WO2012145750A2 - Revêtements nanocomposites lubrifiant-dur-ductile électroplaqués et leurs applications - Google Patents

Revêtements nanocomposites lubrifiant-dur-ductile électroplaqués et leurs applications Download PDF

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WO2012145750A2
WO2012145750A2 PCT/US2012/034678 US2012034678W WO2012145750A2 WO 2012145750 A2 WO2012145750 A2 WO 2012145750A2 US 2012034678 W US2012034678 W US 2012034678W WO 2012145750 A2 WO2012145750 A2 WO 2012145750A2
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phase
coating
oxide
lubricant
composite coating
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PCT/US2012/034678
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WO2012145750A3 (fr
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Danny Xiao
Heng Zhang
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The Nano Group, Inc.
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/22—Servicing or operating apparatus or multistep processes
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • C23C18/1651—Two or more layers only obtained by electroless plating
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1655—Process features
    • C23C18/1662—Use of incorporated material in the solution or dispersion, e.g. particles, whiskers, wires
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • C25D15/02—Combined electrolytic and electrophoretic processes with charged materials
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
    • C25D5/611—Smooth layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/615—Microstructure of the layers, e.g. mixed structure
    • C25D5/617—Crystalline layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance

Definitions

  • Electroplated lubricant nanocomposite coatings and their applications Disclosed herein too are electroplated-hard-ductile-lubricant nanocomposite coatings and their applications.
  • Engineered tribological coatings offer a significant opportunity in the field of coatings as they enhance component reliability and reduce life-cycle cost. These coatings are thermally sprayed and use chromium or tungsten carbide or they are electroplated and use hard chrome. Electrolytic hard chrome, however, suffers from severe environmental problems due to the emission of hexavalent chromium ions, which are carcinogenic. Hard chrome coatings are now being replaced by High Velocity Oxy Fuel (HVOF) coatings. It is estimated that at least 20-30% of the department of defense's chromium plated parts have complex geometries and fall in the category of no-line-of- sight (NLOS) applications that are not amenable to HVOF technology. Therefore, an environmentally friendly electrodeposited tribocoating having properties similar to those of hard chrome will satisfy this NLOS market need and achieve the EPA's goal by offering a clean deposition technology.
  • HVOF High Velocity Oxy Fuel
  • Black oxide coatings result from a conversion of the existing alloys to a black form of rust. Coatings are deposited primarily on components where tight tolerances are useful in mating surfaces, e.g., rotary gears, and may also be used as a decorative coating. These suffer from the drawback that only very limited corrosion protection is afforded under mildly corrosive conditions.
  • black oxide coating should normally be given a supplementary treatment (i.e., oil displacement per Mil-C-16173 Grade 3 or protective treatments of Mil-C-16173).
  • a supplementary treatment i.e., oil displacement per Mil-C-16173 Grade 3 or protective treatments of Mil-C-16173.
  • Techniques of depositing black oxide coatings including (1) alkaline oxidizing on wrought iron, cast and malleable irons, common carbon, and low alloy steels, as well as on certain corrosion resistant steel alloys tempered at less than 900°F, and (2) fused salt oxidizing on corrosion resistant steel alloys which are tempered at 900°F (482°C) or higher.
  • a black finish is produced by immersing tool in a hot oxidizing salt solution. During this treatment all grinding stresses are relieved to improve the toughness of tool. Finish is rust resistant and helps prevent metal to metal contact in machining operations. This finish reduces galling and chip welding and enables tool surface to absorb more lubricant.
  • Solid lubricants are thin films composed of a single solid or combination of solids introduced between two rubbing surfaces for the purpose of reducing friction and wear. Two requirements must be met to achieve effective solid film lubrication, including (1) strong coating to substrate adhesion, and (2) low resistance to crystalline slip during shear. Graphite and M0S 2 are the two most common solid lubricants, used in applications involving severe temps., pressures, and environments, which preclude the use of organic fluids. The development in solid lubricants has been motivated by aerospace requirements and performed at NASA's Glenn Research Ctr. at Lewis Field (Cleveland, OH).
  • Solid lubricant coatings share certain material properties. Specifically, direct microscopic observations of the dynamics of solid lubrication show that sliding is accompanied by severe ductile shear of the solid lubricant film. Hence, low shear strength is critical for lubricity. If the lubricant is crystalline, this occurs by slip along preferred crystallographic planes. Low shear strength alone does not ensure lubrication if the material does not adhere to the lubricated surface. Other important properties include low abrasivity (ratio of hardness of lubricant and substrate) and thermodynamic stability.
