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US20020032073A1 - Highly durable and abrasion resistant composite diamond-like carbon decorative coatings with controllable color for metal substrates - Google Patents

Highly durable and abrasion resistant composite diamond-like carbon decorative coatings with controllable color for metal substrates Download PDF

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US20020032073A1
US20020032073A1 US09/246,976 US24697699A US2002032073A1 US 20020032073 A1 US20020032073 A1 US 20020032073A1 US 24697699 A US24697699 A US 24697699A US 2002032073 A1 US2002032073 A1 US 2002032073A1
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Prior art keywords
product
carbon
coating
dlc
decorative coating
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US09/246,976
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Joseph J. Rogers
Rudolph Hugo Petrmichl
Fred Michael Kimock
Victor Michael Zeeman
Joseph David Sydlo
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Morgan Chemical Products Inc
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Morgan Chemical Products Inc
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Priority to US09/246,976 priority Critical patent/US20020032073A1/en
Assigned to DIAMONEX, INCORPORATED reassignment DIAMONEX, INCORPORATED ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KIMOCK, FRED MICHAEL, PETRMICHL, RUDOLPH HUGO, ROGERS, JOSEPH J., SYDLO, JOSEPH DAVID, ZEEMAN, VICTOR MICHAEL, JR.
Priority to PCT/US1999/004199 priority patent/WO2000047290A1/fr
Assigned to MORGAN CHEMICAL PRODUCTS, INC. reassignment MORGAN CHEMICAL PRODUCTS, INC. MERGER (SEE DOCUMENT FOR DETAILS). Assignors: DIAMONEX, INCORPORATED
Publication of US20020032073A1 publication Critical patent/US20020032073A1/en
Priority to US10/151,222 priority patent/US20030060302A1/en
Abandoned legal-status Critical Current

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    • 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
    • C23C16/006—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterized by the colour of the layer
    • A—HUMAN NECESSITIES
    • A63—SPORTS; GAMES; AMUSEMENTS
    • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
    • A63B53/00—Golf clubs
    • A63B53/04—Heads
    • A—HUMAN NECESSITIES
    • A63—SPORTS; GAMES; AMUSEMENTS
    • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
    • A63B53/00—Golf clubs
    • A63B53/12—Metallic shafts
    • A—HUMAN NECESSITIES
    • A63—SPORTS; GAMES; AMUSEMENTS
    • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
    • A63B60/00—Details or accessories of golf clubs, bats, rackets or the like
    • 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
    • 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
    • C23C16/44—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 method of coating
    • C23C16/458—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 method of coating characterised by the method used for supporting substrates in the reaction chamber
    • 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
    • C23C16/44—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 method of coating
    • C23C16/50—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 method of coating using electric discharges
    • C23C16/505—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 method of coating using electric discharges using radio frequency discharges
    • C23C16/509—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 method of coating using electric discharges using radio frequency discharges using internal electrodes
    • A—HUMAN NECESSITIES
    • A63—SPORTS; GAMES; AMUSEMENTS
    • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
    • A63B2209/00—Characteristics of used materials
    • A63B2209/02—Characteristics of used materials with reinforcing fibres, e.g. carbon, polyamide fibres
    • A—HUMAN NECESSITIES
    • A63—SPORTS; GAMES; AMUSEMENTS
    • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
    • A63B53/00—Golf clubs
    • A63B53/04—Heads
    • A63B53/0416—Heads having an impact surface provided by a face insert
    • A—HUMAN NECESSITIES
    • A63—SPORTS; GAMES; AMUSEMENTS
    • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
    • A63B53/00—Golf clubs
    • A63B53/04—Heads
    • A63B53/0487—Heads for putters
    • A—HUMAN NECESSITIES
    • A63—SPORTS; GAMES; AMUSEMENTS
    • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
    • A63B60/00—Details or accessories of golf clubs, bats, rackets or the like
    • A63B60/004—Striking surfaces coated with high-friction abrasive materials

Definitions

  • This invention relates generally to highly durable and abrasion-resistant decorative coatings. More particularly, the invention relates to a process for depositing a highly durable and abrasion-resistant composite diamond-like carbon coating with controllable color.
  • the invention is particularly suited for applications as a highly durable decorative coating on electrically conducting substrates which are subjected to high wear environments including architectural hardware and fixtures made of brass and other metals, jewelry, medical and dental instruments, writing instruments such as pens and pencils, musical instruments, eyeglass frames, cigar and cigarette lighters, automobile hood ornaments and other components, sporting equipment and other products for leisure activities such as golf club shafts, golf club heads, cycling equipment, and fishing and hunting equipment, and other similar substrates.
  • the cosmetic appearance of these coatings falls into four categories: (i) metal or ceramic coatings with a shiny, metallic appearance, (ii) ceramic coatings with a white color appearance, (iii) metal oxide or ceramic coatings with a black color appearance, and (iv) paints, which can be of any color.
  • Decorative metallic protective coatings with a shiny cosmetic appearance include chrome and nickel. Titanium nitride is a ceramic coating which can have the appearance of brass or gold, depending on the nitrogen content in the material.
  • Buettner U.S. Pat. No. 5,531,444 describes a golf club head coated with a hard coating of titanium nitride having a lustrous gold appearance.
