DE3741292A1 - Process for producing hard multi-ply layers - Google Patents
Process for producing hard multi-ply layersInfo
- Publication number
- DE3741292A1 DE3741292A1 DE19873741292 DE3741292A DE3741292A1 DE 3741292 A1 DE3741292 A1 DE 3741292A1 DE 19873741292 DE19873741292 DE 19873741292 DE 3741292 A DE3741292 A DE 3741292A DE 3741292 A1 DE3741292 A1 DE 3741292A1
- Authority
- DE
- Germany
- Prior art keywords
- layer
- layers
- substrate
- thick
- cvd
- 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.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 41
- 230000008569 process Effects 0.000 title abstract description 13
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 14
- 239000000758 substrate Substances 0.000 claims abstract description 13
- 230000003647 oxidation Effects 0.000 claims abstract description 12
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 12
- 238000005240 physical vapour deposition Methods 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 claims description 2
- 150000004767 nitrides Chemical class 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 53
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ZVWKZXLXHLZXLS-UHFFFAOYSA-N zirconium nitride Chemical compound [Zr]#N ZVWKZXLXHLZXLS-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 238000007733 ion plating Methods 0.000 description 2
- 101100346656 Drosophila melanogaster strat gene Proteins 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- CPABTABABZJYRL-UHFFFAOYSA-N [O-2].[Zr+4].[Ta+5] Chemical compound [O-2].[Zr+4].[Ta+5] CPABTABABZJYRL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000005662 electromechanics Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0635—Carbides
-
- 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
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0641—Nitrides
-
- 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
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0664—Carbonitrides
-
- 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
- C23C14/58—After-treatment
-
- 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
- C23C14/58—After-treatment
- C23C14/5846—Reactive treatment
- C23C14/5853—Oxidation
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/56—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/34—Anodisation of metals or alloys not provided for in groups C25D11/04 - C25D11/32
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Chemical Vapour Deposition (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Physical Vapour Deposition (AREA)
Abstract
Description
Die Erfindung betrifft ein Verfahren zur Herstellung von Schichten auf einem Substrat mittels des CVD-(Chemical Vapour Deposition) oder PVD-(Physical Vapour Deposition) Verfahrens.The invention relates to a method for producing Layers on a substrate using the CVD (Chemical Vapor Deposition) or PVD- (Physical Vapor Deposition) Procedure.
Die Herstellung von Schichten, insbesondere Verschleiß- Schutzschichten unter Anwendung der bekannten PVD/CVD Verfahren ist seit langem bekannt und wird in allen mög lichen Bereichen zur Verschleißminderung von Werkzeugen, Bauteilen und auch zur Verhinderung von deren Korrosion durchgeführt. Generell kann gesagt werden, daß Verschleiß überall dort stattfindet, wo in Berührung befindliche Flächen reibend gegeneinander bewegt werden und/oder wo korrosive Medien auf ungeschützte Flächen einwirken.The production of layers, especially wear Protective layers using the well-known PVD / CVD Process has long been known and is possible in all areas for wear reduction of tools, Components and also to prevent their corrosion carried out. Generally it can be said that wear takes place wherever there is contact Surfaces are rubbed against each other and / or where Affect corrosive media on unprotected surfaces.
Die mittels den vorerwähnten bekannten Verfahren herge stellten Verschleiß- bzw. Korrosionsschutzschichten wei sen bestimmte physikalische und chemische Eigenschaften auf, die grundsätzlich bekannt sind, ebenso wie deren spezielle Nachteile, die bisweilen das eine, das andere oder beide Verfahren ausschließen, wenn es um bestimmte physikalische und chemische Eigenschaft geht, die diese Schichten für bestimmte Anwendungen haben müssen. Ein gesondert zu erwähnender wesentlicher Nachteil der Schich ten, die mit den bekannten CVD-/PVD Verfahren hergestellt werden, besteht darin, daß die damit hergestellten Schich ten zwar hartfest sind, jedoch den erheblichen Nachteil haben, daß diese nicht porenfrei sind.Herge by means of the known methods mentioned above put wear and corrosion protection layers white certain physical and chemical properties that are basically known, as well as theirs special disadvantages, sometimes one or the other or exclude both procedures when it comes to certain physical and chemical property that goes Must have layers for certain applications. A A major disadvantage of the Schich to be mentioned separately ten, which are produced with the known CVD / PVD processes be, is that the layer produced with it ten are hard-wearing, but the considerable disadvantage have that these are not pore-free.