  • Layer lattice is a term used to describe crystal structures that consist of basal planes parallel to each other and consist of hexagonally oriented atoms. The spacing between the planes is the c-spacing. The spacing between the atoms within the basal plane is the a-spacing. Compounds with a high c/a ratio have very anisotropic shear properties with preferred shear parallel to the basal planes or perpendicular to the c-axis of the crystal structure.
  • the dichalcogenides (sulfides, selenides, and tellurides) of molybdenum and tungsten have this structure, So does FeS 2 , which along with MoS 2 and WS 2 , is an intrinsic solid lubricant in that, unlike graphite, it does not require adsorbed materials or additives for lubricating capability, and is therefore attractive for vacuum appls. FeS, in distinction, has demonstrated viability in air. Table 1 lists some of these compounds (other sulfides) and their decomposition temperatures (onset of decomposition as determined by TGA). All the disulfides have coefficients of friction > 0.2. In distinction, Inframat's thermal sprayed FeS/Fei_ x S coatings revealed coefficients of friction ⁇ 0.08.
  • MoS 2 is normally applied to surfaces by several methods, e.g., simple rubbing or burnishing, air spraying of resin-bonded or inorganically bonded coatings, and PVD (e.g., sputtering). Burnished films have limited wear life. Resin-bonded aerosol spray coatings have good wear life in air, likely due to the oxidation protection from the resin binder. The endurance life and friction coefficients of sputtered MoS 2 are not as good in air as in vacuum (where 0.01 has been achieved). Moreover, Spalvins has reviewed the field and points out that sputtered MoS 2 forms columnar-fiber-like structure networks. These columns fracture after a single pass sliding. Lubrication is then provided by the residual film (0.18-0.22 micrometers (Dm)). Hence, thick films are not possible by sputtering. Brushed or painted coatings provide weak bonding to the substrate.
  • PVD e.g., sputtering
  • Iron sulfide has a layered structure hexagonal close packed lattice similar to the graphite lattice, yet maintains lubricating properties at high load or high speed in air as well as in vacuum.
  • the salient physical properties of sulfides are listed in Table 1.
  • FeS is stable up to 1050°C. Because of its relatively low melting temperature and its layered lattice structure, FeS has good lubricating properties. This process, although not
  • a low temperature sulfurizing method is currently under license from HEF France and is utilized in industries in Japan, France, India and China. This method is called
  • SULF-BT or Caubet process and is an anodic sulfurization performed in a suitable molten bath. Its aim is the formation of a thin (a few microns thick) pyrrhotite (Fei_ x S, a metal-deficient iron sulfide) film on steel.
  • Fei_ x S a thin pyrrhotite
  • An example of the SULF-BT process is that the parts or specimens to be coated will undergo an electrolytic sulfurizing after degreasing and pickling. Electrolytic sulfurizing is carried out in a molten salt bath with a bath composition of 75% KSCN + 25% NaSCN, at temperatures of 190°C and a duration of about 20 minutes. Treated specimens are used as anodes; while the cathode is stainless steel.
  • the density of the anodic current is 2.5 Amperes/square decimeter.
  • Plasma spray tribological coatings were first reported by Sliney at NASA Lewis and were composites of CaF 2 , sodium-free glass, and a nickel-chromium alloy binder, with (PS101) and without (PS100) silver to improve low-temperature friction.
  • the PS200 series of coatings were subsequently developed by Sliney and Dellacorte, where the lubricating solids are distributed throughout a wear-resistant matrix of Ni-Co alloy-bonded chromium carbide (Cr 3 C 2 ).
  • Pr 3 C 2 Ni-Co alloy-bonded chromium carbide
  • PS200 contains 10 wt% each of Ag and CaF 2 -BaF 2 eutectic, and PS212 contains each at 15 wt%.
  • Hard chrome plating is a technique that has been in commercial production for over 60 years and is a useful NLOS process for applying protective hard coatings in military as well as commercial applications. Hard chrome plating utilizes carcinogenic hexavalent-Cr. Hence, there are severe environmental problems associated with hard chrome electroplating, including the release into the air of a fine mist containing hexavalent-Cr ions
  • This invention relates to electroplating coating method for the formation of a tenacious film that consists of three components, including (1) a solid lubricant phase having low coefficient of friction or high lubricity, (2) a hard ceramic phase responsible for the structural integrity and wear resistance, (3) ductile metal phase for material toughness.