  • the titanium nitride coating is applied at a relatively high substrate temperature in the range of 650° F. to 950° F. (340° C. to 510° C.), which limits the types of golf head materials which can be coated to high softening point steels and other hard metals. Because of this requirement of high substrate temperature to achieve the desired properties of the coating, substrates which contain plastic or composite components, such as plastic putter inserts, cannot be coated.
  • Decorative and protective ceramic coatings with a white color appearance such as aluminum oxide, zirconium oxide, and other ceramic glazings are also known. These coatings are normally made from fine powders which are applied to the surface of components, and then fired to final form. High substrate temperatures are required to produce a durable finish, and these materials are brittle and prone to cracking and flaking when the substrate is subjected to flexure or high impact conditions.
  • Decorative and protective metal oxide or ceramic coatings with a black color appearance such as black chrome oxide and black aluminum oxide are also known. These coatings typically display a low-gloss black finish, which has low luster. In addition, these coatings are easily scratched by abrasives and exhibit corrosion-resistance which is less than desired.
  • U.S. Patent No. 4,951,953 describes a golf club coated with a material having a high Young's modulus, or with a composite material having a high Young's modulus material as a substantial ingredient in the matrix.
  • the coating may have a thickness in the range of about 1 to 10 mils (25 microns to 250 microns).
  • the materials of choice have a Young's modulus of 50 million pounds per square inch (psi) or greater, and include silicon nitride, aluminum oxide, silicon carbide and diamond.
  • the invention provides products having a highly durable and abrasion-resistant composite diamond-like carbon coating with controllable color which is ideally suitable as a decorative coating on metal substrates.
  • the invention also provides the process for depositing a highly adherent, highly abrasion resistant diamond-like carbon decorative coating to electrically conductive substrates.
  • the products of the present invention include sporting equipment such as shafts and heads of golf clubs (drivers, putters, irons), cycling equipment, fishing and hunting equipment and other leisure activity products.
  • the products of the present invention also include architectural hardware and fixtures made of brass and other metals, jewelry, medical and dental instruments, writing instruments such as pens and pencils, musical instruments, eyeglass frames, cigar and cigarette lighters, automobile hood ornaments and other components, and other similar metal substrates.
  • the composite diamond-like carbon coating structure consists of at least a first layer of Si-doped diamond-like carbon which is comprised of the elements C, H, Si and possibly O and N.
  • An additional coating comprised of layers of Si-doped diamond-like carbon and diamond-like carbon may be applied over top of the first Si-doped diamond-like carbon layer.
  • the optional additional layers of Si-doped diamond-like carbon are also comprised of the elements C, H, Si and possibly 0 and N.
  • the optional additional layers of diamond-like carbon are comprised of the elements C, H and possibly N.
  • the decorative and abrasion-resistant composite diamond-like carbon coating is deposited by ion-assisted plasma deposition including capacitive radio frequency plasma and ion-beam deposition, from carbon-containing and silicon-containing precursor gases consisting of hydrocarbon, silane, organosilane, organosilazane and organo-oxysilicon compounds, or mixtures thereof.
  • the resulting decorative coating has the properties of Nanoindentation hardness in the range of approximately 5 to 35 GPa, modulus in the range of approximately 50 to 300 GPa, and thickness in the range of approximately 1 to 25 micrometers.
  • the colors of the coating unexpectedly can be varied continuously along the spectrum of: light yellow to bronze to copper-gold to burgundy to bluish-black to black.
  • the color range of these coatings is characterized by reflected light chromaticity coordinate values (x, y) in the range of approximately 0.25 to 0.50 for x, and in the range of approximately 0.25 to 0.45 for y as measured with Commission International de 1′Eclairage (“CIE”) 1931 source C standard illuminant and CIE 1931 2-degree standard observer.
  • CIE Commission International de 1′Eclairage
  • the preferred mode of ion-assisted plasma deposition of the decorative and abrasion-resistant diamond-like carbon coating is capacitively-coupled radio frequency (RF) plasma deposition.
  • RF radio frequency
  • the elemental composition, refractive index and thickness of the composite diamond-like carbon coating are chosen to produce the desired reflected optical color.
  • the deposition process parameters such as precursor gas composition, plasma power, pressure, and substrate bias voltage are adjusted to produce coatings with different elemental composition and refractive indexes, which change the reflected optical color, and hardness and elastic modulus, which effect the abrasion resistance and durability of the coating.
  • FIG. 1 is a diagrammatic view, partially in cross-section, of an illustrative capacitively-coupled radio frequency plasma deposition apparatus used to manufacture coated articles of the present invention.
  • FIG. 2 is a diagrammic view, partially in cross-section of an illustrative plasma ion beam deposition apparatus used to manufacture coated articles of the present invention.
  • the present invention substantially reduces or eliminates the disadvantages and shortcomings associated with the prior art techniques by providing for the deposition of a highly durable and abrasion-resistant composite diamond-like carbon decorative coating with controllable color which is ideal for metal and other electrically conductive substrates including architectural hardware and fixtures made of brass and other metals, jewelry, medical and dental instruments, writing instruments such as pens and pencils, musical instruments, eyeglass frames, cigar and cigarette lighters, automobile hood ornaments and other components, sporting equipment and other products for leisure activities such as golf club shafts, golf club heads, cycling equipment, and fishing and hunting equipment, and other similar metal substrates.