Es ist offensichtlich, daß für bestimmte Anwendungsfälle, in denen neben der hochharten Eigenschaft der Oberfläche auch noch deren absolute Geschlossenheit gewünscht wird, Poren in der Oberfläche unakzeptabel sind, so daß die bekannten Verfahren grundsätzlich für die Herstellung solcher Schichten ausgenommen sind.It’s obvious that for certain use cases, in which in addition to the super hard property of the surface their absolute unity is also desired, Pores in the surface are unacceptable, so the known methods basically for the production such layers are excluded.
Ein weiterer Nachteil der nach den vorgenannten bekannten Verfahren hergestellten Schichten besteht darin, daß die se grundsätzlich eine verhältnismäßig geringe Standzeit aufweisen, wenn diese Schichten aus einer Mehrzahl von einzelnen Teilschichten bestehen, die nach- bzw. aufein ander auf einen Substrat (Werkstück) aufgebracht sind. Es hat sich nämlich gezeigt, daß die Hafteigenschaften die ser Schichten bei unterschiedlichen Schichtenzusammen setzungen, obwohl sie mittels des gleichen bekannten Ver fahrens nacheinander aufgebracht worden sind, sehr gering sind, so daß immer wieder Schichtenablösungen nach ver hältnismäßig kurzer Zeit beobachtet wurden.Another disadvantage of the known after the aforementioned Processed layers is that the basically a relatively short service life if these layers of a plurality of individual sub-layers exist that follow or on each other others are applied to a substrate (workpiece). It It has been shown that the adhesive properties layers at different layers together settlements, although using the same known Ver driving have been applied in succession, very low are, so that layer detachments after ver were observed for a relatively short time.
Es ist Aufgabe der vorliegenden Erfindung ein Verfahren zur Herstellung von Schichten zu schaffen, die einerseits eine porenfreie Oberfläche und andererseits gute Haftei genschaften der einzelnen Schichten untereinander bei großer Standzeit der Gesamtschicht aufweisen. The object of the present invention is a method to create layers that one hand a non-porous surface and on the other hand good adhesion properties of the individual layers long service life of the entire layer.
Gelöst wird die Aufgabe gemäß der Erfindung dadurch, daß zur Ausbildung einer mehrlagigen Schicht zunächst mittels des CVD-/PVD Verfahrens auf dem Substrat wenigstens eine hochharte Schicht aufgebracht und nachfolgend darauf mit tels anodischer Oxidation wenigstens eine Oxidschicht erzeugt wird.The object is achieved according to the invention in that to form a multi-layer layer, first by means of of the CVD / PVD method on the substrate at least one applied a hard layer and then with it by means of anodic oxidation, at least one oxide layer is produced.
Der Vorteil dieses Verfahrens besteht darin, daß die sich ausbildende Gesamtschicht extrem haftfest und porenfrei ist. Dieses Ergebnis wird dadurch erzielt, daß im Gegen satz zu herkömmlichen Oxidationsverfahren, bei denen das elementare Metall oxidiert wird, hier beispielsweise eine Metall-Kohlenstoff oder Metall-Stickstoffschicht, die die erste hochharte Schicht bildet, die mittels der bekannten Verfahren aufgebracht ist, oxidiert wird.The advantage of this method is that the forming total layer extremely adhesive and non-porous is. This result is achieved in that in the opposite conventional oxidation processes in which the elemental metal is oxidized, here for example Metal-carbon or metal-nitrogen layer that the forms the first highly hard layer, which by means of the known Process is applied, is oxidized.
Gemäß einer vorteilhaften Ausgestaltung des Verfahrens wird die erste hochharte Schicht durch eine Metall-Ni trid, Metall-Carbid oder Metall-Carbonnitridschicht ge bildet, wobei als Metall beispielsweise Titan verwendet werden kann.According to an advantageous embodiment of the method the first super hard layer is made of a metal Ni trid, metal carbide or metal carbon nitride layer forms, with titanium used as the metal can be.
