EP3423609A1 - Revêtement en carbone exempt d'hydrogène comprenant une couche adhésive de zirconium - Google Patents

Revêtement en carbone exempt d'hydrogène comprenant une couche adhésive de zirconium

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Publication number
EP3423609A1
EP3423609A1 EP17709580.9A EP17709580A EP3423609A1 EP 3423609 A1 EP3423609 A1 EP 3423609A1 EP 17709580 A EP17709580 A EP 17709580A EP 3423609 A1 EP3423609 A1 EP 3423609A1
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EP
European Patent Office
Prior art keywords
layer
zirconium
carbon
layers
hydrogen
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.)
Pending
Application number
EP17709580.9A
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German (de)
English (en)
Inventor
Joerg Vetter
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.)
Oerlikon Surface Solutions AG Pfaeffikon
Original Assignee
Oerlikon Surface Solutions AG Pfaeffikon
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Application filed by Oerlikon Surface Solutions AG Pfaeffikon filed Critical Oerlikon Surface Solutions AG Pfaeffikon
Publication of EP3423609A1 publication Critical patent/EP3423609A1/fr
Pending legal-status Critical Current

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Definitions

  • the present invention relates to a hydrogen-free carbon coating, with a zirconium adhesive layer for substrate surfaces, in particular for tool and component surfaces for tribological applications, the carbon coating a hard carbon layer with a hydrogen-free, amorphous carbon structure depending on the CC sp 3 bond content as aC or as ta -C, and may contain other elements, and is associated with the group of DLC layers, and the zirconium adhesive layer is zirconium, with the zirconium adhesive layer applied between the substrate surface and the hard carbon layer, such that atomic bonds are interposed between the substrate Carbon atoms of the carbon layer and zirconium atoms form the zirconium layer.
  • zirconium is to be understood as meaning the chemical element with the element symbol Zr.
  • a Zn-x Cx is abbreviated to Zr-Cx for the sake of convenience.
  • the adhesive layer is a pure zirconium layer.
  • the range is preferably 10 at% ⁇ X ⁇ 50at%.
  • a carbon layer is to be understood as meaning a layer which has an amorphous state carbon matrix detectable by means of volumetric measurement and which can be detected by means of Raman spectroscopy or other suitable measuring methods.
  • This zirconium layer serves for bonding between the substrate and the hydrogen-free carbon layer. Due to the process, atomic bonds form between the carbon atoms of the hydrogen-free layer and atoms of the zirconium layer. Under certain process conditions, depending on
  • CONFIRMATION COPY Process temperature and the energy of the impinging carbon atoms it may lead to the formation of a thin Zr-Cx layer between the existing zirconium layer and the hydrogen-free, amorphous carbon layer, Furthermore, it is possible targeted zirconium monocarbide form by the simultaneous deposition of zirconium and carbon, wherein the layer of ZrC optionally, the zirconium monocarbide comprising layer is applied directly to the zirconium existing adhesive layer.
  • the transition to the pure carbon layer can also be a multi-layered or graded hydrogen-free aC: Zr layer or ta-C: Zr layer, which is distinguished from the stoichiometric zirconium carbide by a larger atomic proportion of carbon atoms compared to the zirconium atoms.
  • Amorphous, carbon-based hard material layers also called DLC layers
  • DLC layers are known from the prior art.
  • these types of layers do not always have sufficient adhesion to the substrate, especially if they are hard hydrogen-free layers of the type a-C or ta-C. This is due to the high residual stress state of the layers, which makes it difficult to deposit process-stable adherent layers of this type with excellent functionality.
  • Kabushiki teaches that when a nitride or carbonitride is used for the interlayer, the adhesion of the amorphous carbon layer (also called DLC, using DLC as the abbreviation of Diamond like Carbon) even at high temperature or can be improved in a high load area. Therefore, Kabushiki proposes adhesion between the substrate and the amorphous carbon (DLC) layer by depositing a multilayered film system between the substrate and the DLC amorphous carbon film. According to the teachings of Kabushiki, this way can the adhesion between substrate and DLC layer can be improved even at high temperature and in a high load area.
  • DLC amorphous carbon
  • the multi-layer coating system according to Kabushiki comprises:
  • a base layer formed on the substrate comprising a nitride or a carbonitride of an element M and having a composition of the formula Mi-x- y CxN y , wherein x ⁇ 0.5, y 0.03 and 1-xy are greater than zero, and wherein M is at least one element selected from Groups 4A, 5A, 6A of the Periodic Table, Al and Si, and wherein the element M comprises Ti, Zr, V, Nb, Ta, Cr, Mo, W, Al and Si, and preferably M comprises the elements W, Mo and Ta, and
  • a layer of an element formed between the substrate and the base layer which element may be selected from among a Group 4A element in the Periodic Table, a Group 5A element, a Group 6A, Al and Si element.