  • the mechanical and optical properties of the composite diamond-like carbon coatings of the present invention can be varied over a very wide continuous range, and thus the coatings can be tailored to the needs of many diverse applications.
  • the composite diamond-like carbon decorative coatings of the present invention have the following remarkable performance characteristics compared to prior art techniques:
  • [0032] (5) can be made with high luster, or a low-luster finish if desired,
  • the coatings of the present invention have a unique ability to hide fingerprints, when applied over substrates with a variety of surface finishes.
  • the diamond-like carbon materials may also contain dopant atoms such as nitrogen and silicon.
  • DLC materials which are doped with silicon in the range of approximately 2 atomic % to approximately 40 atomic % are termed Si-doped diamond-like carbon, Si-DLC.
  • the Si-DLC materials may also contain nitrogen, and possibly oxygen.
  • the coatings of the present invention are softer and thinner than those disclosed in Kim, U.S. Pat. No. 4,951,953, yet they can be remarkably resistant to scratching when deposited on steel alloys or other metals of comparable hardness.
  • the elastic moduli of the decorative coatings of the present invention are less than the 340 GPa (50 million psi) critical value disclosed in the '953 patent, and are typically less than 200 GPa (29 million psi) as measured by nanoindentation using a Nanoindenter II instrument manufactured by Nano Instruments, Incorporated (Oak Ridge, Tenn.).
  • the preferred thickness range of the coatings of the present invention in the range of approximately 1 micrometer to approximately 25 micrometers, is below the range of 25 to 250 micrometers described in the '953 patent.
  • the coatings of the present invention can be made with excellent adhesion to the substrate such that no delamination occurs under high impact conditions. Even on a soft material such as aluminum, which readily deformed when struck with a harder material, coatings of the present invention adhered so remarkably well that no flaking was observed in the impact area.
  • the coatings of the present invention When applied to metal substrates, the coatings of the present invention exhibit a variety of unique and attractive colors.
  • the color of the composite diamond-like carbon coating can be varied continuously along the spectrum of: light yellow, bronze, copper-gold, burgundy, bluish-black, and black.
  • the appearance of these colors on metal surfaces coated by the process of the present invention is unexpected, because a different color spectrum consisting of: nearly water-clear, light yellow, yellow-brown, brown, and black are obtained on transparent or partially transparent substrates such as glass or plastics.
  • Primary process parameters which control the colors of the coating are the energy of ions bombarding the surface during coating deposition, the feed gas chemistry, and the thickness of the coating.
  • the coating color moves along the unique color spectrum of this invention from the light end, i.e. light colors, to the dark end, i.e. dark colors.
  • the phrase “energetics of the deposition process,” is defined as the energy delivered to the coating surface divided by the deposition rate. Energy is delivered to the coating surface by substrate heating, impacting ions and fast neutral species, and radiated power from the plasma.
  • the energetics of the deposition process can be increased by increasing any of the following independent process control parameters while holding others constant: (i) the power, e.g.
  • the energetics of the deposition process can be increased by decreasing the following independent process control parameters while holding others constant: (v) the total flow rate of process gases, (vi) the flow rate of the precursor feed gases, (vii) the molecular weight of the precursor feed gas, and (viii) the electrically active surface area of the powered electrode and substrates.
  • DLC materials made from a pure hydrocarbon precursor feed gases are black in color, when deposited to thicknesses greater than about 1 micrometer, but the color can be shifted to the light end of the spectrum, i.e. yellow-brown color, by reducing the energetics of the deposition process.
  • the color shifts to the yellow-brown range at such low deposition energy that the resulting coatings are soft and polymeric in nature, and unsuitable for protecting metal substrates from abrasion.
  • the coating color can be controlled by selectively adjusting the precursor feed gas chemistry. It has been found that a color shift toward the light end of the spectrum can be induced in the coating under conditions of high deposition energetics by adding silicon to the carbon-containing precursor feed gas stream.
  • Appropriate sources of silicon for the process of the present invention include, but are not limited to silanes, organosilanes, organosilazanes, and organo-oxysilicon compounds such as organosiloxanes.
  • silicon-containing compounds suitable for the process of the present invention include, but are not limited to silane, disilane, diethylsilane, tetramethylsilane, hexamethyldisilazane, hexamethyldisiloxane, tetramethyldisilazane, tetramethyldisiloxane, octamethylcyclotetrasiloxane, and ethoxytrimethylsilane.
  • Suitable carbon-containing precursors for DLC include, but are not limited to hydrocarbons such as methane, butane, acetylene and cyclohexane, and mixtures thereof.
  • carbon-containing precursors may be used alone or in conjunction with noble gases, hydrogen or nitrogen for the deposition of DLC, or combined with the silicon-containing precursor gases for the deposition of Si-DLC.
  • silicon-containing and carbon-containing precursor feed gases are used in the process of the present invention, the coating color can be further shifted toward the light end of the spectrum by adding nitrogen, oxygen or hydrogen to the precursor feed gas stream.
  • the inventors also speculate that the presence of oxygen or hydrogen further reduces the carbon concentration in the coating, by reacting with the carbon in the feed gas and in the coating and thereby producing highly volatile, stable and unreactive carbon byproducts (such as methane and carbon dioxide) that can be readily removed from the deposition chamber by the vacuum pump. Additionally, since oxygen atoms readily bond with silicon, when oxygen is present in the deposition process gas it may reactively bond into the Si-DLC matrix of the coatings of the present invention. Since there is no absorption of visible light associated with Si—O or C—O bonds, as the oxygen content in the coating is increased, the coating color is shifted toward the lighter end of the spectrum.