Die anodische Oxidation zur Ausbildung der zweiten Schicht kann vorzugsweise in einem wäßrigen Elektrolyten, beispielsweise Schwefelsäure erfolgen, es kann jedoch auch in einer Salzschmelze ausgeführt werden.The anodic oxidation to form the second Layer can preferably be in an aqueous electrolyte, for example sulfuric acid, but it can can also be carried out in a salt melt.
Die gemäß dem Verfahren vorzugsweise hergestellten hoch harten ersten Schichten sind zwischen 5×10-4 bis 10-1 mm dick, vorteilhafterweise ist diese Schicht doch 3× 10-3 mm dick.The highly hard first layers preferably produced according to the method are between 5 × 10 -4 to 10 -1 mm thick, advantageously this layer is nevertheless 3 × 10 -3 mm thick.
Die mittels der anodischen Oxidation erzeugte Schicht ist vorzugsweise bis zu 2×10-3 mm dick, vorzugsweise zwischen 10-4 bis 7×10-3 mm.The layer produced by means of the anodic oxidation is preferably up to 2 × 10 -3 mm thick, preferably between 10 -4 to 7 × 10 -3 mm.
Die Erfindung wird nun anhand eines Ausführungsbeispieles eingehend beschrieben.The invention is now based on an embodiment described in detail.
Die Herstellung von Schichten mittels des CVD-/PVD Ver fahrens ist allgemein bekannt und wird nachfolgend nur des besseren Verständnisses wegen kurz erläutert. Beim CVD- Verfahren (Chemical Vapour Deposition) ist das die Schicht bildende Ausgangsmaterial eine leicht zu verflüch tigende chemische Verbindung, die über Düsen in eine Re aktionskammer, welche die zu beschichtenden Teile ent hält, eingebracht wird. Die chemischen Reaktionen zur Schichtbildung laufen als heterogene Reaktion direkt am Substrat ab. Um die Reaktion zu aktivieren, wird das Sub strat bis auf 1000°C erwärmt, was auf verschiedenste Wei se erfolgen kann. Beim PVD-Verfahren wird die Schicht durch aufdampfen oder aufstäuben sowie ionenplattieren (arc-ionplating) erzeugt. Das Aufbringen der Schicht er folgt dabei in 3 Phasen, nämlich die Überführung des Schichtmaterials in den gasförmigen Zustand, den Trans port des Dampfes von der Quelle zum Substrat und schließ lich die Kondensation des vor dem Substrat angelangten Dampfes auf dessen Oberfläche zur Ausbildung der Schicht.The production of layers using the CVD / PVD Ver driving is well known and will only be described below briefly explained for better understanding. At the CVD (Chemical Vapor Deposition) is the one Layer-forming starting material is an easily cursed chemical compound that is injected into a re action chamber, which ent the parts to be coated holds, is introduced. The chemical reactions to Layer formation takes place directly as a heterogeneous reaction Substrate. To activate the reaction, the Sub strat heated to 1000 ° C, which in various ways se can be done. In the PVD process, the layer by vapor deposition or dusting and ion plating (arc ion plating). Applying the layer follows in 3 phases, namely the transfer of the Layer material in the gaseous state, the trans port of the steam from the source to the substrate and close Lich the condensation of what has reached the substrate Steam on its surface to form the layer.
Ein Verfahren dieser Art, beispielsweise das zum PVD-Ver fahren gehörende Magnetronzerstäuben oder die Lichtbogen inonenplattiertechnik (arc ironplating) wird zur Ausbil dung der ersten hochharten Schicht verwendet, um eine 3× 10-3 mm dicke Zirkoniumnitridschicht auf einem Substrat aufzubringen. Nachfolgend wird diese gebildete Zirkonium nitridschicht (Werkstück bzw. Substrat mit Schicht) in ein Elektrolysebad, das beispielsweise Schwefelsäure (H 2SO 4) enthält, gebracht und dort auf bekannte Weise anodisch oxidiert. Die so erzeugte Oxidschicht weist im Gegensatz zu den herkömmlichen Oxidationsverfahren den Vorteil auf, daß nicht das elementare Metall, im vorlie genden Beispiel das Zirkonium, oxidiert wird, sondern das Zirkoniumnitrid, das mittels dem zuvor genannten bekannten Verfahren zunächst als hochharte Schicht auf dem Substrat ausgebildet wurde.A method of this type, for example the magnetron sputtering associated with the PVD process or the arc iron-plating technique, is used to form the first superhard layer in order to apply a 3 × 10 -3 mm thick zirconium nitride layer to a substrate. This zirconium nitride layer (workpiece or substrate with layer) is subsequently placed in an electrolysis bath which contains, for example, sulfuric acid ( H 2 S O 4 ) and there is anodically oxidized in a known manner. In contrast to the conventional oxidation processes, the oxide layer produced in this way has the advantage that not the elementary metal, in the present example the zirconium, is oxidized, but rather the zirconium nitride, which is initially formed as a highly hard layer on the substrate by means of the known process mentioned above has been.