  • This coating composition is used in mating parts where a combination of high lubricity, wear resistance and ductility is important, including hydraulic cylinders and sleeves, copper mold in steel making industry, rollers in printing, and gear geometries, as well as for critical hard chrome replacement coating applications.
  • a colloidal solution bath comprises of: solid-lubricant phase and a hard phase nanocomposite nanoparticles uniformly dispersed into a metallic phase electrolyte.
  • this nanoparticle colloidal solution bath which consists of hard phase and lubricant phase nanoparticles composite, and metallic electrolyte, under the right processing conditions will form a coating that consists of the following functions:
  • the solid lubricant phase provides the necessary lubrication required for contact or wear surfaces
  • the hard ceramic phase provides the structural integrity and wear resistance
  • the ductile matrix phase provide the toughness or ductility required the mating surfaces
  • the deposition process to convert the nanocomposite bath solution into coatings can be either an electroplating process or electroless deposition process.
  • the workpiece can either be LOS (line of sight) or NLOS (non line of sight) surface geometries.
  • FIG. 1 Schematic diagram showing a triphasic material that has a solid lubricant phase, hard-phase, and a ductile phase;
  • FIG. 2 Schematic diagram showing the wear mechanism of a triphasic material that has a solid lubricant phase, hard-phase, and a ductile phase;
  • FIG. 3 Schematic diagram of the electrolytic co-deposition of (a) mtallic, and lubricant and ceramic nanoparticles, and (b) tribological coating containing high lubricity lubricant and wear resistant ceramic nanoparticles in a metallic matrix;
  • FIG. 4 Effect of particle size on wear track; a rougher wear track resulting from a larger particle or grain size will exhibit a higher friction coefficient and wear rate, while nanometer sized grains will exhibit a low friction coefficient and smooth wear track with low wear rate;
  • FIG. 5 Schematic illustration of the wear mechanisms of triphase composite coatings having different amounts of the solid lubricant phase
  • FIG. 6 SEM micrographs showing the microstructures of the as-coated BN-Si0 2 /Ni nanocomposite coatings (a) tilted top surface, and (b) higher resolution of the surface view;
  • FIG. 7 Cross-sectional view of the nanocomposite coating
  • FIG. 8 Coefficient of friction vs time temperature relationship in the as-coated BN-Si0 2 /Ni nanocomposite coatings
  • FIG. 9 Coating of Bush/sleeve complex surfaces showing (a) schematic drawing of the electrode and the bush internal surface need to be coated, and (b) photographs of the coated parts;
  • FIG. 10 Schematics shown electroplating connections for a simple a simple rod-type shape shock absorber.
  • FIG. 11 Photograph of a partial electrode/gear teeth assembly showing the relationships of the gear teeth, tip-shaped electrode, plastic insulator, and electrical connector.
  • coatings comprising nanometer size particles, which form a true colloidal solution.
  • the use of nanometer sized particles promotes an increase in the surface hardness and ultimately wear resistance of the coating.
  • the coating comprises about 5 to about 50 volume percent of hard ceramic nanoparticles along with about 5 to about 50 vol% of a lubricant.
  • the coating can be incorporated into a nanocomposite electroplating bath and disposed upon a substrate.
  • FIG. la Schematics for the electroplating of nano-colloidal solution are shown in FIG, la, and the coated part is shown in FIG. lb.
  • This colloidal solution are mixed with Ni or Co or other ionic electrolyte solutions to co-deposit a metal matrix containing the lubricant-hard nanoparticles dispersion.
  • the resultant coating will consist of a finely dispersed wear resistant hard phase and lubricant phase nanocomposite in a metal matrix.
  • the metal matrix will comprise a metal that is dependent upon the ionic electrolyte solutions.
  • the metal comprises nickel or cobalt.
  • the novel lubricant-hard-ductile nanocomposite coating comprises lubricant nanoparticles and hard ceramic nanoparticles embedded in a ductile metal matrix as shown in FIG. 2.
  • the solid lubricant phase provides the necessary lubrication required for contact or wear surfaces
  • the hard ceramic phase provides the structural integrity and wear resistance
  • the ductile metal matrix phase provides the toughness or ductility required the mating surfaces.
  • electrophoresis process step To incorporate small particles into an electroplated process uses an electrophoresis process step. Ideally, this process step should be incorporated into the electroplating procedure. This is however difficult, because the electrical and chemical parameters for electroplating and electrophoresis are quite different.