  • the coatings of the present invention which contains Si-DLC exhibit an unusual luster and depth of color. When viewed at different angles, the coatings can appear to shift in color. When viewed in sunlight, the depth of color is accentuated, and the appearance of the coating can be very different than in artificial light. This effect is also noticeable at the dark end of the color spectrum, where shades of purple and blue can be seen in the coatings at certain viewing angles. DLC coatings made from pure hydrocarbon precursor feed gases at high energy are also shiny black in color, but lack the luster achieved by the composite diamond-like carbon decorative coatings of the present invention which contain silicon.
  • the coatings of the present invention can be produced at low substrate temperatures of less than 150° C., whereas coatings of the prior art generally require substrate temperatures greater than 300° C. This enables deposition of the composite diamond-like carbon coatings on temperature sensitive alloys and metals, as well as on composite articles with temperature sensitive components, such as plastic golf putter inserts.
  • the low deposition temperature capability of the process of the present invention means that no special fixturing concepts, such as direct contact water cooling of the substrates are required.
  • the process of the present invention can be used to deposit thick and highly durable coatings at substrate temperatures less than 150° C., without intimate thermal contact between the substrate and a cooled surface. This is particularly important for applications where the majority of the surface area of a substrate needs to be coated, and therefore cannot be placed in intimate contact with a cooled mounting surface. Furthermore, this capability greatly simplifies the fixturing requirements for temperature sensitive substrates with complex shapes.
  • the maximum substrate temperature reached, in the deposition process of the present invention declines significantly when the pressure within the deposition vacuum chamber is decreased below the typical range of 50 ⁇ 10 ⁇ 3 Torr to 500 ⁇ 10 ⁇ 3 Torr employed in prior art RF plasma deposition of DLC coatings.
  • This decrease in substrate temperature was highly unexpected, because the total power required to deposit coatings of equal thickness and hardness at different pressures is approximately constant. It has been found that as the process pressure is decreased, less power is required to maintain the desired substrate bias voltage, but this effect is offset by a reduction in the deposition rate. The observed effect of reduced substrate temperature is too dramatic to be explained by the increased effectiveness of radiative cooling when the instantaneous heat load is low.
  • the inventors have observed that the low pressure deposition plasma is more diffuse than the prior art plasmas, and it is speculated that at low pressures, the plasma power may be dissipated more evenly at the boundaries of the plasma.
  • the coatings of the present invention are amorphous, unlike the coatings on golf clubs described by Kim in the '953 patent.
  • crystalline coatings of the prior art the presence of grain boundaries and other imperfections degrades the ability of the coating to protect the substrate from corrosive agents, reduces the ability of the coating to withstand impact and flexure without cracking, chipping, or flaking from the substrate.
  • the surface morphology of crystalline coatings necessitates post-deposition polishing to achieve a mirror-like appearance.
  • no post-deposition processing is required to achieve the attractive, lustrous surface finish.
  • the thickness of the composite diamond-like carbon coating be greater than approximately 1 micrometer, which is much greater than the wavelengths of visible light (approximately 0.5 micrometer).
  • the perceived color of the coating is significantly influenced by the inherent optical color (a combination of absorption, reflection and refractive index characteristics) of the coating material, and the reflectivity characteristics of the substrate.
  • the perceived color of the coating is not simply generated by thin film optical interference effects, known to those skilled in the art of optical coatings.
  • Representative of prior art thin film optical interference coatings are quarter wavelength stacks of dielectric layers, which may be combined with thin reflective metal films, to generate iridescent colors on substrates such as sunglass lenses.
  • the coating can have a shiny appearance, but lacks the luster or depth of more transparent coatings.
  • the threshold coating thickness for complete absorption is approximately 0.5 micrometer, and above this threshold, these coatings are black. As the absorption coefficient is reduced, by reducing the deposition energetics or by changing the precursor feed gas chemistry as described above, the maximum thickness for which the luster is apparent increases.
  • the composite diamond-like carbon decorative coatings have hardness in the range of approximately 5 to 35 GPa, and modulus in the range of approximately 50 GPa to 300 GPa.
  • a single layer of transparent or partially transparent Si-DLC is deposited on a metal substrate to a thickness in the range of 1 to 25 micrometers.
  • the Si-DLC may also contain O and N.
  • the second composite diamond-like carbon coating structure which provides a lustrous appearance
  • multiple layers of transparent or partially transparent Si-DLC of different elemental composition are sequentially deposited on the metal substrate.
  • all layers in this coating may also contain O and N.
  • the coating structure can be tailored to the requirements of the application.
  • the first layer may be enriched with silicon in order to maximize the adhesion to the substrate.
  • several thin layers with varying refractive indices may be included at the top of the coating (away from the coating-metal interface) in order to control or reduce any thin film interference effects that may be present.
  • a coating is produced by first depositing on a metal substrate one or more layers of the transparent or partially transparent Si-DLC, containing Si, C, H and optionally O and N, and then depositing at least one layer of DLC, consisting essentially of C and H, and optionally N.
