EP0224495A1 - Verfahren zur herstellung von verschleissfesten verbundwerkstoffen - Google Patents
Verfahren zur herstellung von verschleissfesten verbundwerkstoffenInfo
- Publication number
- EP0224495A1 EP0224495A1 EP19860902310 EP86902310A EP0224495A1 EP 0224495 A1 EP0224495 A1 EP 0224495A1 EP 19860902310 EP19860902310 EP 19860902310 EP 86902310 A EP86902310 A EP 86902310A EP 0224495 A1 EP0224495 A1 EP 0224495A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- oxygen
- wear
- titanium
- substrate
- hard material
- 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- Withdrawn
Links
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
- 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
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
-
- 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
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/301—AIII BV compounds, where A is Al, Ga, In or Tl and B is N, P, As, Sb or Bi
-
- 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
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/36—Carbonitrides
Definitions
- the invention relates to a method for producing wear-resistant composite materials on a substrate from a metallic solid, wherein in a recipient a volatile compound of the hard material-forming metal is implemented with the application of energy and is applied to the substrate as a wear-resistant coating and the energy supply is at least partially with a plasma CVD -Procedure done.
- wear-resistant composite materials that consist of a substrate or core of a metallic solid, in particular steel, hard metal, aluminum or Titanium and one or more surface layers are of great importance in practice, for example for the coating of workpieces to produce particularly hard or low-wear wear layers.
- tools such as B. cutters or drills can be specified, which are used for machining.
- Such composite materials are currently produced using known technologies, which include, for example, chemical or physical vapor deposition, which are briefly referred to as CVD and PVD processes.
- CVD chemical or physical vapor deposition
- PVD physical vapor deposition
- the PVD processes which include, for example, the cathode dusting and ion plating, work at much lower temperatures; the upper limit for the temperatures used is usually around 550 ° C. since this The temperature value also represents the upper limit for tempered HSS steels or cutting tools.
- the PVD processes are not free from disadvantages either, because there is, for example, the difficulty in coating the respective workpieces with a uniform layer thickness.
- shadow patterns are also very common because the vaporized metal atoms or hard material molecules fly straight from their source onto the respective substrate.
- the plasma CVD processes have been developed, in which the CVD processes are characterized by a Plasma are supported, more precisely supported by the energy that is in the plasma.
- the activation energy required for the reaction is not supplied thermally to the volatile gases and metal compounds which are in the recipient and serve to coat the respective substrate, but rather by generating a low-pressure plasma.
- a plasma can be generated either by direct voltage glow discharges or by high-frequency discharges, the high-frequency discharges being more universally applicable, since nonconductive substances can also be deposited in this way.
- the object of the invention is now to provide a method for producing particularly high-quality wear-resistant composite materials and a long service life
- oxygen-containing titanium compounds include the group of alkoxides and acetylacetonates.
- the titani is sopropylate
- Ti (OPr i ) 4 is the easiest to handle since it has the highest vapor pressure of all compounds of this type.
- the presence of hydrogen as a reducing agent has proven to be particularly useful.
- titanium dioxide is the most thermodynamically stable compound of the system Ti / N / O / C / H, the titanium dioxide being formed when only the activation energy required for the reaction can be applied.
- This gas stream bubbles through a heated container with the liquid alkoxide or the like and is cooled to a defined temperature in a recooler. It is thus possible to produce a saturated gas stream which contains a quantity of this substance which can be calculated from the vapor pressure of the alkoxide or the volatile compound containing oxygen.
- the solution according to the invention consists in that an oxygen-containing volatile compound of the hard material-forming metal is used and that the reaction takes place at a temperature in the range from room temperature to about 600 ° C., in particular at about 500 ° C.
- Ti (OR) 4 is used as the oxygen-containing volatile compound, wherein for R the residues are -CH 3 ,
- an alkoxide and / or acetylacetonate of the elements Ti, Zr, Hf, V, Nb, Ta, Cr and / or w is used as the volatile metal compound.
- the invention is thus in no way based on the use of titanium as hard material of the metal limited.
- reaction for converting the oxygen-containing compound of the hard material-forming metal takes place in the presence of hydrogen as a reducing agent.
