US3034916A - Method of oxidizing titanium metal - Google Patents
Method of oxidizing titanium metal Download PDFInfo
- Publication number
- US3034916A US3034916A US804557A US80455759A US3034916A US 3034916 A US3034916 A US 3034916A US 804557 A US804557 A US 804557A US 80455759 A US80455759 A US 80455759A US 3034916 A US3034916 A US 3034916A
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- Prior art keywords
- temperature
- layer
- oxidizing
- titanium metal
- magnesium fluoride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims description 14
- 239000010936 titanium Substances 0.000 title claims description 14
- 229910052719 titanium Inorganic materials 0.000 title claims description 14
- 238000000034 method Methods 0.000 title claims description 13
- 230000001590 oxidative effect Effects 0.000 title claims description 12
- 229910052751 metal Inorganic materials 0.000 title claims description 11
- 239000002184 metal Substances 0.000 title claims description 11
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims description 13
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 13
- 230000003647 oxidation Effects 0.000 claims description 11
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 6
- 230000003287 optical effect Effects 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 18
- 239000004408 titanium dioxide Substances 0.000 description 9
- 230000006378 damage Effects 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 208000027418 Wounds and injury Diseases 0.000 description 3
- 208000014674 injury Diseases 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910001922 gold oxide Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000003303 reheating 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
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/10—Oxidising
- C23C8/12—Oxidising using elemental oxygen or ozone
Definitions
- This invention relates to optical devices and their production wherein a layer having a low index of refraction such as a layer of magnesium fluoride or the like is coated with a layer having a high index of refraction such as titanium dioxide. It provides an improved method whereby the multilayer titanium dioxide coating is deposited more rapidly and less expensively than has been possible heretofore.
- Oxidation of a film of titanium metal over an underlying layer having a low index of refraction such as magnesium fluoride in multilayers causes extensive irreparable damage to the low index layer after two hours at 820 F. Four hours at this temperature is usually required for complete oxidation. Gases and vapors absorbed by the low index film almost as soon as it is deposited and trapped when the overlying titanium layer is furnace oxidized at high temperature are believed to produce the damage to the magnesium fluoride layer.
- FIGS. 1 and 2 are perspective and edge views respectively of an optical element with its lower portion broken away.
- FIGS. 3 and 4 are similar views of the same disc with a layer of titanium dioxide thereon but without the gold and copper oxide intervening layers shown in FIG. 2 of Morgan 2,750,832, dated lune 19, 1956.
- FIGS. 5 and 6 show a layer of magnesium fluoride thereon in the usual manner.
- FIGS. 7 and 8 are similar views with a layer of titanium dioxide deposited thereon over the fluoride layer.
- the present invention solves this problem by oxidizing in two steps.
- the first oxidation is continued for approximately thirty-five minutes at about 820 F.
- the coated article is then cooled to a temperature of 400 F. after which the temperature is increased to 820 F. and is maintained at this value until the oxidation is complete.
- the usual time to reach the lower temperature is about forty-five minutes and the usual time to return to the higher temperature is about fifteen minutes. It has been found that oxidation controlled in this manner permits continuing at the high oxidizing temperature for as much as five times the required time without damage to magnesium fluoride layer.
- a method of oxidizing a titanium metal layer in air onto a magnesium fluoride surface having a low index of refraction for an optical device the steps which include preliminarily oxidizing said metal layer at a temperature of the order of 820 F. for a time of the order of 35 minutes, cooling said surface to a temperature of about 400 F. and completing said oxidation at a temperature of the order of 820 F.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Description
y 1962 A. J. ESHNER 3,034,916
METHOD OF OXIDIZING TITANIUM METAL Filed April 6, 1959 2 FIG. 8.
INVENTOR. ALLEN J. ESHNE ATTORNEYS:
hired ates The invention described herein may be manufactured and used by or for the Government for governmental purposes without the payment to me of any royalty thereon.
This invention relates to optical devices and their production wherein a layer having a low index of refraction such as a layer of magnesium fluoride or the like is coated with a layer having a high index of refraction such as titanium dioxide. It provides an improved method whereby the multilayer titanium dioxide coating is deposited more rapidly and less expensively than has been possible heretofore.
in oxidizing these multiple layers of titanium dioxide onto a magnesium fluoride surface it has been heretofore considered necessary but diflicult (1) that the titanium metal be deposited in the same jar of me vacuum system as the underlying film having a low index of 1'61 fraction without breaking the vacuum, and (2) that the magnesium fluoride obtained in one vacuum must not be placed in another vacuum for titanium deposit because gases and vapors absorbed in the magnesium layer, when exposed to air, will remain there to cause serious damage later when the titanium is furnace oxidized. This old method is expensive and time consuming. In accordance with the present invention it is replaced by an improved method which involves furnace oxidizing the titanium metal in air to titanium dioxide, this being accomplished in steps between which the coated object is allowed to cool to a predetermined temperature.
