EP0858520A1 - A method for coating titanium and titanium alloys with ceramics - Google Patents

A method for coating titanium and titanium alloys with ceramics

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Publication number
EP0858520A1
EP0858520A1 EP97917326A EP97917326A EP0858520A1 EP 0858520 A1 EP0858520 A1 EP 0858520A1 EP 97917326 A EP97917326 A EP 97917326A EP 97917326 A EP97917326 A EP 97917326A EP 0858520 A1 EP0858520 A1 EP 0858520A1
Authority
EP
European Patent Office
Prior art keywords
titanium
coating
silver
layer
ceramics
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP97917326A
Other languages
German (de)
French (fr)
Inventor
Jorma Kivilahti
Mauno Könönen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
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Filing date
Publication date
Application filed by Individual filed Critical Individual
Publication of EP0858520A1 publication Critical patent/EP0858520A1/en
Withdrawn legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
    • A61C8/00—Means to be fixed to the jaw-bone for consolidating natural teeth or for fixing dental prostheses thereon; Dental implants; Implanting tools
    • A61C8/0012—Means to be fixed to the jaw-bone for consolidating natural teeth or for fixing dental prostheses thereon; Dental implants; Implanting tools characterised by the material or composition, e.g. ceramics, surface layer, metal alloy
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
    • A61C13/00—Dental prostheses; Making same
    • A61C13/0003—Making bridge-work, inlays, implants or the like
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
    • A61C8/00—Means to be fixed to the jaw-bone for consolidating natural teeth or for fixing dental prostheses thereon; Dental implants; Implanting tools
    • A61C8/0012—Means to be fixed to the jaw-bone for consolidating natural teeth or for fixing dental prostheses thereon; Dental implants; Implanting tools characterised by the material or composition, e.g. ceramics, surface layer, metal alloy
    • A61C8/0013—Means to be fixed to the jaw-bone for consolidating natural teeth or for fixing dental prostheses thereon; Dental implants; Implanting tools characterised by the material or composition, e.g. ceramics, surface layer, metal alloy with a surface layer, coating
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/84—Preparations for artificial teeth, for filling teeth or for capping teeth comprising metals or alloys
    • A61K6/844—Noble metals
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28—Materials for coating prostheses
    • A61L27/30—Inorganic materials
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals

