EP0128383B1 - Process for producing wear-resistant layers on the surfaces of components made of titanium or alloys based on titanium - Google Patents
Process for producing wear-resistant layers on the surfaces of components made of titanium or alloys based on titanium Download PDFInfo
- Publication number
- EP0128383B1 EP0128383B1 EP84105503A EP84105503A EP0128383B1 EP 0128383 B1 EP0128383 B1 EP 0128383B1 EP 84105503 A EP84105503 A EP 84105503A EP 84105503 A EP84105503 A EP 84105503A EP 0128383 B1 EP0128383 B1 EP 0128383B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- titanium
- coating
- nickel
- nickel coating
- tini
- 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.)
- Expired
Links
- 239000010936 titanium Substances 0.000 title claims description 29
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims description 23
- 229910052719 titanium Inorganic materials 0.000 title claims description 23
- 238000000034 method Methods 0.000 title claims description 15
- 229910045601 alloy Inorganic materials 0.000 title claims description 3
- 239000000956 alloy Substances 0.000 title claims description 3
- 230000008569 process Effects 0.000 title description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 51
- 229910052759 nickel Inorganic materials 0.000 claims description 24
- 238000000576 coating method Methods 0.000 claims description 16
- 238000009792 diffusion process Methods 0.000 claims description 16
- 239000011248 coating agent Substances 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- XWROUVVQGRRRMF-UHFFFAOYSA-N F.O[N+]([O-])=O Chemical compound F.O[N+]([O-])=O XWROUVVQGRRRMF-UHFFFAOYSA-N 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 230000004913 activation Effects 0.000 claims description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 claims description 2
- 238000005530 etching Methods 0.000 claims description 2
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 claims description 2
- -1 hexafluorosilicic acid Chemical compound 0.000 claims description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 2
- 229910010381 TiNi3 Inorganic materials 0.000 claims 3
- 229910009972 Ti2Ni Inorganic materials 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 239000010410 layer Substances 0.000 description 32
- 229910010380 TiNi Inorganic materials 0.000 description 6
- 239000011241 protective layer Substances 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000008646 thermal stress Effects 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229910001000 nickel titanium Inorganic materials 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002347 wear-protection layer Substances 0.000 description 1
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
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
-
- 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
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/60—After-treatment
Definitions
- the invention relates to a method for producing wear protection layers on surfaces of components made of titanium or titanium-based alloys, by applying a nickel layer adhering to the component surface, subsequent heat treatment to form a diffusion layer and subsequent removal of the residual Ni layer.
- the object of the present invention is to provide a method with which a protective coating layer can be produced, which has a particularly high resistance to friction and erosion and which maintains its intimate connection with the titanium material even under extreme operating conditions.
- the object is achieved in that for the formation of two defined diffusion layers of Ti 2 Ni and TiNi 3 between the titanium base material on the one hand and the nickel layer on the other hand, before the nickel layer is applied, the surface is activated in a bath of chromic acid, hydrofluoric acid and hexafluorosilicic acid and the heat treatment takes place in air or in vacuum at a temperature of 400-600 ° C.
- the components are protected from excessive thermal stresses and therefore from the risk of warping due to the relatively low diffusion temperature.
- Another advantage of the method according to the invention is that the diffusion layers form very uniformly over the entire surface of the titanium component, both with regard to the thickness distribution and with regard to the composition. To this extent, the method according to the invention is suitable for series production, since there is a high degree of reproducibility.
- the activation of the component surface is preceded by an etching of the surface, preferably in a nitric acid-hydrofluoric acid solution.
- the nickel layer is preferably chemically deposited by reacting the titanium surface with a bath of nickel salt, a complexing agent and a chemically reductive agent, for example hypophosphite.
- the TiNi 3 layer should also be removed in addition to the residual nickel layer, so that the Ti 2 Ni layer remains as the top layer.