  • the electrolyte concentration is high, the current densities are low, the electric fields are small, and the ionic conductivity is high.
  • electrophoresis the electrolyte concentration is low, current densities are high, electric fields are high, and electrolyte ionic conductivity is low.
  • the high electric field is the most important for electrophoresis. If one can produce a high electric field at or very near the surface to be plated, the current density, concentration, and ionic conductivity for electrophoresis are of secondary importance.
  • the process that is used for electroplating of a species onto a conducting substrate has several process regions. These regions are, (1) the bulk electrolyte, the major volume of electrolyte and occupies most of the volume of the plating bath, (2) the diffusion layer - close to the substrate surface where plating is occurring, there is a concentration gradient that is established by the depletion of the ionic species being plated, and diffusion from the bulk electrolyte replenishes the depleted ionic species close to the substrate, (3) the electrical double layer, and (4) the charge transfer interface where electron transfer to metal ions occurs, and metal is plated onto the conducting substrate.
  • the electrical double layer resides in the area adjacent to the conducting substrate that is being plated. Simplistically described (and ignoring ionic solvation), the substrate is negatively charged and attracts positive ions immediately adjacent to the substrate.
  • the combination of the layer of positive ions next to the negative substrate is called the compact, or Helmholtz Electrical Double Layer (HEDL).
  • HEDL Helmholtz Electrical Double Layer
  • the solution is dynamic due to factors such as Brownian motion, the replication of multiple layers outwards from the substrate decreases as the distance increases from the substrate. The multiple layers become more diffuse.
  • the charge transfer interface is the plane at which electrons neutralize positive (metal) ions at the substrate surface and then deposit the metal on the conducting substrate. This is the electrodeposition step.
  • nano-particles can enter the region of the GCDEDL and HEDL. If the nano-particles have a positive surface charge (either intrinsic or imparted by additives), then they will be preferentially attracted to the cathode (the negatively charged electrode) in the GCDEDL and HEDL. During electroplating, these particles will be driven onto the substrate surface and incorporated into the electroplated metal. This process provides a method of forming a matrix of nano-particles embedded in an electroplated metal. For larger particles, incorporation mechanism will be dominated by trapping due to agitation of the electrolyte/particle impinge onto the electrodes, thus the amount of trapped small particles onto the matrix phase will be statistical.
  • a colloidal bath of two types of nanoparticles solid lubricant nanoparticles, and hard ceramic nanoparticles. These nanoparticles are uniformly distributed in a metal ion electrolyte bath, along with bath additives.
  • this design is anticipated to obtain a coating with the function of: a lubricant/soft phase for providing lubrication to a surface; a hard ceramic phase for providing structural integrity and wear resistance to the surface; and a ductile metal phase for providing ductility to the surface.
  • the effect of particle size is schematically illustrated in FIG. 4.
  • the coefficient of friction has been found to decrease with grain size.
  • the wear tracks of nanocoatings are expected to have a lower surface roughness compared to black oxide coatings and electrodeposited coatings containing 0.5-2 ⁇ silicon carbide particles, currently being used. Also, these particles are generally not metallurgically bonded to the coating matrix causing particle pull-out, and both of these phenomena are expected to increase the friction coefficient and wear rate of the coating.
  • microfracture-controlled wear process is dominant wear mechanism for most ceramic coatings due to their inherent high brittleness and low strain tolerance.
  • the electroplated nanocomposite coating is verified to have a high toughness, cohesive and adhesive bonding strength.
  • the improved ductility and integrity of the nanostructured coating was responsible for improved friction and wear properties due to nanoscale plastic deformation, reduced microfracture, delamination and grain tearing-out. It is generally accepted that the wear behavior of a materials is directly related to its microhardness, toughness, grain size, mating material properties.
  • Suitable lubricant materials include but are not limited to compositions of a family of layered hexagonal lattice structures, boron nitride (BN), graphite (C), tungsten disulfide (WS 2 ), molybdenum disulfide (M0S 2 ), iron sulfide Fei_ x S, calcium fluoride (CaF 2 ), diamond or diamond-like nanoparticles, and others such as Fe 3 0 4 , and Teflon.
  • BN boron nitride
  • C graphite
  • WS 2 tungsten disulfide
  • M0S 2 molybdenum disulfide
  • Fei_ x S iron sulfide Fei_ x S
  • CaF 2 calcium fluoride
  • diamond or diamond-like nanoparticles and others such as Fe 3 0 4 , and Teflon.