Definitions

  • the invention relates to a method for coating titanium or titanium alloy based medical and dental implants, prostheses and their parts with ceramics.
  • Metal-ceramic restorations have been increasingly used in dentistry since the 1960s.
  • the metal framework for this kind of dental crowns and bridges has usually been made of gold alloys containing different amounts of platinum and palladium. The results have been good regarding the durability and biological combatibility of the framework material.
  • a significant drawback has also been the high price of the noble metals used. Therefore transition metal alloys like Co- Cr- and Ni-Cr-alloys have been used.
  • titanium has made a breakthrough in odontology especially as regards the success of clinical application of artificial tooth roots, i.e. dental implants.
  • Reasons for that have been the good strength- and corrosion properties of titanium and its excellent compatibility with the living tissues.
  • Titanium's good corrosion properties and excellent biocompatibility are due to the thick and very stable oxide layer on the surface of the bulk metal.
  • the good biocompatibility of titanium has led to several attempts to develop methods to apply the use of titanium also to the production of dental prostheses, above all crowns and bridges.
  • the framework of crowns and bridges will be coated with several layers of porcelain giving natural tooth outlook and a hard functional surface which tolerates high biting forces.
  • the coating with porcelain occurs by sintering suitable mineral powders, eg. of three layers of different powders, onto the surface of the given metal framework.
  • the first layer forms an opaque layer on the surface ofthe metal
  • the second layer gives to the metal framework the desired dental bone hue
  • the outmost transparent layer after glazing gives the impression of tooth luster
  • the sintering occurs around temperatures of 750 °C
  • the ceramic powders contain usually mainly silicon dioxide (Si ⁇ 2) and/or aluminium oxide (AkOs)
  • titanium its weakness is the tendency to dissolve great amounts of several gaseous species, mainly oxygen, hydrogen and nitrogen
  • gaseous species mainly oxygen, hydrogen and nitrogen
  • titanium 's great tendency to dissolve great amounts of oxygen (ab 33 %) and its affinity to silicon in the firing temperatures generates, when sintering with Si ⁇ 2 -based ceramics, a proportionally thick reaction layer composed of titanium and solid solution of titanium and oxygen ⁇ -Ti(O)3, and above of it a layer composed of titanium and silicon, i.e TisSi3(O)
  • titanium silicides are also brittle compounds
  • These brittle interlayers have the effect that the joint between titanium and porcelain is mechanically weak and during the cooling, thermal stresses induce crack formation in the reaction layer parallel to the metal surface
  • the aim of the present invention is to bring into use a method to coat titanium and especially dental crowns and bridges of titanium with ceramics, e.g with Si ⁇ 2-based porcelain, which lacks of the drawbacks related to the previous technics
  • the method according to the invention is characterised by, what is presented in the first claim.
  • the weaknesses of the known technics in the coating of titanium with eg. Si-based porcelain powders are due to the ability of titanium to dissolve great amounts of oxygen at the sintering temperatures and to the activity of titanium and silicon to form brittle intermetallic compounds.
  • the natural oxide layer of titaniun should be removed, and access of oxygen to the surface of titanium and the chemical reactions between titanium and silicon hindered as far as possible.
  • the solution according to the present invention is to coat titanium before sintering with a thin layer of metal which accomplishes these requirements.
  • the metal in question should be soft enough to relax the thermal stresses which due to the differences in thermal expansion coefficients of titanium and porcelain are created during the cooling phase after sintering. Rapid temperature changes are possible also when using these prosthetic devices.
  • the interlayer composed of gold or ceramics according to the known revisits does not fulfil these requirements.
  • the present invention is based on extensive research, which for the first time revealed that the soft nobel metal silver (Ag) is the only metal that fulfils all the requirements needed for a well functioning interlayer. Compared eg with gold silver reacts very sluggishly with titanium at the sintering temperatures. This is caused by the comparatively low driving force ofthe reaction between silver and titanium. The reaction rate between titanium and silver is, however, enough to quarantee good attachment of silver layer to the surface of titanium Another good property of silver is titanium ' s low diffusion rate in it. During sintering titanium is diffused through the silver layer just enough to create preconditions for good attachment of porcelain onto the silver layer. Being a soft and having the best thermal conductivity, silver metal is suitable to relax effectively temperature variation dependant stresses in the porcelain-titanium joint.
  • the coating method of titanium according to the present invention contains, eg. in the manufacture of metalloceramic dental crown, the following stages
  • Stage 1 The surfaces to be coated will be roughened with sandblasting in order to obtain a bigger, mechanically better interlocking surface which improves the strength of the joint
  • Stage 2 The oxide layer is removed from the surface ofthe titanium by treating titanium to be coated about 5 minutes in concentrated hydrochloric acid in the temperature of +95 °C
  • Stage 3 Electrolytic presilvering in silver-kaliumsyanide water solution in the temperature of +18 °C during 2 minutes.
  • Stage 4 The actual silvering occurs in the same solution as the presilvering, the silver syanide concentration of the solution is only increased The thickness of the silver layer is adjusted by current density and time to ab. 10 ⁇ m. In both cases a 99% pure silver plate is used as an anode
  • Stage 5 The sintering of porcelain layers onto the silver plated titanium surface occurs in several stages First is to be coated the opaque layer, then the dental bone imitating layer and finally the luster layer which will be glazed. The sintering ofthe ceramic layers occurs at temperatures around 750°C
  • the bending test results obtained with the specimen coated according to the present invention fulfil the requirements of the above mentioned standards and are clearly and significantly (p ⁇ 0.001) better than the results obtained by the specimen coated according to the known technics.

Landscapes

  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Epidemiology (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • Ceramic Engineering (AREA)
  • Orthopedic Medicine & Surgery (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Electrochemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Plastic & Reconstructive Surgery (AREA)
  • Transplantation (AREA)
  • Dermatology (AREA)
  • Inorganic Chemistry (AREA)
  • Dental Preparations (AREA)

Abstract

The invention relates to a method for coating medical as well as dental titanium or titanium alloy implants, prosthesis and their parts with ceramics. It is characteristic for the invention that metallic surfaces of implants, prosthesis and their parts are coated with a thin layer of electrochemical silver (Ag). It is also in accordance with the invention to overcoat the silver layer with one of the following metals: gold, platinum, palladium, tin or indium.

