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
  • C23C16/26—Deposition of carbon only
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
  • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
• • 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
  • C23C16/02—Pretreatment of the material to be coated
  • C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
• • 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
  • C23C16/02—Pretreatment of the material to be coated
  • C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
  • C23C16/029—Graded interfaces
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
  • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
  • Y10T428/264—Up to 3 mils
  • Y10T428/265—1 mil or less
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/30—Self-sustaining carbon mass or layer with impregnant or other layer

Definitions

• the invention relates to a conductive material made of a copper-containing alloy for use as a plug or Klemm ⁇ connection according to the preamble of claim 1. Further, a contact piece according to claim 18, and a semifinished product according to claim 19 or a band or profile according to claim 20 ,
• Copper-containing conductive materials are also known from the prior art, such as the good suitability of copper materials for the application of galvanic layers for Ober ⁇ surface refinement.
• PVD, CVD or PVD / CVD layers have hitherto been used little on the relatively soft copper materials, since, for example, in the case of a sliding stress with high load, as can occur when mounting plug-in or clamped connections, the layer In the base material is pressed or breaks and many used for the tool coating layer system too high a coefficient of friction (for example, the carbides WC, or Cr x Cy have a coefficient of friction of about 0.5 and greater), have too high roughness or poor electrical conductivity which makes them unsuitable for such an application.
• the carbides WC, or Cr x Cy have a coefficient of friction of about 0.5 and greater
• DE 1 802 932 discloses a high-frequency plasma method for coating electrical contacts with carbide wear protection layers. Similar to DE 3011694, wherein inter alia the application of a galvanic adhesive layer on various hardened or hardened metallic Werk ⁇ materials and an adjoining PVD coating in High-frequency plasma is described in which, inter alia, a carbide hard material layer is deposited. This achieves good electrical conductivity and increased wear protection, but the carbide coating results in a relatively high coefficient of friction.
• the invention is based on the object to provide a copper-containing control material, in which the disadvantages of the prior art are avoided and better electrical properties and a better service life and sliding behavior compared to conventionally coated materials are achieved.
• modified carbon-containing sliding or hard coatings having a carbon content of greater than or equal to 40 but less than or equal to 70 atomic percent, which are deposited on copper or copper alloys, it is possible the hardness of the surface and thus the To increase the wear and abrasion resistance of the materials without significantly changing their excellent electrical properties.
• the carbon content is understood as meaning the content of carbide-bound and free carbon which, together with the carbide former and additional optional elements added to 100%.
• a hard layer having defined tribological and electrical properties is deposited with a method as described in more detail below, which leads to an extension of the service life of the guide materials.
• the layers are slightly less hard than conventional hard carbides, for example, but significantly harder than the carrier material and thus protect it against abrasive wear. Surprisingly, these layers better protect the carrier material in plug-in and clamping applications than conventional hard-coating systems, wherein a support layer may additionally be provided for applications with high surface pressure. In the case of existing hard coatings, this could also be attributed to the relatively low coefficient of friction, which has advantageous effects, for example when used in a plug connection, since this simultaneously reduces the insertion forces and prevents scratching of a possibly uncoated counterpart.
• galvanically coated conductive materials examples include Cr, Ni or CrNi layers, which are applied before the support layer.
• plasma CVD, PVD or PVD / CVD hybrid processes are particularly suitable for the deposition of Me-DLC layers for the coating of, for example, hardenable copper materials.
• an additional support layer comprising at least one metal Me from the elements of subgroups IV, V, and VI of the Periodic Table of the Elements (ie Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W) or aluminum or Si included, could further impressions even at very high loads are avoided.
• Stauer ⁇ layers have proven to be particularly advantageous in addition to the metallic phase and a non-metal such as C, N, B, or 0 or the HartstoffVerbin ⁇ containing the metals with these non-metals.
• the backing layer systems TiN or Ti / TiN (ie, a metallic titanium layer with an adjoining Titannitridhart für), CrN or Cr / CrN, Cr x C ⁇ or Cr / Cr x C y, Cr x (CN) ⁇ or Cr / Cr x (CN) y , TiAl or TiAlN and TiAl / TiAlN mentioned.