- the device is generally designated with the reference number 10, which can be a commercially available plasma nitriding system.
- a recipient 12 is optionally provided with a heating device 14 and has in its interior a substrate holder 16 on which the respective samples can be arranged.
- An insulator 18 can be seen on the underside of the recipient 12;
- supply lines 19 and 21 are provided, which are connected to a voltage supply 20, for example a DC voltage supply, the housing wall of the recipient 12 being connected as an anode and being at ground potential.
- the recipient 12 can be evacuated via suction lines 23 and 25, possibly with the interposition of a separator 22, which may be a dust separator and / or a cold trap, with a pump which is indicated schematically by the arrow 24 is.
- the respective substances are fed into the interior of the recipient 12 using a conduit system which is shown schematically in the left area in the drawing.
- Supply lines 26, 28 and 30 are provided, which are used, for example, to introduce argon, nitrogen and hydrogen.
- a container 32 which can be equipped with a heating device (not shown), there is a liquid which, for example, consists of liquid alkoxide and through which the gas stream mentioned bubbles, in order to finally reach the recipient 12 via the main feed line 50.
- valves in the respective lines are provided with the reference symbols 36, 37, 38, 39, 40 and 41, while pressure gauges are identified with the reference symbols 43 and 44. Furthermore, a cooling device 34 is provided in the feed line from the container 32 in order to bring the gas stream saturated with the alkoxide or the like to a defined temperature.
- the samples to be treated are arranged on the cathode after thorough cleaning, in particular degreasing, in the commercially available plasma nitriding system described above.
- This can be the substrate holder 16 indicated schematically in the drawing.
- hydrogen (H 2 ) or argon (Ar) is first introduced, with a pressure of the order of about 1 mbar.
- the DC glow discharge is then ignited. Due to the electrical power supplied by the glow discharge, the cathode and the samples made of steel or hard metal heat up to the desired temperature.
- the temperature control can be carried out in a manner not shown with a thermocouple, which is placed in a reference sample on the substrate holder.
- the pressure prevailing in the interior of the recipient 12 is then gradually and gradually increased, for example to egg pressure of 5 mbar at a temperature of about 500 ° C
- the inflow of hydrogen or argon is interrupted and then a defined gas mixture is introduced into the recipient; in one embodiment, a mixture of hydrogen (H 2 ), nitrogen (N 2 ) and titanium isopropylate (Ti (0Pr i ) 4 ) initiated in a ratio of 140: 20: 1.
- a defined gas mixture in one embodiment, a mixture of hydrogen (H 2 ), nitrogen (N 2 ) and titanium isopropylate (Ti (0Pr i ) 4 ) initiated in a ratio of 140: 20: 1.
- the supply takes place via the heated main feed line 50 until shortly before the samples located in the recipient 12.
- the glow discharge is then maintained over a period of six hours at a temperature of 500 ° C. and a pressure of 5 mbar.
- the supply of the gas mixture is then ended and the direct voltage of the direct voltage supply 20 is switched off. After the arrangement has cooled to room temperature, the recipient 12 is aerated and the samples are removed.
- the method according to the invention is by no means restricted to such a substance.
- Other alkoxides and acetylacetonates can also be used.
- the temperatures of the evaporator and the pipeline to the recipient must be increased accordingly because of the lower vapor pressure.
- the volatile, oxygen-containing compounds of titanium can be used to form the hard material layers, but also other metals or oxygen-containing compounds of the hard material-forming metals can be used, such as, for. B. the volatile alkoxides and / or acety lacetonate of the hard substance-forming elements Zr, Hf, V, Nb, Ta, Cr and / or W. The reaction conditions are then adjusted accordingly.