Description

A method for coating titanium and titanium alloys with ceramics
The invention relates to a method for coating titanium or titanium alloy based medical and dental implants, prostheses and their parts with ceramics.
Metal-ceramic restorations have been increasingly used in dentistry since the 1960s. The metal framework for this kind of dental crowns and bridges has usually been made of gold alloys containing different amounts of platinum and palladium. The results have been good regarding the durability and biological combatibility of the framework material. Recently it has been reported sensitivity and allergic reactions caused by these metals, and even gold has been pointed out to be a possible cause for these reactions. A significant drawback has also been the high price of the noble metals used. Therefore transition metal alloys like Co- Cr- and Ni-Cr-alloys have been used.
During the last two decades titanium has made a breakthrough in odontology especially as regards the success of clinical application of artificial tooth roots, i.e. dental implants. Reasons for that have been the good strength- and corrosion properties of titanium and its excellent compatibility with the living tissues. There are no reports of sensitivity or allergic reactions between oral cavity tissues and titanium. Titanium's good corrosion properties and excellent biocompatibility are due to the thick and very stable oxide layer on the surface of the bulk metal. The good biocompatibility of titanium has led to several attempts to develop methods to apply the use of titanium also to the production of dental prostheses, above all crowns and bridges. The low price of titanium, one percent of that of gold, has encouraged these efforts.
The framework of crowns and bridges will be coated with several layers of porcelain giving natural tooth outlook and a hard functional surface which tolerates high biting forces. The coating with porcelain occurs by sintering suitable mineral powders, eg. of three layers of different powders, onto the surface of the given metal framework. The first layer forms an opaque layer on the surface ofthe metal, the second layer gives to the metal framework the desired dental bone hue and the outmost transparent layer after glazing gives the impression of tooth luster The sintering occurs around temperatures of 750 °C The ceramic powders contain usually mainly silicon dioxide (Siθ2) and/or aluminium oxide (AkOs)
Besides the good properties of titanium, its weakness is the tendency to dissolve great amounts of several gaseous species, mainly oxygen, hydrogen and nitrogen First of all titanium's great tendency to dissolve great amounts of oxygen (ab 33 %) and its affinity to silicon in the firing temperatures generates, when sintering with Siθ2 -based ceramics, a proportionally thick reaction layer composed of titanium and solid solution of titanium and oxygen α-Ti(O)3, and above of it a layer composed of titanium and silicon, i.e TisSi3(O) It is well known, that a few percent of dissolved oxygen makes titanium very brittle. Titanium silicides are also brittle compounds These brittle interlayers have the effect that the joint between titanium and porcelain is mechanically weak and during the cooling, thermal stresses induce crack formation in the reaction layer parallel to the metal surface
Attempts have been made to avoid the weaknesses related to the coating of titanium with ceramics by using vacuum during sintering, using coating ceramics with low sintering temperatures, and by using metallic interlayers
Eg in dentistry the durability of the ceramic coating on titanium has clearly been improved by using gold or a special ceramics as an interlayer The application of gold or special ceramics as an interlayer causes several drawbacks, which tend to weaken the bond between the porcelain and the titamiun framework In the case of gold the main reason for these drawbacks is the tendency of gold and titanium to form brittle intermetallic compounds with each other and the high diffusion rate of titanium in gold This leads to formation of several layers of brittle chemical compounds of variable compositions The most of the benefits aimed at with the use of gold has thus been lost The use of the ceramic interlayers leads also to the formation of brittle compounds and thus to the problems described above
The aim of the present invention is to bring into use a method to coat titanium and especially dental crowns and bridges of titanium with ceramics, e.g with Siθ2-based porcelain, which lacks of the drawbacks related to the previous technics The method according to the invention is characterised by, what is presented in the first claim.