  • the thickness of the single DLC layer, or multiple DLC layers is less than the maximum for complete absorption of visible light within the composite coating, and the total thickness of the composite coating is in the range of approximately 1 to 25 micrometers.
  • the third composite diamond-like carbon coating structure has the advantage that the composite coating with the DLC top layer generally affords maximum chemical resistance, with the exception of oxidizing environments, for which the Si-DLC top layer is preferred.
  • the DLC layers in this structure may be further refined to suit the mechanical requirements of the application by adding small amounts of other elemental constituents. For example, small amounts of metal may be incorporated in the top DLC layer to reduce the friction of the coating in high humidity environments.
  • a nontransparent layer of DLC consisting essentially of C, H and optionally N
  • layers of transparent Si-DLC consisting of Si, C, H, and optionally O and N.
  • the purpose of the Si-DLC layer adjacent to the metal interface is to provide good adhesion, while the purpose of the top layer of Si-DLC is to provide luster and depth of color to the coating. While visible light entering the DLC layer or layers is completely absorbed, some of the light impinging on the interface between the Si-DLC and the DLC is reflected due to refractive index mismatch.
  • the advantage of the fourth composite diamond-like carbon coating structure is that a shiny black coating with luster and depth of color is produced.
  • a highly durable shiny black composite diamond-like carbon decorative coating having a structure of a first layer of Si-DLC consisting of Si, C, H, and optionally O and N, and at least a second layer of DLC consisting essentially of C, H and optionally N, which DLC layer is thick enough and of sufficient optical density to not allow visible light to reach the Si-DLC layer can be made by the ion-assisted plasma deposition process of the present invention.
  • the top layer of DLC in this structure has a thickness of greater than 0.5 micrometer, and the total thickness of the composite coating is in the range of approximately 1 to 25 micrometers.
  • This type of composite diamond-like carbon coating has the properties of outstanding adhesion, superior abrasion resistance, corrosion resistance, but has a shiny black color, rather than the lustrous colors of the Si-DLC containing coatings of the present invention.
  • these shiny black composite diamond-like carbon coatings can have high hardness in the range of approximately 15 to 35 GPa, and high modulus, in the range of approximately 120 GPa to 300 GPa, both of which are at the upper end of the range of these properties for the coatings of the present invention.
  • the characteristics and appearance of this shiny black composite diamond-like carbon decorative coating is ideal for sporting equipment including golf club shafts, and golf club heads such as putters, drivers and irons.
  • the thickness of the first Si-DLC layer is in the range of approximately 0.1 to 15 micrometers. This thickness range has been found to produce the best adhesion to the substrate for the multiple-layer coatings of the present invention.
  • the preferred method of the present invention comprises the following steps.
  • the substrate is first chemically cleaned to remove contaminants.
  • the substrate is inserted into a vacuum coating chamber and the air in the chamber is evacuated.
  • the substrate surface is sputter-etched by a flux of energetic ions or other reactive species to assist in the removal of residual contaminants such as residual hydrocarbons and surface oxides, and to activate the surface.
  • the fourth step after the substrate surface has been etched and activated, at least a first layer of Si-DLC is deposited by an ion-assisted plasma deposition process, preferably capacitively-coupled RF plasma deposition, from carbon-containing and silicon-containing precursor gas compounds.
  • an additional coating consisting of at least one layer of DLC or Si-DLC may be deposited by an ion-assisted plasma deposition process, preferably capacitively-coupled RF plasma deposition, from precursor gases.
  • the deposition of the desired thickness and number of DLC and Si-DLC layers is continued until the desired optical color and total coating thickness is achieved, at which point the deposition process on the substrates is terminated.
  • the vacuum chamber pressure is increased to atmospheric pressure, and the coated metal substrates having a highly durable and abrasion-resistant composite diamond-like carbon decorative coating are removed from the vacuum chamber.
  • the process of the present invention can be carried out in a batch-type vacuum deposition system, in which the main vacuum chamber is evacuated and vented to atmosphere after processing each batch of parts; a load-locked deposition system, in which the main vacuum deposition chamber is maintained under vacuum at all times, but batches of parts to be coated are shuttled in and out of the deposition zone through vacuum-to-air load locks; or in-line processing vacuum deposition chambers, in which parts are flowing constantly from atmosphere, through differential pumping zones, into the deposition chamber, back through differential pumping zones, and returned to atmospheric pressure.
  • FIG. 1 A preferred ion-assisted plasma deposition apparatus for producing the preferred embodiment of the present invention by capacitively-coupled RF plasma deposition, in accordance with Holland, U.S. Pat. No. 4,382,100, which is incorporated herein by reference, is illustrated schematically in FIG. 1.
  • the process is carried out inside vacuum chamber 10 , which is fabricated according to techniques known in the art.
  • Vacuum chamber 10 is evacuated by first pumping with a rough vacuum pump (not shown) and then by an optional high vacuum pump (not shown).
  • a high vacuum pump allows for removal of greater levels of air and contaminants from the chamber prior to initiating the deposition process, and also enables operation of the plasma at lower pressures than can be achieved with a rough vacuum pump.
  • the high vacuum pump can be a diffusion pump, turbomolecular pump, or other high vacuum pumps known in the art.
  • substrates 13 are mounted either in recessed holes directly in the powered electrode, or equivalently in recessed holes 14 in electrically conductive mounting block 15 which in turn rests on powered electrode 20 .