• the support layer has a minimum layer thickness. This depends above all on the surface pressure occurring depending on the application. For example, with a low surface pressure even with layer thicknesses of 0.5 .mu.m, a sufficient supporting effect of the DLC layer could be achieved, while with a support layer of 0.3 .mu.m, the supporting effect was no longer sufficient. In general, however, a layer thickness of at least 1 to about 3 microns is recommended. For applications in which particularly high surface pressures occur, larger layer thicknesses, for example 6 ⁇ m, may also be advantageous.
• a metallic intermediate layer with or without a graded transition, or directly a transition layer, for example in the form of a gradient layer with increasing carbon content towards the sliding layer can be applied become .
• the DLC overlay itself is therefore advantageously carried out as follows: Directly on the support layer, a metallic intermediate layer comprising at least one metal Me from the elements of the IV, V, VI subgroup, Al or Si deposited.
• a metallic intermediate layer comprising at least one metal Me from the elements of the IV, V, VI subgroup, Al or Si deposited.
• an intermediate layer of the elements Cr or Ti is used, which have been found to be particularly suitable for this purpose.
• nitridic, carbidic, boridic or oxidic interlayers, or interlayers which are a mixture of one or more metals with one or more of the said non-metals, which, if required, can be used even on a metallic base layer with or without graded Transition can be constructed.
• this intermediate step can be omitted if the adhesion layer itself consists of a metal or a compound suitable as an adhesion-promoting layer.
• a transition layer in particular in the form of a gradient layer, preferably adjoins, in the course of which, perpendicular to the workpiece surface, the metal content decreases and the C content increases.
• the increase in the carbon can be effected by increasing possibly different carbide phases, by increasing the free carbon, or by a mixture of such phases with the metallic phase of the intermediate layer.
• the thickness of the gradient layer can be adjusted by setting suitable process ramps.
• the increase of the C-content or decrease of the metallic phase can take place continuously or stepwise, furthermore, at least in one part of the gradient layer, a sequence of metal-rich and C-type metals can also be obtained.
• a MeC layer which is applied for example by sputtering, and the proportion of free carbon by adding a carbon-containing reactive gas continuously or gradually increased.
• tungsten carbide-based layers for example, a ratio of about 50: 1 to about 2: 1 of the carbide bound to the free carbon has proved favorable. Similar dependencies could also be found for layers based on chromium carbide, tantalum carbide or molybdenum carbide.
• the material properties (for example modulus of elasticity, structure etc.) of the support layer and the DLC layer are substantially continuously adapted to each other and thus the risk of crack formation along an otherwise occurring metal or Si / DLC interface counteracted.
• the conclusion of the DLC sliding layer can be made by switching off the sputtering and / or bias supply upon reaching a defined flow of the carbon-containing process gas or upon reaching a certain pressure. Another possibility is to keep the coating parameters constant during the last process phase in order to keep the properties of the outer functional layer constant over a desired minimum layer thickness.
• the hardness of the entire carbon layer is set to a value greater than 0.8 GPa, preferably greater than or equal to 10 GPa, and even at layer thicknesses> 1 .mu.m, preferably> 2 .mu.m, an adhesive strength is better on a steel test specimen having a hardness of about 60 HRC or equal to HF 3, but preferably equal to HF 1 according to VDI 3824 sheet 4 is achieved.
• the growth rate is about 1-3 ⁇ m / h and depends, in addition to the process parameters, also on the loading and mounting. In particular, this affects whether the parts to be coated 1-, 2- or 3-turn, on magnetic brackets, or clamped or plugged attached. Also, the total mass and plasma transmittance of the supports is important, for example, with lightly constructed brackets, e.g. achieved by using storage plates, instead of plates made of solid material, higher growth rates and an overall better layer quality.
• the layer stress can be at 0.8 GPa and thus in the usual range of hard DLC layers. Furthermore, such layers, with a slightly lower hardness (9 to 15 GPa), a significantly lower coefficient of friction on the insertion forces occurring reduced.