  • the layer structure described above is complex and therefore requires a complicated reactive coating process, which is mostly used in industrial production, e.g. in large-scale production is not desirable because the complexity of the process steps represents a higher risk in terms of a sufficient coating result.
  • Hard material coating which comprises a hard hydrogen-free amorphous carbon-based layer, wherein the hard coating a possible simple Layer structure and a very good adhesion to the substrate, even in applications in areas with high loads, has.
  • the carbon coating comprises a hard carbon layer and a zirconium adhesive layer, wherein the carbon layer has a hard, hydrogen-free, amorphous carbon structure and the zirconium adhesive layer is zirconium, and the zirconium adhesive layer is applied between the substrate surface and the hard carbon layer such that process-related atomic bonds between carbon atoms of the hard carbon layer and zirconium atoms of the zirconium adhesive layer, thereby forming a zirconia-carbon Zr-Cx layer having a layer thickness of a few atomic layers or up to several nanometers.
  • Figure 1 b shows the photograph of a Rockwell C impression in a carbon coating according to the present invention.
  • Figure 2 shows a carbon coating according to the invention with supporting layer.
  • the Zr-Cx layer is exclusively formed by process-related atomic bonds between carbon atoms of the hard, hydrogen-free, amorphous carbon layer and zirconium atoms of the Zirconium adhesive layer formed such that this Zr-Cx layer has a layer thickness in the atomic region range.
  • the layer thickness of the Zr-Cx layer can be, for example, 2 to 10 atomic layers in this embodiment.
  • the process conditions are selected such that after deposition of the zirconium adhesive layer, in particular the process temperature and the energy of the carbon atoms impinging on the surface of the zirconium adhesive layer, formation of atomic bonds between carbon atoms of the hard, hydrogen-free , amorphous carbon layer and zirconium atoms promote the zirconium adhesive layer so that in this way the necessary conditions for forming a Zr-Cx layer having a layer thickness of at least 2 atomic layers to about 100 nm are given.
  • a process is carried out such that a ZrC layer comprising zirconium monocarbide is formed between the zirconium adhesive layer and the hard, hydrogen-free, amorphous carbon layer.
  • the zirconium monocarbide-containing ZrC layer can be formed by simultaneously depositing zirconium and carbon.
  • the layer thickness of the zirconium monocarbide-containing ZrC layer is, for example, 5 nm to 500 nm in this embodiment.
  • the hydrogen-free, amorphous carbon layer is an a-C or ta-C layer.
  • the hydrogen-free carbon layers which the person skilled in the art designates as aC layers or ta-C layers, can be produced, for example, by the Are method (unfiltered or filtered) or else by sputtering methods (DC, pulsed DC, RF, HiPIMS), preferably in the case of aC- Layers are deposited.
  • AC layers are referred to when the relative proportion of the sp 3 - bonding moieties of the CC bonds is equal to or smaller than the proportion of the sp 2 - bonding moieties of the CC bonds in the layers. These layers then have hardnesses below 50 GPa. If the proportion of sp 3 bond portions exceeds that of the sp 2 bond portions, mention is made of ta-C layers (tetrahedral hydrogen-free amorphous carbon layers) which typically cure above of 50 GPa. It goes without saying that methods known to those skilled in the art for measuring the hardness of thin layers are used.
  • the zirconium adhesive layer can be deposited, for example, by means of the Are method (unfiltered or filtered) or else by sputtering methods (DC, pulsed DC, RF, HiPIMS).
  • a peculiarity of ion-cleaning processes based on accelerated metal ions ie, metal ion-cleaning processes, usually with an applied bias of 500V to 1500V
  • metal ion-cleaning processes usually with an applied bias of 500V to 1500V
  • zirconium is that such process parameters are selectable, so that a thin zirconium layer in the thickness range of a few nm to several 10 nm forms, which forms the zirconium adhesive layer.
  • substrates of, for example, steel, hard metal, aluminum alloys, Cu alloys, ceramics, cermet, or other metallic alloys can be coated. Since the coating temperature for producing the carbon coatings according to the present invention is down to 100 ° C, extremely temperature-sensitive substrates can be coated in terms of substrate materials or other properties.
  • cutting tools and forming tools can be coated.
  • Component components such as valve parts, vane pumps, or automotive parts such as piston pin, piston rings, finger followers, bucket tappets, or household appliances such as cutting blades, scissors, razor blades or medical parts such as implants and surgical instruments, or decorative parts such as watch case can u.a. also be coated with a carbon coating according to the present invention.
  • zirconium layers As sources of evaporation for the deposition of the zirconium layers, both Are sources with filters and without filters can be used. Likewise, suitable zirconium layers may be sputtered, such as RF, DC; pulsed DC or HiPIMS are deposited. Also, vapor deposition methods such as electron beam evaporation, low-voltage arc evaporation or