- the hardness of this layer is still remarkable and is about 600 HV; however, it is more ductile than the TiNi 3 layer.
- both diffusion zones TiNi 3 and Ti 2 Ni are formed in a layer thickness of approx. 4 pm each.
- the layer sequence from outside to inside is: nickel, TiNi 3 , Ti 2 Ni, titanium or titanium material.
- the hardness of the diffusion produced in this way sion layers differ significantly from the starting materials nickel on the one hand and titanium on the other hand, which results from the following hardness table:
- the nickel cover layer or the nickel cover layer and the TiNi 3 layer are removed chemically by the action of HN0 3 or by a nitroaromatic solution (cyanide) at temperatures between 10 and 60 ° C.
- the stripping times are between 15 minutes and 2 hours, depending on the remaining layer thickness of the nickel, the concentration of the stripping bath and the bath temperature.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating Methods And Accessories (AREA)
- Chemically Coating (AREA)
- Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
Description
Die Erfindung bezieht sich auf ein Verfahren zur Herstellung von Verschleißschutzschichten auf Oberflächen von Bauteilen aus Titan oder Titanbasislegierungen, durch Aufbringen einer auf der Bauteiloberfläche haftenden Nickelschicht, anschließende Wärmebehandlung zur Ausbildung einer Diffusionsschicht und nachfolgender Entfernung der Ni-Restschicht.The invention relates to a method for producing wear protection layers on surfaces of components made of titanium or titanium-based alloys, by applying a nickel layer adhering to the component surface, subsequent heat treatment to form a diffusion layer and subsequent removal of the residual Ni layer.
Aufgrund der relativ geringen Verschleißbeständigkeit von Titanwerkstoffen ist es seit geraumer Zeit bekannt, diese mit Oberflächenschutzschichten zu versehen. Es sind chemische und elektrochemische Verfahren zur Beschichtung von Titanwerkstoffen bekannt geworden. So ist es z.B. aus der Druckschrift MTU-Berichte 83/37 der MTU MOTOREN- UND TURBINEN-UNION MÜNCHEN GMBH durch einen Aufsatz von M. Thoma mit dem Titel "Oberflächentechnik von Titan" bekannt, Beschichtungswerkstoffe aus galvanischen Bädern auf der Oberfläche von Titanwerkstoffen abzuscheiden. Es hat sich gezeigt, daß mit diesen Verfahren im allgemeinen haftfeste Schutzschichten erzielt werden können, daß aber bei erhöhter mechanischer oder thermischer Beanspruchung der so beschichteten Bauteile noch größere Haftfestigkeit der Verschleißschutzschichten wünschenswert wäre.Due to the relatively low wear resistance of titanium materials, it has been known for some time to provide them with surface protective layers. Chemical and electrochemical processes for coating titanium materials have become known. So it is e.g. known from the MTU Reports 83/37 publication by MTU MOTOREN- UND TURBINEN-UNION MÜNCHEN GMBH through an article by M. Thoma entitled "Surface technology of titanium" to deposit coating materials from galvanic baths on the surface of titanium materials. It has been shown that, in general, adhesive protective layers can be achieved with these methods, but that with increased mechanical or thermal stress on the components coated in this way, even greater adhesive strength of the wear protective layers would be desirable.