The following presents the benefits of the method according to the present invention compared with the methods of the known technics. As it has become obvious from the above the weaknesses of the known technics in the coating of titanium with eg. Si-based porcelain powders are due to the ability of titanium to dissolve great amounts of oxygen at the sintering temperatures and to the activity of titanium and silicon to form brittle intermetallic compounds. To avoid these difficulties, the natural oxide layer of titaniun should be removed, and access of oxygen to the surface of titanium and the chemical reactions between titanium and silicon hindered as far as possible. The solution according to the present invention is to coat titanium before sintering with a thin layer of metal which accomplishes these requirements. The metal in question should be soft enough to relax the thermal stresses which due to the differences in thermal expansion coefficients of titanium and porcelain are created during the cooling phase after sintering. Rapid temperature changes are possible also when using these prosthetic devices. The interlayer composed of gold or ceramics according to the known tehnics does not fulfil these requirements.
The present invention is based on extensive research, which for the first time revealed that the soft nobel metal silver (Ag) is the only metal that fulfils all the requirements needed for a well functioning interlayer. Compared eg with gold silver reacts very sluggishly with titanium at the sintering temperatures. This is caused by the comparatively low driving force ofthe reaction between silver and titanium. The reaction rate between titanium and silver is, however, enough to quarantee good attachment of silver layer to the surface of titanium Another good property of silver is titanium's low diffusion rate in it. During sintering titanium is diffused through the silver layer just enough to create preconditions for good attachment of porcelain onto the silver layer. Being a soft and having the best thermal conductivity, silver metal is suitable to relax effectively temperature variation dependant stresses in the porcelain-titanium joint.
The following presents a detailed description of one method according to the present invention for coating titanium with silicon based porcelain powders and comparative test results obtained with test specimen according to ISO 9693 - and DIN 13279 standards coated with the method of the present invention and compared with the methods of known technics
For the coating of titanium it is important that the interlayer of silver is deposited onto the pure metallic titanium surface
The coating method of titanium according to the present invention contains, eg. in the manufacture of metalloceramic dental crown, the following stages
Stage 1 The surfaces to be coated will be roughened with sandblasting in order to obtain a bigger, mechanically better interlocking surface which improves the strength of the joint
Stage 2 The oxide layer is removed from the surface ofthe titanium by treating titanium to be coated about 5 minutes in concentrated hydrochloric acid in the temperature of +95 °C
Stage 3 : Electrolytic presilvering in silver-kaliumsyanide water solution in the temperature of +18 °C during 2 minutes.
Stage 4 The actual silvering occurs in the same solution as the presilvering, the silver syanide concentration of the solution is only increased The thickness of the silver layer is adjusted by current density and time to ab. 10 μm. In both cases a 99% pure silver plate is used as an anode
Stage 5: The sintering of porcelain layers onto the silver plated titanium surface occurs in several stages First is to be coated the opaque layer, then the dental bone imitating layer and finally the luster layer which will be glazed. The sintering ofthe ceramic layers occurs at temperatures around 750°C
It is also accordig to the present invention to use metals like gold, platinum, palladium or tin as coating material above the silver layer. It is also according to present invention to vary the composition of the electrolytic bath used in the coating processes, the current rate and the holding time depending on the size and form ofthe item to be coated. Table 1 presents the results of the bending tests obtained with the specimen coated by the method of the present invention and by the methods of the known technics. The bending tests have been carried out according to standards ISO 9693 and DIN 13267 The results are averages of 10 tests. The standard deviations of the test results are presented in brackets
Table 1.
Specimen Breaking force, MPa
Coating according to inv 55,4 (3,2)
Ceramic interlayer 42,4 (6, 1)
No interlayer 36,4 (4,4)
The bending test results obtained with the specimen coated according to the present invention fulfil the requirements of the above mentioned standards and are clearly and significantly (p<0.001) better than the results obtained by the specimen coated according to the known technics.