Oxidation of a film of titanium metal over an underlying layer having a low index of refraction such as magnesium fluoride in multilayers causes extensive irreparable damage to the low index layer after two hours at 820 F. Four hours at this temperature is usually required for complete oxidation. Gases and vapors absorbed by the low index film almost as soon as it is deposited and trapped when the overlying titanium layer is furnace oxidized at high temperature are believed to produce the damage to the magnesium fluoride layer.
FIGS. 1 and 2 are perspective and edge views respectively of an optical element with its lower portion broken away.
FIGS. 3 and 4 are similar views of the same disc with a layer of titanium dioxide thereon but without the gold and copper oxide intervening layers shown in FIG. 2 of Morgan 2,750,832, dated lune 19, 1956.
FIGS. 5 and 6 show a layer of magnesium fluoride thereon in the usual manner.
FIGS. 7 and 8 are similar views with a layer of titanium dioxide deposited thereon over the fluoride layer.
In multilayer uses of these layers as beam splitters in an optical device 1, i.e. in which some of the layers transmit and absorb light differently from other layers, the suggestion for a magnesium fluoride layer 3 between layers 2 and 4 of titanium dioxide is not new. This invention may be viewed as a method whereby the titanium may be oxidized more rapidly yet without injury to the magnesium fluoride in absorbed gas.
From these considerations it is evident that the problem to be solved is that of furnace oxidizing titanium metal in air in such a Way as to coat a surface having a low index of refraction with titanium dioxide without injury to the low index surface.
The present invention solves this problem by oxidizing in two steps. The first oxidation is continued for approximately thirty-five minutes at about 820 F. The coated article is then cooled to a temperature of 400 F. after which the temperature is increased to 820 F. and is maintained at this value until the oxidation is complete. The usual time to reach the lower temperature is about forty-five minutes and the usual time to return to the higher temperature is about fifteen minutes. It has been found that oxidation controlled in this manner permits continuing at the high oxidizing temperature for as much as five times the required time without damage to magnesium fluoride layer.
it is of course possible to oxidize the titanium metal onto a layer of material having a low index of refraction at temperatures lower than 820 F. Without injury to the low index surface. It is found, however, that oxidation at these lower temperatures greatly extends the time required to complete the oxidation. As the result of extensive tests it has been found that the herein described oxidizing method reduces the required time to a minimum for the best product. It is to be understood that the temperature of 820 F. may be varied by five degrees in either direction without considerably extending the time required to complete the oxidation. This range of temperatures is hereinafter designated as a tempera-v ture of the order of 820 F.
It is not definitely known why cooling at an intermediate stage in the deposition of the titanium dioxide eliminates the deleterious effect of the gas and vapor in the magnesium fluoride layer. It is possible that at this stage of the operation, the deposit is porous enough to allow the gas and vapor to be driven out by the heat and that the cooling time is such as to permit ejection of the gas and vapor to be completed. However this may be, it is evident that the herein disclosed method is less expensive and involves much less time than the method previously used.
I claim:
-1. In a method of oxidizing a titanium metal layer in air onto a magnesium fluoride surface having a low index of refraction for an optical device, the steps which include preliminarily oxidizing said metal layer at a temperature of the order of 820 F. for a time of the order of 35 minutes, cooling said surface to a temperature of about 400 F. and completing said oxidation at a temperature of the order of 820 F.
2. A method according to claim 1 in which the cooling to about 400 F. is at a rate taking about 45 minutes, the return to 820 F. is at a more rapid rate than the cooling and is at a rate taking about 15 minutes, and the reheating at 820 F. is continued for about 4 hours until oxidation of the titanium is completed.