  • Suitable hard ceramic phase include but are not limited to (1) metal oxide family of aluminum oxide A1 2 0 3 , silica Si0 2 , chromium Cr 2 0 3 , zironia Zr0 2 , ceria Ce0 2 , yttria Y 2 0 3 , (2) carbide family of tungsten carbide WC, titanium carbide TiC, vanadium carbide VC, chromium carbide Cr 3 C 2 , tantalum carbide TaC, silicon carbide SiC, (3) nitride family of aluminum nitride A1N, silicon nitride Si 3 N 4 , zirconium nitride, zirconia nitride ZrN, and (4) boride family of titanium diboride TiB 2 , and zirconium boride.
  • the hard phase can also be diamond nanoparticles.
  • Suitable metal matrix phase include but are not limited to transition metals or their alloys of Co, Ni, Fe, Mo, Cr.
  • the electrolyte in the bath solution will comprise, but not limited to metallic salts of cobalt, nickel, chromium, iron, and molybdenum.
  • the coating deposition process can be either LOS or NLOS processes of electroplating or electroless plating.
  • gear tip shape is exact from the shape of space profile between the two gear tips as shown in FIG. 11.
  • BN-Si0 2 /Ni solution 200 grams of BN and 220 grams of Si0 2 nanoparticles were mixed with 100 grams of nickel sulphamate solution, 880 ml DI water and desired amount of surfactants. This mixture is then transferred into a ball milling jar and milled overnight. Different amounts of the solution mixture were added to the electroplating vessel of 11 liters so as to have 4400 grams of nickel sulphamate in the solution mixture. Other plating additives such as phosphor and brightener were then added into the bath, and DI water was finally added to make up a 11 -liter plating solution.
  • the BN-Si0 2 compositions of the electroplating bath is 40g/l for electroplating.
  • Table 3 An exemplary plating bath is shown in Table 3. Table 3. Current Inframat plating bath solution composition for plating BN-Si0 2 /Ni nanocomposite coatings (using 11 liters of solution)
  • BN-Cr 2 0 3 /Ni solution 220 grams of BN and 220 grams of Cr 2 0 3 nanoparticles were mixed with 220 grams of nickel sulphamate solution, 880 ml DI water and desired amount of surfactants. This mixture is then transferred into a ball milling jar and milled overnight. Different amounts of the solution mixture were added to the electroplating vessel of 11 liters so as to have 4400 grams of nickel sulphamate. Other plating additives such as a phosphor and a brightener were then added into the bath, and DI water was finally added to make up an 11-liter plating solution.
  • the BN-Cr 2 0 3 composition of the electroplating bath is 40g/l for electroplating.
  • BN-SiC/Ni solution 220 grams of BN and 220 grams of SiC nanoparticles were mix with 220 grams of nickel sulphamate solution, 880 ml DI water and desired amount of surfactants. This mixture is then transferred into a ball milling jar and milled overnight. Different amount of the solution mixture were added to the electroplating vessel of 11 liters so as to have a 4400 grams of nickel sulphamate. Other plating additives such as phosphor and brightener were then added into the bath, and DI water was finally added to make up an 11 -liter plating solution.
  • the BN-SiC compositions of the electroplating bath is 40g/l for electroplating.
  • BN-diamond/Ni solution 220 grams of BN and 220 grams of diamond nanoparticles were mix with 220 grams of nickel sulphamate solution, 880 ml DI water and desired amount of surfactants. This mixture is then transferred into a ball milling jar and milled overnight. Different amount of the solution mixture were added to the electroplating vessel of 11 liters so as to have a 4400 grams of nickel sulphamate. Other plating additives such as phosphor and brightener were then added into the bath, and DI water was finally added to make up an 11 -liter plating solution.
  • the BN-Diamond compositions of the electroplating bath is 40g/l for electroplating.
  • the bath sequence is schematically illustrated in the flow diagram below.
  • the electrolytic bath has capabilities to vary and control different factors such as temperature, agitation, current density, pH and other process parameters.
  • the base metal substrate used at this point is carbon steel and copper alloy for uses in bush /sleeves in steel mill applications.
  • the first step is to remove the surface dirt by rubbing against sandpaper, followed by acetone washing and rinsed with DI water. The fresh surface is the immersed in the degrease bath for 10 min., and rinsing thoroughly in the rinse bath. The next step is to immerse the sample in the neutralize bath for 10 min., followed by rinsing. This sample is then immersed in the activation bath for 10 min., followed by rinsing. The sample is now ready for plating.