Die erzeugte Oxidschicht ist vorzugsweise 10-4 bis 7× 10-3 mm dick.The oxide layer produced is preferably 10 -4 to 7 × 10 -3 mm thick.
Ein weiterer Vorteil des erfindungsgemäßen Verfahrens besteht darin, daß auch ein gegenüber dem herkömmlichen Verfahren dichtes Oxidschichtwachstum generell sowie die Herstellung dickerer Oxidschichten möglich ist. Die er haltenen Schichten sind elektrisch hoch isolierend, che misch hoch korrosionsbeständig, sehr reibarm und, wenn die erste hochharte Schicht eine Metall-Nitridschicht ist, zudem noch verschleißfest.Another advantage of the method according to the invention is that a compared to the conventional Process dense oxide layer growth in general as well as the Production of thicker oxide layers is possible. Which he holding layers are electrically highly insulating, che mix highly corrosion-resistant, very low-friction and, if the first super hard layer is a metal nitride layer is also wear-resistant.
Es sie in diesem Zusammenhang erwähnt, daß die Ausbildung der Schichten gemäß der Erfindung sich nicht auf 2-lagige Schichten beschränkt, denn es sind gemäß dem Verfahren Schichten herstellbar, die aus beliebig vielen Einzel schichten aufgebaut sind, die in beliebiger Reichenfolge durch Anwendung der Verfahrenschritte gemäß der Erfindung erzeugt werden können.It mentioned in this context that training the layers according to the invention are not 2-ply Strata limited because it is according to the procedure Layers that can be made from any number of individual layers layers are built up in any order by using the process steps according to the invention can be generated.
Der wesentliche Vorteil des erfindungsgemäßen Verfahrens liegt darin, daß die auf diese Weise hergestellten Schic hten untereinander eine extreme Haftfestigkeit besitzen und ein sehr gutes Langzeitverhalten aufweisen.The main advantage of the method according to the invention is that the Schic would have extreme adhesive strength among themselves and have a very good long-term behavior.
Schichten, die gemäß dem erfindungsgemäßen Verfahren her gestellt sind, bieten vielfältige Anwendungsmöglichkei ten, beispielseise in der Elektromechanik für bewegte Stifte, die elektrisch hoch isolierend sein müssen, für Gleit- und Reibpaarungen, die hohe Korrosionsbeständig keit erfordern bei gleichzeitig hoher Reib- und Gleitbe anspruchung, und in der Medizintechnik beispielsweise bei Batterie- und Membrangehäusen für Herzschrittmacher. Es sei in diesem Zusammenhang erwähnt, daß als letzte Schicht d.h. als der Schicht, die mittels anodischer Oxidation erzeugt wird, Titanoxid, Zirkonoxid oder Misch oxide aus Zirkoniumtantaloxid sich als besonders physio logisch verträgliche Stoffe gezeigt haben, die in der zuvor genannten medizinischen Anwendung von großer Bedeu tung sind.Layers made according to the inventive method offer a wide range of possible applications ten, for example in electromechanics for moving Pins that must be highly electrically insulating for Sliding and friction pairings that are highly corrosion-resistant speed with high friction and sliding requirements stress, and in medical technology for example Battery and membrane housings for pacemakers. It in this context it should be mentioned that the last Layer i.e. than the layer that is anodized Oxidation is generated, titanium oxide, zirconium oxide or mixed Oxides made of zirconium tantalum oxide are particularly physio have shown logically compatible substances in the previously mentioned medical application of great importance are.