Aus der japanischen Patentanmeldung JP 58-91165 ist ein Verfahren der eingangs genannten Gattung bekannt, bei dem durch die Wärmebehandlung eine Nickeldiffusionsschicht erzeugt wird und eine an der Oberfläche zurückgebliebene Nickelschicht beseitigt wird. Bei der dort offenbarten Beschichtung wird jedoch aufgrund eines hohen Temperaturniveaus und einer langen Dauer der Wärmebehandlung nur eine Diffusionsschicht erzeugt, die relativ große Dicke aufweist. Für extrem beanspruchte Bauteile, wie z.B. Triebwerksbauteile, ist die nach dem vorbekannten Verfahren erzielbare Härte unter Umständen nicht ausreichend, und es besteht darüber hinaus die Gefahr, daß der Übergang zwischen dem Titangrundwerkstoff und der einen Diffusionsschicht zu abrupt erfolgt, was die Gefahr einer Ablösung der Diffusionsschicht in sich birgt. Schließlich ist aufgrund des hohen Temperaturniveaus, bei dem dort die Wärmebehandlung erfolgt, eine Gefährdung der Bauteile durch Wärmeverzug gegeben.From the Japanese patent application JP 58-91165 a method of the type mentioned is known, in which a nickel diffusion layer is generated by the heat treatment and a nickel layer remaining on the surface is removed. In the coating disclosed there, however, due to a high temperature level and a long duration of the heat treatment, only one diffusion layer is produced which has a relatively large thickness. For extremely stressed components, e.g. Engine components, the hardness achievable by the previously known method may not be sufficient, and there is also the risk that the transition between the titanium base material and the one diffusion layer takes place too abruptly, which entails the risk of the diffusion layer becoming detached. Finally, due to the high temperature level at which the heat treatment takes place, there is a risk to the components due to heat distortion.
Aus der Druckschrift "Titanium Sci. Technol., Proc. lnt. Conf., 2nd 1972 (Publ. 1973) 4, Seiten 2487 bis 2499" sind Verfahren zur Wärmebehandlung von mit Nickel beschichteten Titanlegierungen bekannt, bei denen Wärmebehandlungstemperaturen zwischen 400°C und 790°C angewendet werden, um eine Diffusionszone aus Ni, Ni3Ti und NiTi2 auf dem Titangrundwerkstoff zu erzeugen. Bei den dort hergestellten Diffusionsschichten handelt es sich um eine Mischdiffusionsschicht, die jeweils alle drei Werkstoffkomponenten enthält, wobei sich der mengenmäßige Anteil der einzelnen Komponenten nur mit der Entfernung von der Oberfläche ändert.Processes for the heat treatment of nickel-coated titanium alloys are known from the publication "Titanium Sci. Technol., Proc. Lnt. Conf., 2nd 1972 (Publ. 1973) 4, pages 2487 to 2499", in which heat treatment temperatures between 400 ° C. and 790 ° C can be used to create a diffusion zone of Ni, Ni 3 Ti and NiTi 2 on the titanium base material. The diffusion layers produced there are mixed diffusion layers, each containing all three material components, with the quantitative proportion of the individual components only changing with the distance from the surface.
Aufgabe der vorliegenden Erfindung ist es, ein Verfahren anzugeben, mit dem eine Verschließschutzschicht erzeugbar ist, die besonders hohe Widerstandsfähigkeit gegen Reibung und Erosion aufweist und die auch unter extremen Betriebsbedingungen ihre innige Verbindung mit dem Titanwerkstoff beibehält.The object of the present invention is to provide a method with which a protective coating layer can be produced, which has a particularly high resistance to friction and erosion and which maintains its intimate connection with the titanium material even under extreme operating conditions.
Erfindungsgemäß wird Aufgabe dadurch gelöst, daß zur Ausbildung von zwei definierten Diffusionsschichten aus Ti2Ni und TiNi3 zwischen dem Titangrundwerkstoff einerseits und der Nikkelschicht andererseits vor dem Aufbringen der Nickelschicht eine Aktivierung der Oberfläche in einem Bad aus Chromsäure, Flußsäure und Hexafluor-Kieselsäure erfolgt und die Wärmebehandlung in Luft oder im Vakuum bei einer Temperatur von 400-600°C stattfindet.According to the invention, the object is achieved in that for the formation of two defined diffusion layers of Ti 2 Ni and TiNi 3 between the titanium base material on the one hand and the nickel layer on the other hand, before the nickel layer is applied, the surface is activated in a bath of chromic acid, hydrofluoric acid and hexafluorosilicic acid and the heat treatment takes place in air or in vacuum at a temperature of 400-600 ° C.