  • the anode is Ni
  • the cathode is the substrate coupon (or gear specimen).
  • the electrodeposition current can be monitored using an amperometer with an accuracy of 0.1 mA, under a controlled temperature and acid concentration.
  • the deposition parameters include: these parameters, 4.2-4.5 plating pH, mechanical stirring, and 20-40 amp/ft current density. Detailed electroplating steps are described below:
  • Step 1 Following removal of obvious loose particles from the sample surface (e.g., by light san blasting), connect the sample to the degreasing bath sample holder
  • Step 2 Anodize the samples for 20 to 30 minutes in the degreasing bath between porous nickel cathodes. Current typically should be about 1.6 A for a sample of about 6 square inches. This should be “tuned” depending on the iron based alloy. Successful “cleaning” should show faint cloud of dark particles surrounding the sample. 20 A per square foot is a good value to start with. Step 3. Disconnect, remove sample from the degreasing bath Rinsing after Degreasing
  • Step 1 Immerse the components into the rinsing bath and shake for 10 times Neutralizing Procedure
  • Step 1 Immerse the components into the neutralizing bath and shake for 10 times Rinsing before Activation
  • Step 1 Immerse the components into the rinsing bath and shake for 10 times Activation Procedure
  • Step 1 Mount the sample as cathode in the activation bath between porous nickel anodes.
  • Step 2 Plate samples between nickel electrodes at current densities in the range 20 to 100 A/sq-dm (150 to 900 A/sq-ft). You only need a very thin layer of "strike” nickel, barely enough to give the sample a "color.” Plating only takes minutes. Also, gassing is normal. This plating process in relatively inefficient. Focus a bright light on the sample (a good flashlight will do) so that the color change can be observed.
  • Step 3 Transfer the "strike” plated sample immediately to the main plating bath and immerse the sample in the electrolyte. Allow a film of strike electrolyte to "carry-over" with the sample, i.e., don't shake off excess electrolyte. The carry-over electrolyte protects the sample from air oxidation.
  • Step 1 Adjust the plating current density to be somewhere in the range 20 to 50 A/ft 2 . Try to keep the current as high as possible to help the electrophoresis effect on the Si0 2 /BN nanoparticles. Plating time will depend on how thick you need the plate has to be. Make sure the plating power supply will cope with the upper limit of current. Step 2. When you have everything ready to start plating (electrolyte up to temperature, stirring on, but out of the way of where the sample will be, hooks/suspension clips ready to receive the sample, power supply on, but turned to a low value - about 10% of your estimated plating current, etc), transfer the sample quickly from the "Strike" bath.
  • Step 3 When you are satisfied with the positioning of the sample, slowly raise the plating current to the value that you have chosen. Raise the current over a period of 15 to 30 seconds. Plate for the desired time and reduce the current to close to zero. Remove the sample. Wash and inspect.
  • the plated BN-Si0 2 /Ni nanocoatings for are smooth, uniform, dense, and with metallic or satin finishing. Most importantly, there is no evidence of non-uniformity in sharp-cornered angles. Without nanoparticulate additives, the pure nickel plated surface is bright, smooth, dense, and has uniform thickness throughout all sections of the coated surfaces. As the percentage of both Si0 2 and BN nanoparticles increased in the plating solution, the gloss appearance of the coating gradually starting to disappear in a order of 5g/l, lOg/1, 15g/l, 20g/l, 25g/l, 30g/l, 40g/l, and 50g/l. At a 40g/l nanoparticles solution, the coating is being a satin finish, with high density and other desirable characteristics.
  • FIG. 6 Surface morphology of the as plated BN-Si0 2 /Ni nanocomposite coating is shown in FIG. 6.
  • SEM Cross-sectional scanning electron microscopy
  • FIG. 7 Look at the coating-substrate intersections using transmission electron microscopy techniques, it revealed the perfect bonding between the substrate and the coating, all atomic bonding of the coating has been achieved.
  • Microhardness is measured at cross-section surface of the coated specimen using Vickers hardness machine. In the optimization experiments, hardness is one of the most important parameters used to determine the coating quality, as it relates to coating density, and strength.
  • the coating hardness values are plotted as a function of BN/S1O 2 ratio, as a function of particulate (BN:Si0 2 ratio of 1:1), and as a function of heat treatment temperature.