Claims

Claims
1. A method for coating titanium or titanium alloys with ceramics wherein the method comprises that a silver layer is deposited on the titanium or titanium alloy surface before coating it with ceramics.
2. A method according to 1 wherein the silver layer is deposited on the titanuim or titanium alloy surfac by using an electrochemical method
3. A coating method according to claim 1 wherein the thickness of the silver layer is 1-50 μm, more favorably 1 -20 μm.
4. A coating method according to claim 3 wherein another metal layer consisting of one of the following metals: gold, platinum, palladium, indium or tin is deposited onto the silver layer.
AMENDED CLAIMS
[received by the International Bureau on 16 September 1997 ( 16.09.97 ) ; origi nal claims 1 -4 replaced by amended claims 1-4 ( 1 page) ]
1. A method for coating protheses used in medicine or dentistry with ceramics wherein the method comprises that a silver layer is deposited chemically or electrochemically on titanium or titanium alloy surface before coating them with ceramics.
2. A coating method according to claim 1 wherein the thickness of the silver layer is 1-50 μm, preferably in the range of 1-20 μm.
3. A coating method according to claim 1 wherein another metal layer composing of one of the following metals: gold, platinum, palladium, indium or tin is deposited onto the silver layer.
4. A coating method according to claim 1 wherein the method contains the following stages:
Stage 1 : The surfaces to be coated will be roughened by sandblasting in order to obtain a larger, mechanically better interlocking surface which increases the strength of tiie joint. Stage 2: The surface oxide layer of titanium is removed immersing the titanium into the concentrated hydrochloride acid (HCI) at the temperature of +95 °C for about 5 minutes. Stage 3: Electrolytic presilver-coating occurs in water-based silver- and potassiumcyanide solution at the temperature of +18 °C for 2 minutes.
Stage 4: The actual silver-coating is produced in the presilver-coating solution after increasing its silvercyanide concentration. About 10 μm thick silver layer is fabricated by adjusting the current density and deposition time. In both cases 99% pure silver is used as an anode. Stage 5: The sintering of porcelain layers onto the silver- plated titanium surface is performed in several stages: firstly the opaque layer, secondly, the dental bone imitating layer and finally the luster layer which is glazed. The sintering of the ceramic layers is carried out at the temperatures of about 750°C.
EP97917326A 1996-04-19 1997-04-21 A method for coating titanium and titanium alloys with ceramics Withdrawn EP0858520A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FI961728 1996-04-19
FI961728A FI961728A (en) 1996-04-19 1996-04-19 Process for coating titanium and titanium alloys with ceramics
PCT/FI1997/000244 WO1997040209A1 (en) 1996-04-19 1997-04-21 A method for coating titanium and titanium alloys with ceramics

Publications (1)

Publication Number Publication Date
EP0858520A1 true EP0858520A1 (en) 1998-08-19

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EP97917326A Withdrawn EP0858520A1 (en) 1996-04-19 1997-04-21 A method for coating titanium and titanium alloys with ceramics

Country Status (3)

Country Link
EP (1) EP0858520A1 (en)
FI (1) FI961728A (en)
WO (1) WO1997040209A1 (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2832427B1 (en) * 2001-11-16 2004-03-19 A R V PROCESS FOR THE SURFACE TREATMENT OF TITANIUM AND ITS ALLOYS, PRODUCTS OBTAINED, AND DENTAL APPLICATIONS
US6994550B2 (en) * 2002-12-23 2006-02-07 Nano-Write Corporation Vapor deposited titanium and titanium-nitride layers for dental devices
KR100845156B1 (en) 2007-03-14 2008-07-09 주식회사 금강기건 Abutment screw
SE545102C2 (en) 2018-04-25 2023-04-04 Bactiguard Ab A surface coating for use in the prophylaxis of allergy
JP7441508B2 (en) * 2020-08-19 2024-03-01 日歯研株式会社 Antibacterial partial denture and its manufacturing method

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59232693A (en) * 1983-06-17 1984-12-27 Ngk Spark Plug Co Ltd Clad brazing filler metal for joining ceramics and metal or the like and composite body composed of ceramics and metal or the like using said brazing filler metal
JPS6272472A (en) * 1985-09-27 1987-04-03 Hitachi Ltd Joining method for ceramics and metal or the like
EP0380200A1 (en) * 1989-01-11 1990-08-01 Sumitomo Special Metals Co., Ltd. Composite foil brazing material
US5372298A (en) * 1992-01-07 1994-12-13 The Regents Of The University Of California Transient liquid phase ceramic bonding

Non-Patent Citations (1)

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Title
See references of WO9740209A1 *

Also Published As

Publication number Publication date
WO1997040209A1 (en) 1997-10-30
FI961728A0 (en) 1996-04-19
FI961728A (en) 1997-10-20

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