Durch die Ausbildung zweier definierter Diffusionsschichten, von denen die obere extrem hohe Härte aufweist (bis zu 1000 HV), während die Zwischenschicht aus Ti2Ni eine niedrigere Härte, dafür jedoch entsprechend höhere Duktilität aufweist, wird erreicht, daß ein vollkommen homogener Übergang vom Titangrundkwerkstoff zu der extrem harten Außenschicht besteht und dadurch die gewünschte hohe Widerstandsfähigkeit sowohl gegen Reibung als auch gegen Erosion gewährleistet ist.The formation of two defined diffusion layers, of which the upper one has extremely high hardness (up to 1000 HV), while the intermediate layer made of Ti 2 Ni has a lower hardness but correspondingly higher ductility, ensures that a completely homogeneous transition from the titanium base material to the extremely hard outer layer, thereby ensuring the desired high resistance to both friction and erosion.
Darüber hinaus werden beim erfindungsgemäßen Verfahren die Bauteile aufgrund der relativ niedrigen Diffusionstemperatur vor übergroßen Wärmespannungen und damit vor der Gefahr des Verzugs bewahrt. Ein weiterer Vorteil des erfindungsgemäßen Verfahrens besteht schließlich darin, daß sich die Diffusionsschichten sehr einheitlich über die gesamte Oberfläche des Titanbauteils ausbilden und zwar sowohl bezüglich der Dickenverteilung als auch bezüglich der Zusammensetzung. Insoweit ist das erfindungsgemäße Verfahren für Serienproduktion geeignet, da in hohem Maß Reproduzierbarkeit gegeben ist.In addition, in the method according to the invention, the components are protected from excessive thermal stresses and therefore from the risk of warping due to the relatively low diffusion temperature. Another advantage of the method according to the invention is that the diffusion layers form very uniformly over the entire surface of the titanium component, both with regard to the thickness distribution and with regard to the composition. To this extent, the method according to the invention is suitable for series production, since there is a high degree of reproducibility.
Vorteilhaft ist es, wenn der Aktivierung der Bauteiloberfläche ein Ätzen der Oberfläche vorzugsweise in einer Salpetersäure-Flußsäurelösung vorausgeht.It is advantageous if the activation of the component surface is preceded by an etching of the surface, preferably in a nitric acid-hydrofluoric acid solution.
Eine chemische Abscheidung der Nickelschicht erfolgt vorzugsweise durch Reaktion der Titanoberfläche mit einem Bad aus Nickelsalz, einem Komplexbildner und einem chemisch reduktiven Mittel, beispielsweise Hypophosphit.The nickel layer is preferably chemically deposited by reacting the titanium surface with a bath of nickel salt, a complexing agent and a chemically reductive agent, for example hypophosphite.
Sollen Bauteile mit Versschließschutzschichten versehen werden, die rotierend und/oder schwingend belastet sind, so soll gemäß weiterer Ausbildung der Erfindung zusätzlich zur Nickelrestschicht auch die TiNi3-Schicht abgetragen werden, so daß als Deckschicht die Ti2Ni-Schicht verbleibt. Auch die Härte dieser Schicht ist noch beachtlich und beträgt etwa 600 HV; sie ist jedoch in höherem Maß duktil als die TiNi3-Schicht.If components are to be provided with protective layers which are subject to rotating and / or vibrating loads, then according to a further embodiment of the invention, the TiNi 3 layer should also be removed in addition to the residual nickel layer, so that the Ti 2 Ni layer remains as the top layer. The hardness of this layer is still remarkable and is about 600 HV; however, it is more ductile than the TiNi 3 layer.