  • the hardness of the coating varies ranges from 400 up to 1,000 VHN. With pure BN, the hardness of the coating is about 250 VHN.
  • FIG. 8 shows the friction coefficient of the BN-Si0 2 /Ni nanocomposites under different lubricating conditions. Samples were measured with (1) no oil (completely dry), and (2) with a thin oil film (carefully wiped dry with tissue) lubrication in Castrol SAE 10W-40 oil. The data show that boron nitride provides a dry lubricity when incorporated in nickel matrix. It is of note that the coefficient of friction values of the "oil film" are close to the full lubrication values. Tests for coated pieces with different conditions are shown in Table 4 below.
  • the corresponding coating coefficient for the BN-Si0 2 /Ni coating is in the neighborhood of 0.15 to 0.20 range, either have a lubricant film or not.
  • the BN-Si0 2 /Ni coating seems to have the lowest value of coefficient of friction, with reasonable good hardness>400 VHN, and the best wear resistance. It should be noted that during the wear experiments, both the tool steel and silicon nitride balls were worn, while the was even a notice scar or wear track appeared on the coated specimen.
  • the experimental conditions are similar as compared to the coating of BN-Si0 2 /Ni on coupons. Briefly, carbon steel or copper alloy were used as coupons, with size of ID: 15 mm, OD: 30 mm, and height: 10 mm.
  • the plating parameters are also similar to the BN-Si0 2 /Ni plating parameter as described in Example 3, except, here the pH is around 2 to 2.5 for the best coating.
  • the corresponding coating coefficient is 0.063 with full oil lubrication, 0.079 with a thin oil film (wiped off), and 0.118 in absolute dry for the coated gear substrate.
  • the property of this coating is not stable, thus, we changed the pH to a range of 2.0 to 4.0, and the coefficient of friction also ranges from 0.08 to 0.5, almost a 10 folds of difference.
  • the exact reason for this property instability is currently unknown, but we believe it could be related to the double layer effect or the GCDEDL and HEDL phenomena associated in the coating process, due to the fact that Cr 2 0 3 nanoparticles maybe conductors in the presence of nickel electrolyte, thus significantly complicate the electroplating process.
  • the experimental conditions are similar as compared to the coating of BN-SiC/Ni on coupons. Briefly, carbon steel or copper alloy were used as coupons, with size of ID: 15 mm, OD: 30 mm, and height: 10 mm.
  • the plating parameters are also similar to the BN-Si0 2 /Ni plating parameter as described in Example 3, except, here the pH is around 4.0 for the best coating. Coating of about 20 micron thick coating takes about 30 minutes.
  • the corresponding coating coefficient is 0.6-0.8 with a thin oil film (wiped off).
  • the coating also have a hardness in the neighborhood of 650 to 700 VHN.
  • the component has a size of ID: 70 mm, OD: 85 mm, and height: 70 mm.
  • a male electrode anode
  • the relative relationship between the electode, sleeve, and the electrical connector is shown in FIG. 9.
  • the male electrode is reversed (or acted as the cathode).
  • the uncoated surfaces are masked with tapes.
  • the plating current density are then calculated according to the effective area of the component.
  • the deposition parameters include: These parameters, 4.2-4.5 plating pH, mechanical stirring, and 20-40 amp/ft current density. Coating of about 100 micron thick coating takes about 240 minutes. The obtained coating has a smooth surface, characteristics of the coating is similar to as those described in Example 2. A photograph of the coated components are shown in FIG. 10.
  • Example 7 Coating of BN-Si0 2 /Ni on Shock Absorbers for Automotive Applications
  • the component has a size of ⁇ 15.81x290.75 mm.
  • an electrical connector is attached at each end of the shock absorber, as schematically shown in FIG. 10. The uncoated surfaces are masked with tapes. The plating current density is then calculated according to the effective area of the component.
  • the plating procedures used as, degrease, rinse, neutralize, rinse, activation, and plating include: These parameters, 4.2-4.5 plating pH, mechanical stirring, and 20 amp/ft current density. Coating of about 15-20 micron thick coating takes about 30 minutes.
  • Inframat had sent its previously obtained auto transmission gears to Shilin for coating.
  • a gear-tip shaped individual electrodes with respect to the gear are assemblied as shown in FIG. 11.
  • the uncoated surfaces are masked with tapes.
  • the plating current density is then calculated according to the effective area of the component.