  • Hollow cathode arc evaporation is suitable for depositing the zirconium adhesive layer for the carbon coatings of the present invention.
  • a-C and ta-C layers it is also possible to prepare a-C: Me layers or Ta-C: Me layers in a targeted manner. These layers contain at least one metal as a doping element and have compared to the a-C and ta-C layers without doping element changed property profiles, for example, the electrical conductivity is greater. This may thus be advantageous in certain applications.
  • the adhesive layer should be made of zirconium according to the present invention, it would be advantageous to use zirconium as the Me method.
  • the simplest process management results if the zirconium evaporation is carried out simultaneously with the operation of the carbon evaporation by means of Are.
  • Another method is the use of carbon targets in which zirconium has been added.
  • Another embodiment according to the present invention are hydrogen-free, amorphous a-C: X layers or ta-C: X layers.
  • non-metallic elements In addition to metallic elements (commonly referred to as Me) which are added to the layers and thus lead to the a-C: Me layers, it is also possible to add other non-metallic elements (generally designated X) as doping elements for layer optimization, depending on the application. These non-metallic elements may be nitrogen, boron, silicon, fluorine or others. For example, doping with N or Si leads to stress reduction and F leads to a change in the wetting properties (higher wetting angle), as is generally known to the person skilled in the art.
  • the hydrogen-free, amorphous layer is designed as a multilayered layer, wherein the multilayered layer structure comprises alternately arranged individual layers of a type A and a type B, the individual layers of the type A consisting of aC or ta-C and the individual layers of the type B from Me or from aC: Me or ta- C: Me are.
  • zirconium may be used as Me, for example, such that a multilayer coating of the type aC / Zr or ta-C / Zr or aC / aC: Zr or ta-C / ta-C: Zr and also further combinations such as ta- C / aC: Zr or aC / ta-C: Zr is formed.
  • the same process is driven as in the embodiment from the phase of deposition of the metallic layer, the layer thickness limited to about 500 nm and then driven the same process many times, for example 6 times, so that in addition to the zirconium adhesive layers further 5 intermediate layers and a Total layer thickness of more than 3 pm arise. This leads to a higher load capacity and wear resistance.
  • the hydrogen-free, amorphous layer is designed as a multilayer layer, wherein the multilayered layer structure comprises alternately arranged individual layers of a type A and a type B, wherein the individual layers of the type A are degraded from aC or ta-C and the individual layers of type B from aC: X or from ta-C: X are.
  • the multilayered layer structure comprises alternately arranged individual layers of a type A and a type B, wherein the individual layers of the type A are degraded from aC or ta-C and the individual layers of type B from aC: X or from ta-C: X are.
  • silicon or nitrogen can be used as X.
  • Additional arc evaporators may be used to deposit such layers which evaporate the X-element alloyed graphite cathodes, or other suitable PVD methods could be used, e.g. Sputtering method with which the element X is sputtered.
  • the thickness of the single layers of the type A is not more than 2000 nm and not less than 5 nm.
  • the thickness of the single layers of the type B is not more than 2000 nm and not less than 5 nm.
  • An advantage of this embodiment is also the possibility of a higher layer thickness combined with an optimized stress ratio within the same coating.
  • the Zr layer is applied to the substrate to be coated by means of a metal-ion-cleaning method.
  • the hydrogen-free, amorphous layer is a layer of a nanocomposite material which comprises a matrix material and a material embedded in the matrix material, wherein the matrix material is preferably aC or ta-C and the embedded material is metallic carbides with dimensions in the nanometer range, eg with metal-doped amorphous carbon layers, depending on the metal, eg tungsten carbide (WC) or chromium carbides (Cr23C6, Cr3C2) or other carbides of the metallic elements, preferably made of ZrC.
  • WC tungsten carbide
  • Cr23C6, Cr3C2 chromium carbides
  • Hard material layers according to the present invention may also include support layers between the substrate and the zirconium adhesive layer on which the hydrogen-free, amorphous carbon layer is deposited, as shown in FIG. Shown is a substrate 205 on which only a support layer 207, then a Zr-Cx layer 209 and then a hydrogen-free amorphous carbon layer is provided.
  • This support layer increases the mechanical strength of the surface. It preferably consists of a material which has a higher toughness than the hydrogen-free, amorphous carbon layers.
  • this support layer may consist of ZrN.
  • nitridic e.g., CrN, AITiN
  • carbonitridic e.g., TiCN, ZrNC
  • carbidic e.g., TiC, CrC
  • oxynitridic e.g., CrNO
  • these layers are deposited by means of arcs or sputtering.
  • Hard coatings according to the present invention may also be deposited to include one or more further metallic adhesive layers between the substrate and the zirconia adhesive layer.