Schließlich sei darauf verwiesen, daß gemäß dem erfin dungsgemäßen Verfahren auch Abdeckungen, wie sie bei spielsweise in der Halbleiterindustrie erforderlich sind, ausgeführt werden können, um gezielt elektrisch leitende und nichtleitende Oberflächen erzeugen zu können.Finally, it should be noted that according to the invented method according to the invention also covers, as in for example in the semiconductor industry, can be run to selectively electrically conductive and to be able to produce non-conductive surfaces.
Claims (8)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19873741292 DE3741292A1 (en) | 1987-12-05 | 1987-12-05 | Process for producing hard multi-ply layers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19873741292 DE3741292A1 (en) | 1987-12-05 | 1987-12-05 | Process for producing hard multi-ply layers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| DE3741292A1 true DE3741292A1 (en) | 1989-06-15 |
| DE3741292C2 DE3741292C2 (en) | 1989-11-23 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19873741292 Granted DE3741292A1 (en) | 1987-12-05 | 1987-12-05 | Process for producing hard multi-ply layers |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE3741292A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT1669U1 (en) * | 1996-11-22 | 1997-09-25 | Plansee Ag | OXIDATION PROTECTIVE LAYER FOR REFRACTIVE METALS |
| EP0746266A4 (en) * | 1992-07-27 | 1999-08-18 | Smith & Nephew Richards Inc | Artificial heart components with improved biocompatible coating |
| RU2615941C1 (en) * | 2015-12-21 | 2017-04-11 | Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский технологический университет "МИСиС" | Procedure for application of coating on hardmetal |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2149542A1 (en) * | 1971-08-19 | 1973-03-30 | Totota Jidosha Kogyo Kk | Electrolytically oxidising chromium impregnated - steel - to prevent scale formation |
| US3809627A (en) * | 1968-11-19 | 1974-05-07 | Western Electric Co | Anodized cermet film components and their manufacture |
| US4463033A (en) * | 1976-07-10 | 1984-07-31 | Mitsubishi Kinzoku Kabushiki Kaisha | Process for production of coated super-hard alloy articles |
| EP0120632B1 (en) * | 1983-03-25 | 1987-09-23 | General Electric Company | Improved oxide bond for aluminum oxide coated cutting tools |
-
1987
- 1987-12-05 DE DE19873741292 patent/DE3741292A1/en active Granted
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3809627A (en) * | 1968-11-19 | 1974-05-07 | Western Electric Co | Anodized cermet film components and their manufacture |
| FR2149542A1 (en) * | 1971-08-19 | 1973-03-30 | Totota Jidosha Kogyo Kk | Electrolytically oxidising chromium impregnated - steel - to prevent scale formation |
| US4463033A (en) * | 1976-07-10 | 1984-07-31 | Mitsubishi Kinzoku Kabushiki Kaisha | Process for production of coated super-hard alloy articles |
| EP0120632B1 (en) * | 1983-03-25 | 1987-09-23 | General Electric Company | Improved oxide bond for aluminum oxide coated cutting tools |
Non-Patent Citations (1)
| Title |
|---|
| NL-Z.: Thin Solid Films 77, 1981, S. 259-270 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0746266A4 (en) * | 1992-07-27 | 1999-08-18 | Smith & Nephew Richards Inc | Artificial heart components with improved biocompatible coating |
| AT1669U1 (en) * | 1996-11-22 | 1997-09-25 | Plansee Ag | OXIDATION PROTECTIVE LAYER FOR REFRACTIVE METALS |
| US6214474B1 (en) | 1996-11-22 | 2001-04-10 | Plansee Aktiengesellschaft | Oxidation protective coating for refractory metals |
| RU2615941C1 (en) * | 2015-12-21 | 2017-04-11 | Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский технологический университет "МИСиС" | Procedure for application of coating on hardmetal |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3741292C2 (en) | 1989-11-23 |
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Legal Events
| Date | Code | Title | Description |
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| OP8 | Request for examination as to paragraph 44 patent law | ||
| D2 | Grant after examination | ||
| 8363 | Opposition against the patent | ||
| 8331 | Complete revocation |