  • substrates 13 may be mounted on metal mounting studs 16 , which are in electrical contact with powered electrode 20 and may or may not be recessed into mounting block 15 .
  • Powered electrode 20 may be stationary, or may incorporate a rotation mechanism.
  • Powered electrode 20 is shown with cooling water inlet 22 and cooling water outlet 24 of a typical cooling system 25 for RF chamber 10 .
  • RF power circuit 30 is electrically connected to grounded electrode 12 and powered electrode 20 via cables or connectors as shown by means well known in the art. Electrically grounded dark space shield 32 is separated from powered electrode 20 by a small gap 34 .
  • DC blocking capacitor 36 in RF power circuit 30 allows the entire electrode assembly, i.e., substrates 13 , mounting block 15 , mounting studs 16 , and powered electrode 20 , to develop a negative voltage (also known in the art as DC self-bias voltage) upon ignition of plasma 37 by application of suitable RF power from RF generator 38 in the presence of process gases.
  • the process gases which may include argon for sputter-etching of the substrates prior to coating deposition, and precursor gases for deposition, pass through gas line 40 into shower head distributor 42 and out through orifices 44 into chamber 10 .
  • the effluent gases are exhausted through exhaust pumping port 50 .
  • An automated variable throttle valve in the exhaust port (not shown in FIG. 1) is used to control the rate of gas removal from the vacuum chamber. The pressure in the chamber is thus controlled by throttle valve position and total gas flow into the chamber.
  • RF blocking inductor 52 in circuit 30 permits measurement of the DC bias voltage via voltmeter 54 .
  • Matching network 56 in circuit 30 is tuned to assure optimum delivery of RF power into plasma 37 .
  • Typical process operating conditions include gas pressure in the range of approximately 1 ⁇ 10 ⁇ 3 Torr to 500 ⁇ 10 ⁇ 3 Torr, RF frequency of 13.56 MHZ, peak-to-peak RF voltages in the range of approximately 500 to 2000 Volts, and DC self-bias voltages in the range of approximately ⁇ 100 to ⁇ 1,000 Volts.
  • the surface area of grounded surfaces is normally substantially larger than the surface area of powered electrode 20 and substrates 13 .
  • ion bombardment energies and fluxes are much larger on the powered electrode than they are on the grounded surfaces including grounded electrode 12 .
  • Bombardment by positive ions from an inert gas (e.g. Ar) plasma results in sputter-etching of the exposed surfaces of the substrate assembly which includes substrates 13 , mounting block 15 , mounting studs 16 , and powered electrode 20 .
  • ion bombardment by positive ions of the precursor gases such as hydrocarbon gases (e.g.
  • the apparatus of FIG. 1 may also be used to perform DC plasma deposition by replacing RF power circuit 30 with a DC power supply.
  • the negative terminal of the DC power supply is connected to electrode 20 , and a DC plasma is ignited between the substrates and the grounded components such as electrode 12 within vacuum chamber 10 .
  • DC power supplies capable of negative bias voltages up to ⁇ 3000 Volts are suitable for the DC plasma deposition method.
  • the advantage of the DC plasma method of ion-assisted plasma deposition is the simplicity of the power supply configuration. However, this configuration is susceptible to formation of arcs during the deposition of insulating Si-DLC and DLC coatings. The arcs may be overcome by using arc suppression method known in the art.
  • the primary control parameters are the precursor composition and flow rate, the bias voltage, and the substrate temperature.
  • the useful range of the latter is, however, limited for metal alloy substrates of low melting point or softening point, and substrates which contain temperature sensitive components, such as plastic inserts which are used in golf putters.
  • Other process parameters that affect the coating properties in the ion-assisted plasma process are the total flow rate, discharge power, pressure, size and shape of electrodes, and the presence of external magnetic fields.
  • the apparatus illustrated in FIG. 2 may be utilized to perform the ion-assisted deposition process of the present invention by plasma ion beam deposition.
  • the process is carried out inside vacuum chamber 61 , which is pumped by high vacuum pump 62 which is typically a turbomolecular pump or diffusion pump.
  • Fixture 63 is used to hold substrates 71 , in this case on rotating drum 70 .
  • drum 70 and substrates 71 both rotate in opposite directions, but the type and degree of substrate rotation is chosen depending on the configuration of the substrates, to obtain adequate uniformity of the coating thickness and properties.
  • Deposition of the Si-DLC and DLC layers is carried out by ion plasma beam deposition using ion source 64 , which is operated on inert gases introduced via inlet 65 , and silicon-containing and carbon-containing precursor gases which may be introduced via inlets 66 or 67 .
  • Inlets 68 and 69 are available for adding dopant gases such as oxygen, nitrogen and hydrogen to the chamber during deposition to modify the properties of the depositing Si-DLC or DLC layer.
  • An example of the use of FIG. 2 for the decorative coatings of the present invention would be in the coating of golf club shaft substrates 71 , mounted on rotating spindles 70 of drum planetary fixture 63 . The long axis of the golf club shafts would be perpendicular to the plane of the drawing of FIG. 2.
  • ion source 64 could be replaced by a magnetron sputtering cathode to perform deposition of the coatings of the present invention by ion-assisted sputter deposition.