• these properties can be achieved by adding, for example by co-sputtering, evaporation, alloying to the target materials or the like, small amounts of the elements -S
• Ag, Au, Cu, Fe, Ir, Mo, Ni, Pd, Pt, Os, Rh, Ru, W and / or their alloys are improved and / or stabilized against corrosion / oxidation. If it is desired to achieve particularly good conductive properties, it is advantageous to provide a residual metal content of at least 30 to at most 60%, preferably between 40 and 50%, in the final layer package.
• a metal-containing DLC sliding layer on a CuSn ⁇ bronze in the final, ie outer layer area was formed by means of chromium adhesion layer, but applied without additional support layer.
• a chromium adhesion layer was first applied as in process example 1 of DE 100 18 143.
• the WC targets are run for 6 minutes at constant Ar flow and 3.5 kW power, then the acetylene gas flow is increased to 200 sccm in 11 minutes and held constant for 60 minutes at the parameters described in Table 1. Subsequently, the coating process is stopped.
• Example 2 Differs from Example 1 in that the acetylene gas flow in the last stage of the process in 5 min. only increased to 80 sccm and held there for 60 minutes.
• Example 2 Differs from Example 1 in that the acetylene gas flow in the last process phase in 2 min. increased to 30 sccm and held there for 60 minutes constant.
• Example 5 Differs from Example 1 in that no acetylene added in the last stage of the process and the WC targets are operated after switching off the Cr targets, 60 min at constant Ar flow.
• Example 5 Differs from Example 1 in that no acetylene added in the last stage of the process and the WC targets are operated after switching off the Cr targets, 60 min at constant Ar flow.
• Example 5 a CrN support layer was first deposited and then applied to Example 3 a Me-DLC conductive layer on the support layer.
• the deposition of the CrN supporting layer was carried out in accordance with the parameters given in Table 5), in which case a low-voltage arc discharge ignited in the central axis between a hot cathode and an auxiliary anode was additionally operated to increase the plasma density.
• Example 6 a chromium adhesion layer was first applied as in Example 1. The subsequent WC-containing functional layer was doped with Ag.
• WC targets For activated Cr targets, four WC targets each with 1 kW power are activated and both target types are simultaneously run for 2 minutes, whereby the power of the WC targets is 1 kW within 2 minutes with the Ar flow remaining constant is increased to 3.5 kW.
• Two silver targets also incorporated in the coating system are ignited simultaneously with the WC targets and their power increased from 0 to 1 kW in the same period.
• the negative substrate voltage on the components is ramped up from 0 V applied at the end of the Cr adhesion layer to 300 V in 2 minutes.
• the Cr targets are switched off.
• the WC and Ag targets are operated together for 6 min at constant Ar flow, then the Acetylengaspound in 2 min. increased to 30 sccm and during the last coating phase the parameters according to Table 6 were kept constant for 60 minutes.
• Example 1 is a typical example of an a-C: H: Me or Me-DLC layer, with a strongly increasing C-content towards the surface.
• Example 4 represents a carbide layer, without appreciable amounts of free carbon. The indicated measured values were determined by averaging at 5 different measuring points in each case 10 s after application of a contact weight of 100 g. The tip of the Kunststoff ⁇ weight consists of gold with a diameter of 3 mm. The determination of the individual value was confirmed by a preceding and subsequent reference measurement of gold.
• the frictional force of the connectors was determined on a macro wear test bench for
• Test duration 3000 cycles 25 cycles
• the indication of the frictional force after a defined number of cycles shows the frictional wear of the sample.
• the tinned standard plug has a friction force of 1000 ⁇ iN after 25 cycles. Increasing the number of cycles to more than 30 leads to complete destruction.
• the values for DLC coated connectors are in the third column.

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• 2005
  • 2005-06-15 EP EP05747049A patent/EP1771596A1/de not_active Withdrawn
  • 2005-06-15 WO PCT/CH2005/000333 patent/WO2006005200A1/de active Application Filing
  • 2005-06-15 JP JP2007519589A patent/JP5133057B2/ja not_active Expired - Fee Related
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