Bei einer Wärmebehandlung von 600°C und 8 Stunden Dauer bilden sich beide Diffusionszonen TiNi3 und Ti2Ni in einer Schichtdicke von je ca. 4 pm aus. Die Schichtenfolge von außen nach innen ist dabei: Nickel, TiNi3, Ti2Ni, Titan bzw. Titanwerkstoff. Die Härte der so erzeugten Diffusionsschichten unterscheidet sich sehr wesentlich von den Ausgangswerkstoffen Nickel einerseits und Titan andererseits, was sich aus folgender Härtetabelle ergibt:
Vorteilhaft ist es, wenn das Entfernen der Nikkeldeckschicht oder der Nickeldeckschicht und der TiNi3-Schicht chemisch durch Einwirkung von HN03 oder durch eine Nitroaromatlösung (cyanidisch) bei Temperaturen zwischen 10 und 60°C erfolgt. Dabei liegen die Abziehzeiten je nach der Restschichtdicke des Nickel der Konzentration des Abziehbades und der Badetemperatur zwischen 15 Minuten und 2 Stunden.It is advantageous if the nickel cover layer or the nickel cover layer and the TiNi 3 layer are removed chemically by the action of HN0 3 or by a nitroaromatic solution (cyanide) at temperatures between 10 and 60 ° C. The stripping times are between 15 minutes and 2 hours, depending on the remaining layer thickness of the nickel, the concentration of the stripping bath and the bath temperature.
Claims (5)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3321231A DE3321231C2 (en) | 1983-06-11 | 1983-06-11 | Process for the production of wear protection layers on the surfaces of components made of titanium or titanium-based alloys |
| DE3321231 | 1983-06-11 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0128383A1 EP0128383A1 (en) | 1984-12-19 |
| EP0128383B1 true EP0128383B1 (en) | 1988-11-09 |
Family
ID=6201312
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP84105503A Expired EP0128383B1 (en) | 1983-06-11 | 1984-05-15 | Process for producing wear-resistant layers on the surfaces of components made of titanium or alloys based on titanium |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US4588480A (en) |
| EP (1) | EP0128383B1 (en) |
| DE (1) | DE3321231C2 (en) |
Families Citing this family (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4683648A (en) * | 1984-12-21 | 1987-08-04 | Allied Corporation | Lead-titanium, bipolar electrode in a lead-acid battery |
| GB2188942B (en) * | 1986-04-11 | 1990-04-04 | Rolls Royce Plc | Protective coating |
| DE3716937C1 (en) * | 1987-05-20 | 1987-11-26 | Mtu Muenchen Gmbh | Process for the production of wear protection layers on surfaces of components made of titanium or titanium-based alloys |
| US5300159A (en) * | 1987-12-23 | 1994-04-05 | Mcdonnell Douglas Corporation | Method for manufacturing superplastic forming/diffusion bonding tools from titanium |
| US4970560A (en) * | 1988-12-22 | 1990-11-13 | Xerox Corporation | Lubricated metal cleaning blade for use in dry electrophotographic processes |
| DE3906187C1 (en) * | 1989-02-28 | 1989-10-26 | Mtu Muenchen Gmbh | Titanium alloy component with a protective layer and process for its production |
| DE3926151C1 (en) * | 1989-02-28 | 1990-05-10 | Mtu Muenchen Gmbh | |
| USRE33800E (en) * | 1989-07-03 | 1992-01-21 | United Technologies Corporation | Method for electroplating nickel onto titanium alloys |
| US4902388A (en) * | 1989-07-03 | 1990-02-20 | United Technologies Corporation | Method for electroplating nickel onto titanium alloys |
| JPH03162532A (en) * | 1989-11-20 | 1991-07-12 | Nippon Yakin Kogyo Co Ltd | Manufacture of ni-ti intermetallic compound |
| DE69102553T2 (en) * | 1990-02-09 | 1994-10-20 | Nihon Parkerizing | Process for the surface treatment of titanium-containing metal objects. |