  • the one further metallic adhesion layer may be a Cr adhesion layer produced by means of metal ion cleaning with Cr ions, onto which the zirconium adhesion layer is then deposited.
  • Hard material layers according to the present invention can also be produced according to the invention with the aid of HiPIMS technology.
  • the hydrogen-free, amorphous layer and / or the support layer and / or the zirconium adhesive layer and / or the one or more intermediate layers can be deposited by means of a HiPIMS method.
  • only the a-C layer is deposited by HiPIMS.
  • both the Zr adhesion layer and the a-C layer are both deposited with HIPIMS.
  • An advantage of these embodiments is the formation of particularly smooth a-C layers.
  • Hard material layers according to the present invention can also be produced according to the invention by means of a hybrid technology which combines the HiPIMS and the Are technology.
  • the hydrogen-free amorphous layer and / or the supporting layer may be deposited by a hybrid Arc / HiPIMS method and the zirconium adhesive layer deposited using a Zr ion metal ion-cleaning process based on the HiPIMS process.
  • a deposition of a thicker Zr adhesive layer can also be carried out directly with the HiPIMS method.
  • the hydrogen-free, amorphous layer can be deposited by means of a hybrid Are process
  • the support layer can be deposited by means of a HiPIMS or a hybrid Arc / HiPIMS process
  • the Zr adhesion layer can be deposited by means of a Zr ion metal ion cleaning process.
  • the layer deposits of a-C (hardness of about 40 GPa) and ta-C layers (hardness of about 55 GPa) were realized in a commercial coating plant equipped with arc evaporators.
  • the coating steps were initially pumped to high vacuum (0.001 Pa), then a heating step taking into account compliance with a maximum substrate temperature temperature of about 150 ° C. Subsequently, an ion cleaning by means of the AEGD method, then the arc evaporator were ignited with Cr or Zr to deposit the metallic adhesive layer of about 120 +/- 40 nm. For this purpose, appropriate breaks were taken in order not to exceed a maximum temperature of about 150 ° C. In the transition phase for the deposition of the pure carbon layer, the arc evaporators were ignited with suitable graphite cathodes and a voltage of at least 500 V was applied to the substrates, resulting in bombardment with C ions of the metallic intermediate layer.
  • FIG. 1 a shows the photograph of a Rockwell C impression in a carbon coating with chromium adhesive layer
  • zirconium adhesive layers according to the present invention will not form a more brittle phase but rather a more "ductile" phase, which under some circumstances may comprise zirconium monocarbide (ZrC) of one or more inert process gases (eg, helium, neon, or argon) and / or metals and acceleration of these onto the substrate surface may produce a sputtering or implantation effect on the surface, when these ion cleaning processes are primarily intended for impurities such as native Oxides or even organic impurities, it is often sufficient to work only with inert gas ions.
  • ZrC zirconium monocarbide
  • inert process gases eg, helium, neon, or argon
  • AEGD arc enhanced glow discharge
  • a metal ion cleaning method (or called metal ion etching) another etching method.
  • metal ion cleaning method one or more metal sources of, for example, chromium or zirconium are operated, which have the effect of accelerating ionized metals onto the substrate surface.
  • the energy and amount of vaporized (eg in Arc processes) or sputtered (eg sputtering or HIPIMS processes) material can be adjusted specifically.
  • hydrogen-free amorphous carbon layers are understood as meaning all carbon layers whose hydrogen content is ⁇ 5 at.%, Preferably ⁇ 2 at.%, Whereby any impurities are not taken into consideration.
  • suitable characterization methods such as elastic recoil detection analysis (ERDA), rutherford backscattering (RBS) or secondary ion mass spectroscopy (SIMS) for determining the chemical composition of the layers according to the invention are known to the person skilled in the art.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Physical Vapour Deposition (AREA)
  • Cutting Tools, Boring Holders, And Turrets (AREA)

Abstract

La présente invention concerne un substrat revêtu pourvu d'un revêtement en matière dure qui comprend une couche dure de carbone du type couche de carbone amorphe exempte d'hydrogène, le revêtement comprenant entre le substrat et la couche de carbone amorphe exempte d'hydrogène une couche constituée de zirconium. Une couche de Zr-Cx comprenant du monocarbure de zirconium peut être formée entre la couche de zirconium et la couche de carbone amorphe exempte d'hydrogène, laquelle couche de Zr-Cx comprenant du monocarbure de zirconium est appliquée directement sur la couche adhésive de zirconium.
EP17709580.9A 2016-03-01 2017-02-28 Revêtement en carbone exempt d'hydrogène comprenant une couche adhésive de zirconium Pending EP3423609A1 (fr)

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US10844493B2 (en) 2020-11-24
KR20180123508A (ko) 2018-11-16
WO2017148582A1 (fr) 2017-09-08
CN108884550A (zh) 2018-11-23
CN108884550B (zh) 2022-08-30

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