3. A product of the process of claim 2 in which the magnesium fluoride is substantially freed from gaseous impurities.
References Cited in the file of this patent UNITED STATES PATENTS 2,586,752 Weber et a1. Feb. 19, 1952 2,732,313 Cusano et a1. Ian. 24, 1956 2,750,832 Morgan June 19, 1956 2,789,062 Cusano et a1. Apr. 16, 1957
Claims (1)
1. IN A METHOD OF OXIDIZING A TITANIUM METAL LAYER IN AIR ONTO A MAGNESIUM FLUORIDE SURFACE HAVING A LOW INDEX OF REFRACTION FOR AN OPTICAL DEVICE, THE STEPS WHICH INCLUDE PRELIMINARILY OXIDIZING SAID METAL LAYER AT A TEMPERATURE OF THE ORDER OF 820*F. FOR A TIME OF THE ORDER OF 35 MINUTES, COOLING SAID SURFACE TO A TEMPERATURE OF ABOUT 400*F. AND COMPLETING SAID OXIDATION AT A TEMPERATURE OF THE ORDER OF 820*F.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US804557A US3034916A (en) | 1959-04-06 | 1959-04-06 | Method of oxidizing titanium metal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US804557A US3034916A (en) | 1959-04-06 | 1959-04-06 | Method of oxidizing titanium metal |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3034916A true US3034916A (en) | 1962-05-15 |
Family
ID=25189264
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US804557A Expired - Lifetime US3034916A (en) | 1959-04-06 | 1959-04-06 | Method of oxidizing titanium metal |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3034916A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3722977A (en) * | 1971-08-30 | 1973-03-27 | Beckman Instruments Inc | Optical scattering filter |
| US3971869A (en) * | 1973-03-05 | 1976-07-27 | Optical Coating Laboratory, Inc. | Liquid crystal display device and method |
| US4072782A (en) * | 1976-01-07 | 1978-02-07 | Westinghouse Electric Corporation | Composite erosion resistant optical window |
| US6143358A (en) * | 1998-10-01 | 2000-11-07 | Nanofilm, Ltd. | Hydrophobic thin films on magnesium fluoride surfaces |
| WO2003045865A1 (en) * | 2001-11-21 | 2003-06-05 | Optical Coating Laboratory, Inc. | Glass panel with barrier coating and related methods |
Citations (4)
| 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 |
| US2732313A (en) * | 1956-01-24 | Titanium | ||
| US2750832A (en) * | 1951-06-08 | 1956-06-19 | Libbey Owens Ford Glass Co | Electrically conducting filters and mirrors |
| US2789062A (en) * | 1952-04-03 | 1957-04-16 | Gen Electric | Transparent fluoride luminescent screen and method for preparing same |
-
1959
- 1959-04-06 US US804557A patent/US3034916A/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2732313A (en) * | 1956-01-24 | Titanium | ||
| US2586752A (en) * | 1946-09-26 | 1952-02-19 | Polytechnic Inst Brooklyn | Alloy resistance element and method for manufacturing same |
| US2750832A (en) * | 1951-06-08 | 1956-06-19 | Libbey Owens Ford Glass Co | Electrically conducting filters and mirrors |
| US2789062A (en) * | 1952-04-03 | 1957-04-16 | Gen Electric | Transparent fluoride luminescent screen and method for preparing same |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3722977A (en) * | 1971-08-30 | 1973-03-27 | Beckman Instruments Inc | Optical scattering filter |
| US3971869A (en) * | 1973-03-05 | 1976-07-27 | Optical Coating Laboratory, Inc. | Liquid crystal display device and method |
| US4072782A (en) * | 1976-01-07 | 1978-02-07 | Westinghouse Electric Corporation | Composite erosion resistant optical window |
| US6143358A (en) * | 1998-10-01 | 2000-11-07 | Nanofilm, Ltd. | Hydrophobic thin films on magnesium fluoride surfaces |
| US6472073B1 (en) | 1998-10-01 | 2002-10-29 | Nanofilm Ltd. | Hydrophobic thin films on magnesium fluoride surfaces |
| WO2003045865A1 (en) * | 2001-11-21 | 2003-06-05 | Optical Coating Laboratory, Inc. | Glass panel with barrier coating and related methods |
| US6730373B2 (en) * | 2001-11-21 | 2004-05-04 | Optical Coating Laboratory, Inc. | Glass panel with barrier coating and related methods |
| US20040134233A1 (en) * | 2001-11-21 | 2004-07-15 | Optical Coating Laboratory, Inc. | Method of applying barrier coatings to glass panels |
| US6857290B2 (en) * | 2001-11-21 | 2005-02-22 | Jds Uniphase Corporation | Method of applying barrier coatings to glass panels |
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