  • the carbon-containing and silicon-containing deposition flux is achieved by sputtering from carbon-containing and silicon-containing cathode materials such as carbon, silicon, and silicon carbide.
  • the substrate is first chemically cleaned to remove contaminants, such as residual hydrocarbons and other contaminants, from the substrate manufacturing and handling processes.
  • Ultrasonic cleaning in solvents, or other aqueous detergents as known in the art is effective. Details of the cleaning procedure depend upon the nature of the contamination and residue remaining on the part after manufacture and subsequent handling. It has been found that it is critical for this chemical cleaning step to be effective in removing surface contaminants and residues, or the resulting adhesion of the coating will be poor.
  • the substrate is inserted into a vacuum chamber, and the air in the chamber is evacuated.
  • the vacuum chamber is then typically evacuated to a pressure of approximately 1 ⁇ 10 ⁇ 3 Torr or less.
  • the exact level of vacuum is dependent upon the nature of the substrate material, the sputter-etching rate of the substrate, the constituents present in the vacuum chamber residual gas, and the details of the coating process. It is not desirable to evacuate to lower pressures than necessary, as this increases the overall process cycle time, and reduces the throughput of the coating system.
  • non-depositing gases such as argon, xenon, krypton, nitrogen and hydrogen are flowed into the chamber, and a plasma is initiated by applying RF power to the substrates. Ions in the plasma are extracted by the bias voltage on the substrates, and impact the substrate with sufficient energy to sputter-etch the substrate surface to remove residual contaminants, such as hydrocarbons, surface oxides and other unwanted materials not removed in the first cleaning step, and to activate the surface. This sputter-etching of the substrate surface generates an atomically clean surface, and is required to achieve high adhesion between the substrate surface and the coating.
  • argon, xenon, krypton, nitrogen and hydrogen are flowed into the chamber, and a plasma is initiated by applying RF power to the substrates. Ions in the plasma are extracted by the bias voltage on the substrates, and impact the substrate with sufficient energy to sputter-etch the substrate surface to remove residual contaminants, such as hydrocarbons, surface oxides and other unwanted materials not removed in the first cleaning
  • the bias voltage is set to ⁇ 500 V or more, and the chamber pressure is maintained as low as possible (less than approximately 50 ⁇ 10 ⁇ 3 Torr) by completely opening the automated throttle valve in the exhaust port.
  • Bias voltages as high as approximately ⁇ 2000 Volts can be used, but lower bias voltages are usually used in order to minimize heating of the substrate.
  • At least a first layer of Si-DLC is deposited by ion-assisted plasma deposition, preferably capacitively-coupled RF plasma deposition, from carbon-containing and silicon-containing precursor gases which are introduced into the vacuum chamber.
  • carbon-containing and silicon-containing precursor gases consist of hydrocarbon, silane, organosilane, organosilazane and organo-oxysilicon compounds, or mixtures thereof.
  • the flow of non-depositing gas or gases used to sputter-etch the substrate may be shut off entirely at this point in the process, or alternatively, may continue along with the flow of precursor gases.
  • Other gases, such as nitrogen, hydrogen or oxygen, may be added to the precursor gas flow in order to modify the optical and mechanical properties of the depositing Si-DLC coating.
  • a second coating consisting of at least one layer of DLC or Si-DLC may be deposited by ion-assisted plasma deposition, preferably capacitively-coupled RF plasma deposition, from precursor gases.
  • DLC is deposited from hydrocarbon precursor gases, and possibly nitrogen, hydrogen, and inert gases.
  • Additional layers of Si-DLC are deposited from carbon-containing and silicon-containing precursor gases, including hydrocarbon, silane, organosilane, organosilazane and organo-oxysilicon compounds, or mixtures thereof.
  • gases such as nitrogen, hydrogen or oxygen, may be added to the precursor gas flow in order to modify the optical and mechanical properties of the additional layers of Si-DLC.
  • the thickness, refractive index, and number of the layers in the composite coating are chosen to produce the desired optical color, as well as the required durability characteristics such as resistance to scratches and abrasion.
  • the physical thickness of individual layers in the second coating is typically approximately 0.5 micrometer or greater. If a shiny black coating is desired, the thickness of the DLC layer in the second coating is greater than 0.5 micrometer.
  • the additional layer of DLC or Si-DLC is deposited immediately after completion of the first coating layer, in the same vacuum chamber and in the same vacuum cycle. This eliminates the added cost of additional pumpdown cycles, and improves the quality of the interface between the first coating layer and the second coating.
  • the deposition of the desired thickness and number of DLC and Si-DLC layers is continued until the desired optical color and total coating thickness in the range of approximately 1 to 25 micrometers is achieved, at which point the deposition process on the substrates is terminated. Then, the vacuum chamber pressure is increased to atmospheric pressure, and the substrates having a highly durable and abrasion-resistant composite diamond-like carbon decorative coating having thickness in the range of approximately 1 to 25 micrometers, hardness in the range of approximately 5 to 35 GPa, and modulus in the range of approximately 50 to 300 GPa is removed from the vacuum chamber.
  • Appropriate types of precursor feed gases for the process for depositing the decorative composite diamond-like carbon coatings of the present invention include, but are not limited to hydrocarbon compounds, silanes, organosilanes, organosilazanes, and organo-oxysilicon compounds such as organosiloxanes.
