09 | Gen Electric | Method of making superconducting wire |
US3637421A (en) * | 1969-08-27 | 1972-01-25 | Joseph Paul Gimigliano | Vacuum vapor coating with metals of high vapor pressure |
US4357368A (en) * | 1978-12-26 | 1982-11-02 | Rca Corporation | Method of making a photosensitive electrode and a photosensitive electrode made thereby |
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