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Vapour Deposition (AREA)
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19853512825 DE3512825A1 (de) | 1985-04-10 | 1985-04-10 | Verfahren zur herstellung von verschleissfesten verbundwerkstoffen |
DE3512825 | 1985-04-10 |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0224495A1 true EP0224495A1 (de) | 1987-06-10 |
Family
ID=6267624
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19860902310 Withdrawn EP0224495A1 (de) | 1985-04-10 | 1986-04-02 | Verfahren zur herstellung von verschleissfesten verbundwerkstoffen |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP0224495A1 (de) |
DE (1) | DE3512825A1 (de) |
WO (1) | WO1986006105A1 (de) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3905417C2 (de) * | 1989-02-22 | 1997-07-10 | Sueddeutsche Kalkstickstoff | Verfahren zur Herstellung von dünnen Niob- und/oder Nioboxidfilmen |
DE19506579C2 (de) * | 1995-02-24 | 1996-12-12 | Fraunhofer Ges Forschung | Verfahren zur Herstellung von TiN-Schichten und die mit diesem Verfahren hergestellte Schicht |
JPH1179788A (ja) * | 1997-08-29 | 1999-03-23 | Central Glass Co Ltd | 被膜形成ガラスおよびその製法 |
FR2769922B1 (fr) * | 1997-10-17 | 1999-12-03 | Univ Bourgogne | Obtention par mocvd de couches de composes ti(o,n) a stoechiometrie reglable |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE600374C (de) * | 1929-03-01 | 1934-07-18 | Franz Skaupy Dr | Verfahren zur Herstellung von UEberzuegen aus Oxyden, Nitriden oder Carbiden |
US3114652A (en) * | 1960-04-15 | 1963-12-17 | Alloyd Corp | Vapor deposition process |
FR1493110A (fr) * | 1966-07-16 | 1967-08-25 | Radiotechnique Coprim Rtc | Procédé de dépôt de couches minces sur un substrat par la voie d'une décharge électrique luminescente et appareillage pour la mise en oeuvre de ce procédé |
DE1621358A1 (de) * | 1966-11-08 | 1971-04-29 | Texas Instruments Inc | Verfahren zur Aufbringung duenner Filme aus dielektrischem Material auf ein Substrat |
GB1295061A (de) * | 1969-11-05 | 1972-11-01 | ||
DE2143827C3 (de) * | 1971-09-01 | 1978-04-06 | Siemens Ag, 1000 Berlin Und 8000 Muenchen | Verfahren zur Herstellung von Schutzschichten durch thermische Zersetzung eines Acetylacetonats |
ATA261878A (de) * | 1978-04-14 | 1979-05-15 | Ver Edelstahlwerke Ag | Verfahren zur herstellung beschichteter hart- metallkoerper |
US4297150A (en) * | 1979-07-07 | 1981-10-27 | The British Petroleum Company Limited | Protective metal oxide films on metal or alloy substrate surfaces susceptible to coking, corrosion or catalytic activity |
EP0055459A1 (de) * | 1980-12-29 | 1982-07-07 | Rikuun Electric co. | Verfahren zur Herstellung von Oxiden durch chemische Dampf-Abscheidung (CVD) |
FR2511047A1 (fr) * | 1981-08-07 | 1983-02-11 | Solarex Corp | Procede pour appliquer un revetement antireflechissant et/ou dielectrique pour des cellules solaires |
US4504522A (en) * | 1984-03-15 | 1985-03-12 | Ford Motor Company | Method of making a titanium dioxide oxygen sensor element by chemical vapor deposition |
-
1985
- 1985-04-10 DE DE19853512825 patent/DE3512825A1/de not_active Withdrawn
-
1986
- 1986-04-02 EP EP19860902310 patent/EP0224495A1/de not_active Withdrawn
- 1986-04-02 WO PCT/DE1986/000138 patent/WO1986006105A1/de not_active Application Discontinuation
Non-Patent Citations (1)
Title |
---|
See references of WO8606105A1 * |
Also Published As
Publication number | Publication date |
---|---|
DE3512825A1 (de) | 1986-10-16 |
WO1986006105A1 (en) | 1986-10-23 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 19870115 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT CH DE FR GB IT LI NL |
|
RBV | Designated contracting states (corrected) |
Designated state(s): AT CH DE FR GB LI NL |
|
17Q | First examination report despatched |
Effective date: 19880906 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
|
18D | Application deemed to be withdrawn |
Effective date: 19901103 |
|
RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: MAYR, PETER Inventor name: STOCK, HEINZ-ROLF |