| US5258098A (en) * | 1991-06-17 | 1993-11-02 | Cycam, Inc. | Method of production of a surface adapted to promote adhesion |
| US5616432A (en) * | 1994-06-14 | 1997-04-01 | Ovonic Battery Company, Inc. | Electrochemical hydrogen storage alloys and batteries fabricated from Mg containing base alloys |
| US6800326B1 (en) * | 1997-01-14 | 2004-10-05 | Seiko Epson Corporation | Method of treating a surface of a surface of a substrate containing titanium for an ornament |
| US6463992B1 (en) | 2000-03-22 | 2002-10-15 | Pratt & Whitney Canada Corp. | Method of manufacturing seamless self-supporting aerodynamically contoured sheet metal aircraft engine parts using nickel vapor deposition |
| TW511180B (en) * | 2000-07-31 | 2002-11-21 | Mitsubishi Chem Corp | Mixed acid solution in etching process, process for producing the same, etching process using the same and process for producing semiconductor device |
| US6932897B2 (en) * | 2003-03-03 | 2005-08-23 | Com Dev Ltd. | Titanium-containing metals with adherent coatings and methods for producing same |
| US6913791B2 (en) * | 2003-03-03 | 2005-07-05 | Com Dev Ltd. | Method of surface treating titanium-containing metals followed by plating in the same electrolyte bath and parts made in accordance therewith |
| US8065898B2 (en) | 2008-07-29 | 2011-11-29 | Hamilton Sundstrand Corporation | Method and article for improved adhesion of fatigue-prone components |
| JP2012511411A (en) * | 2008-12-10 | 2012-05-24 | ボストン サイエンティフィック サイムド，インコーポレイテッド | Method for forming a joint between a titanium alloy member and a steel alloy member and a medical device comprising said joint |
| US10687956B2 (en) | 2014-06-17 | 2020-06-23 | Titan Spine, Inc. | Corpectomy implants with roughened bioactive lateral surfaces |
| TWI726940B (en) | 2015-11-20 | 2021-05-11 | 美商泰坦脊柱股份有限公司 | Processes for additively manufacturing orthopedic implants |
| AU2017307558B2 (en) | 2016-08-03 | 2022-08-11 | Titan Spine, Inc. | Implant surfaces that enhance osteoinduction |
| CN111748818B (en) * | 2020-06-30 | 2022-04-26 | 中国航发动力股份有限公司 | Solution and method for quickly removing nickel-cadmium diffusion layer on surface of structural steel |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2946728A (en) * | 1955-06-23 | 1960-07-26 | Cleveland Pneumatic Ind Inc | Adherent electroplating on titanium |
| US3647647A (en) * | 1969-02-19 | 1972-03-07 | United Aircraft Corp | Process for plating titanium |
| US3560274A (en) * | 1969-10-10 | 1971-02-02 | Ibm | Wear-resistant titanium and titanium alloys and method for producing same |
| US4236940A (en) * | 1979-06-12 | 1980-12-02 | United Technologies Corporation | Wear resistant titanium alloy coating |
| DE3133189C2 (en) * | 1981-08-21 | 1984-02-09 | MTU Motoren- und Turbinen-Union München GmbH, 8000 München | "Process for activating titanium surfaces" |
| JPS5891165A (en) * | 1981-11-27 | 1983-05-31 | Fujitsu Ltd | Manufacture of hammer |
-
1983
- 1983-06-11 DE DE3321231A patent/DE3321231C2/en not_active Expired
-
1984
- 1984-05-15 EP EP84105503A patent/EP0128383B1/en not_active Expired
- 1984-05-22 US US06/612,793 patent/US4588480A/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| Titanium Sci. Technolog., Proc. Int. Conf., 2nd. 1972 (Publ. 1973). 4, Seiten 2487-2499 * |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3321231C2 (en) | 1985-10-31 |
| US4588480A (en) | 1986-05-13 |
| DE3321231A1 (en) | 1984-12-13 |
| EP0128383A1 (en) | 1984-12-19 |
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