  • Examples of specific compounds suitable for the process of the present invention include, but are not limited to carbon-containing precursors such as methane, butane, cyclohexane and acetylene, and silicon-containing precursors such as silane, disilane, diethylsilane, tetramethylsilane, hexamethyldisilazane, tetramethyldisilazane, hexamethyldisiloxane, tetramethyldisiloxane, and ethoxytrimethylsilane.
  • Noble gases such as argon, krypton and xenon, and other gases such as nitrogen, oxygen and hydrogen may be added to the flow of precursor gases to modify the properties of the depositing coatings.
  • silicon-containing precursors such as diethylsilane and tetramethylsilane also contain carbon atoms
  • some of the silicon-containing precursors such as hexamethyldisilazane and tetramethyldisilazane also contain C and N atoms
  • some of the silicon-containing precursors such as hexamethyldisiloxane, tetramethyldisiloxane, and ethoxytrimethylsilane also contain C and O atoms.
  • the coatings were deposited in a capacitively-coupled RF plasma deposition apparatus, consisting of a 24-inch diameter ⁇ 36-inch high vacuum chamber with a 6-inch diameter water-cooled powered electrode.
  • the vacuum chamber was evacuated by a roots blower/mechanical pump combination, and a turbomolecular high vacuum pump.
  • the golf clubs including shafts and heads, were cleaned by wiping with isopropyl alcohol, allowed to dry, and then were mounted vertically, with the handle end attached to the powered electrode by a simple metal mounting stud. Individual golf club shafts and golf club shafts with attached heads were coated one at a time.
  • the chamber was evacuated to less than 1 ⁇ 10 ⁇ 3 Torr, and then argon was introduced at a flow of 25 sccm and the pressure increased to 22 ⁇ 10 ⁇ 3 Torr.
  • a plasma was initiated by applying RF power to the powered electrode and golf club, and the RF power was increased t 0 6360 W until a ⁇ 625 V substrate bias was achieved.
  • the golf clubs were sputter-etched in the argon plasma for 3 minutes, before 25 sccm of tetramethylsilane was added to the argon gas flow.
  • the pressure increased to 28 ⁇ 10 ⁇ 3 Torr, and the power was increased to 400 W to maintain the ⁇ 625 V bias.
  • a first layer of Si-DLC was deposited from the tetramethysilane/argon mixture to a thickness of about 0.5 micrometer.
  • 25 sccm cyclohexane was introduced, and the argon and tetramethylsilane flows were both shut off, to initiate the deposition of DLC.
  • the pressure decreased to 27 ⁇ 10 ⁇ 3 Torr, and the power was adjusted to 390 W to maintain the ⁇ 625 V bias.
  • the DLC deposition was continued for a total of 30 minutes, to achieve a top layer of DLC which was approximately 2 micrometers thick.
  • the coated golf club shafts and heads had a uniform shiny black appearance, and were highly resistant to scratching with 400 grit SiC sandpaper.
  • a plasma was ignited at a RF frequency of 13.56 MHZ, and a power of approximately 400 Watts, resulting in a self-bias voltage of ⁇ 700 Volts on the powered electrode and the substrates.
  • the substrates were sputter-etched for a period of 10 minutes under these conditions to remove residual hydrocarbon contamination and oxide layers from the surface.
  • composite diamond-like carbon coatings containing at least one layer of Si-DLC were deposited using ion-assisted plasma deposition from silicon-containing precursor gases, using the conditions presented in Table 1 below. Properties of the deposited composite diamond-like carbon coatings on polished aluminum, ZA12 zinc-aluminum alloy, and stainless steel substrates are also summarized in Table 1.
  • the coatings presented in Table 1 demonstrated excellent adhesion in boiling water-to-ice water thermal shock adhesion tests, and in impact tests in which the coated substrates were impacted with a sharp corner of a hard metal wedge golf club head, to simulate aggressive banging together of unprotected golf club heads.
  • Reflected light chromaticity coordinates of the coupons were measured using a Hunter UltraScan XE dual beam, xenon source, flash spectrophotometer with a wavelength range of 360 to 750 nm. A six-inch diameter, barium coated integrating sphere was used to measure reflected light. Tristimulus integrations using CIE 1931 source C standard illuminant and CIE 193 1 2-degree standard observer were performed to obtain the chromaticity coordinates were based on a triangular bandpass of 10 nm and a wavelength interval of 10 nm. The appearance color, and chromaticity coordinate data for the test coupons are presented in Table 2 below.
  • the chromaticity coordinate values of (x,y) in Table 2 also indicate some of the representative color coordinates for the lustrous bronze, copper-gold, burgundy, bluish-black, and shiny black coatings of the present invention.
  • the range of chromaticity coordinates presented in Table 2 is only a subset of the range of colors which can be made by the present invention.
  • the range of chromaticity coordinate values for x are from approximately 0.25 to 0.50, and for y are from approximately 0.25 to 0.45, and values for Y are from approximately 5 to 50.
  • the present invention provides an improved method for producing highly durable, lustrous protective coatings on a variety of metal substrates.
  • Highly important technical advantages of the ion-assisted plasma deposited composite diamond-like carbon coatings present invention includes attractive cosmetic appearance with a variety of colors, tailorable shiny, high-luster or low-luster finish, outstanding adhesion and durability, outstanding resistance to scratches, abrasion and corrosion, and ease and flexibility of mass production.

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