  • the plating procedures used as, degrease, rinse, neutralize, rinse, activation, and plating include: These parameters, 4.2-4.5 plating pH, mechanical stirring, and 20 amp/ft current density. Coating of about 15-20 micron thick coating takes about 30 minutes. The obtained coating has a smooth surface, with uniform coatings on both valley tips, and slopes.

Abstract

L'invention concerne un procédé d'observation indirecte (« NLOS ») pour l'électroplaquage de revêtements nanocomposites sur un substrat. Ce revêtement révèle une combinaison de compositions de revêtement nanocomposite lubrifiant-dur-ductile. L'invention concerne également des applications des revêtements. Dans un mode de réalisation, le procédé de plaquage utilise une électrode de nickel ou un procédé de dépôt autocatalytique. Dans un autre mode de réalisation, le revêtement obtenu est une composition de revêtement nanocomposite qui comprend une phase lubrifiante/souple pour fournir une lubrification à une surface ; une phase céramique dure pour fournir une intégrité structurale et une résistance à l'usure à la surface ; et une phase métallique ductile pour fournir une ductilité à la surface. Dans un troisième mode de réalisation, cette composition de revêtement a des applications dans des pièces en contact où une combinaison de pouvoir lubrifiant élevé, de résistance à l'usure élevée et de ductilité élevée est importante, comprenant les vérins hydrauliques et les manchons hydrauliques, un moule en cuivre dans l'industrie de la fabrication de l'acier, des rouleaux dans l'imprimerie et des géométries d'engrenage.
PCT/US2012/034678 2011-04-22 2012-04-23 Revêtements nanocomposites lubrifiant-dur-ductile électroplaqués et leurs applications WO2012145750A2 (fr)

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EP2774846A1 (fr) * 2013-03-07 2014-09-10 Bell Helicopter Textron Inc. Aéronef avec un revêtement nano
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CN106119905A (zh) * 2016-08-15 2016-11-16 亚太水处理(天长)有限公司 一种浮动曝气机轴承内轴套复合镀涂液的制备方法
CN108699697A (zh) * 2016-03-10 2018-10-23 博格华纳公司 具有含有硬质颗粒的无电镀镍涂层的链条
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CN111826691A (zh) * 2020-08-21 2020-10-27 东北大学 一种溶剂化离子液体制备锌钽合金的方法
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CN112680761A (zh) * 2020-12-16 2021-04-20 江西瑞顺超细铜线科技协同创新有限公司 一种镀镍铈合金软铜线生产工艺
CN113249712A (zh) * 2021-04-28 2021-08-13 南京航空航天大学 一种钛合金丝材铜/氧化钇复合改性方法及应用
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CN114635127A (zh) * 2022-03-17 2022-06-17 台州学院 一种用于熔喷模头的低摩擦系数涂层及其制备方法
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US11242613B2 (en) 2009-06-08 2022-02-08 Modumetal, Inc. Electrodeposited, nanolaminate coatings and claddings for corrosion protection
US9352829B2 (en) 2013-03-07 2016-05-31 Bell Helicopter Textron Inc. Aircraft with protective nanocoating
EP2774846A1 (fr) * 2013-03-07 2014-09-10 Bell Helicopter Textron Inc. Aéronef avec un revêtement nano
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US11168408B2 (en) 2013-03-15 2021-11-09 Modumetal, Inc. Nickel-chromium nanolaminate coating having high hardness
US11118280B2 (en) 2013-03-15 2021-09-14 Modumetal, Inc. Nanolaminate coatings
US10808322B2 (en) 2013-03-15 2020-10-20 Modumetal, Inc. Electrodeposited compositions and nanolaminated alloys for articles prepared by additive manufacturing processes
US11851781B2 (en) 2013-03-15 2023-12-26 Modumetal, Inc. Method and apparatus for continuously applying nanolaminate metal coatings
US10844504B2 (en) 2013-03-15 2020-11-24 Modumetal, Inc. Nickel-chromium nanolaminate coating having high hardness
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US11560629B2 (en) 2014-09-18 2023-01-24 Modumetal, Inc. Methods of preparing articles by electrodeposition and additive manufacturing processes
US11692281B2 (en) 2014-09-18 2023-07-04 Modumetal, Inc. Method and apparatus for continuously applying nanolaminate metal coatings
US10781524B2 (en) 2014-09-18 2020-09-22 Modumetal, Inc. Methods of preparing articles by electrodeposition and additive manufacturing processes
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