USRE29285E - Method for concomitant particulate diamond deposition in electroless plating, and the product thereof - Google Patents

Method for concomitant particulate diamond deposition in electroless plating, and the product thereof Download PDF

Info

Publication number
USRE29285E
USRE29285E US05/694,047 US69404776A USRE29285E US RE29285 E USRE29285 E US RE29285E US 69404776 A US69404776 A US 69404776A US RE29285 E USRE29285 E US RE29285E
Authority
US
United States
Prior art keywords
diamond
electroless
plating
bath
particles
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US05/694,047
Other languages
English (en)
Inventor
Theodore Peter Christini
Albert Lawrence Eustice
Arthur Hughes Graham
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=26992553&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=USRE29285(E) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
US case filed in International Trade Commission litigation https://portal.unifiedpatents.com/litigation/International%20Trade%20Commission/case/337-TA-160 Source: International Trade Commission Jurisdiction: International Trade Commission "Unified Patents Litigation Data" by Unified Patents is licensed under a Creative Commons Attribution 4.0 International License.
Priority claimed from US05/341,529 external-priority patent/US3936577A/en
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority to US05/694,047 priority Critical patent/USRE29285E/en
Application granted granted Critical
Publication of USRE29285E publication Critical patent/USRE29285E/en
Publication of USRE29285F1 publication Critical patent/USRE29285F1/en
Priority to US07/393,821 priority patent/USRE33767E/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • 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
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • 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
    • 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
    • C23C18/31—Coating with metals
    • C23C18/38—Coating with copper
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02J—FINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
    • D02J1/00—Modifying the structure or properties resulting from a particular structure; Modifying, retaining, or restoring the physical form or cross-sectional shape, e.g. by use of dies or squeeze rollers
    • D02J1/08—Interlacing constituent filaments without breakage thereof, e.g. by use of turbulent air streams
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles

Definitions

  • this invention consists of a method for depositing on an article a coating containing at least one member of the group metals and metal alloys and incorporating therein particulate dispersed diamond comprising contacting the surface of the article with a stable electroless plating bath consisting essentially of: (1) an aqueous solution of soluble constituents of the group, (2) electroless reducing agent therefor, (3) a suspension of diamond particles in concentration in the range maintaining fluidity of the bath, (4) a stabilizer for the bath of concentration in the range from that sufficient to prevent decomposition of the bath upon addition of diamond particles thereto to that retaining plating capability of the bath, and (5) additives facilitating electroless plating per se, and maintaining the diamond particles in suspension throughout the bath during coating of the article for a time sufficient to produce a preselected depth of coating on the article, together with the product of the method.
  • a stable electroless plating bath consisting essentially of: (1) an aqueous solution of soluble constituents of the group, (2) electroless reducing agent therefor, (3)
  • FIG. I is a typical photographic plan view (6340X) of an electroless Ni-B alloy/12 ⁇ synthetic diamond "A" composite with the several most important structural features indicated by characteristic numerals,
  • FIG. II is a typical photographic plan view (6480X) of an electroless Ni-B alloy/9 ⁇ natural diamond composite, with individual structural features identified,
  • FIGS. III(A)-(E), inclusive are partially schematic representations of the Accelerated Wear Test apparatus employed, and the results obtained, in the evaluation of the best composite coatings laid down by this invention, as to which (A) is a plan view of the test apparatus (B) is an inset perspective of the running yarn course over the surface of a specimen in test, (C) is a side elevation view, partly in section, taken on line IIIC--IIIC, FIG. IIIA, (D) is a perspective view of the relationship of running yarn line to specimen in an invalid Standard Test which yields corner notching [FIG. IIIE(M)] without a wear track on the mid-specimen surface between the notches and III(E) [N] is a showing of a typical normal groove obtained during a valid Accelerated Wear Test,
  • FIG. IV is a typical photographic plan view (2860 X) of an electroless Ni-B alloy/9 ⁇ natural diamond composite indicating the diagonal running test yarn course and showing structural features as affected by the Standard Wear Test,
  • FIG. V is a typical photographic plan view (2640X) of an electroless Ni-B alloy/9 ⁇ synthetic diamond "A" composite indicating the running test yarn course and showing structural features as affected by the Accelerated Wear Test,
  • FIG. VI is a typical photographic plan view (250X) of an electroless Ni-B alloy/9 ⁇ synthetic diamond "A" specimen in the as-plated condition (A) and after an Accelerated Wear Test (B),
  • FIG. VII is a typical photographic plan view (250X) of an electroless Ni-B alloy/9 ⁇ natural diamond specimen in the as-plated condition (A) and after an Accelerated Wear Test (B),
  • FIG. VIII is a typical photographic plan view (250X) of an electroless Ni-B alloy/9 ⁇ synthetic diamond "B" specimen in the as-plated condition (A) and after an Accelerated Wear Test (B),
  • FIG. IX is a sectional perspective view of a preferred embodiment of apparatus which is employed to lay down the composite coatings of this invention
  • FIG. X is a fragmentary, cross-sectional, side elevation view of a multi-filament yarn interlacing air jet which is advantageously coated according to this invention
  • FIG. XI is an end elevation view, partly in cross section, of a multiplicity of interlacing jets of the design of FIG. X in assembled relationship, and
  • FIG. XII is a section on line XII--XII, FIG. XI.
  • Applicants have now discovered a method of concurrently depositing, by the electroless plating technique, as a disperse phase, particulate diamond in composite with Ni(B), Ni(P), Co(B), Co(P) and other metals and metal alloys singly, or as mixtures of any two or more of these substances together, as well as metallic copper as the continuous phase or matrix.
  • the coatings produced are highly adherent, relatively non-porous and possessed of a truly remarkable abrasive wear resistance.
  • the diamond particle pull-out characteristics are very good, so that objectionable detritus is not carried over into the surrounding environment which could, possibly, act as an abrasive agent to gall or otherwise damage the fine finish of bearings or other metal-to-metal contact surfaces.
  • the combination of properties displayed by the diamond composites of this invention are such that they have great potential value as abrasion-resistant surfaces for both dry and wet service, writing instrument nibs, cutting tool surfaces, piston ring and other sliding contacting surfaces, textile wear surfaces and other extremely demanding uses.
  • the composites of applicant' invention are usually used as relatively thin self-adhered coatings deposited on the surfaces of a substrate consisting of a metal, polymer, ceramic, glass, wood or other relatively rigid material.
  • a temporary substrate such as thin metal, water-resistant paper, film or foil, polymer sheeting or the like and the coating stripped therefrom (or the temporary substrate melted or dissolved away) and thereafter utilized as a wear-resistant shell per se, which can be adhered to any firm supporting base material which is, in itself, suited to the particular use environment's requirements, by adhesives, cement, heat treatment or in other conventional manner known to the art.
  • Applicants have prepared composite coatings on substrates of unfilled ABS (acrylonitrile-butadiene-styrene copolymer), filled ABS, ABS reinforced with glass fibers and with acicular TiO 2 , polyimides, polyolefins, polyesters, "Delrin” acetal resins, “Zytel” nylon resins, and “Nomex” aromatic polyamide resins, and, while all have not been tested as thoroughly as some hereinafter described, all have supported coatings that were visually uniform and well-adhered.
  • ABS acrylonitrile-butadiene-styrene copolymer
  • Polymers are, of course, especially preferred in moderate temperature corrosive service environments, because of their low cost, relatively high resistance to corrosion and low contamination potentiality.
  • metals are preferred, since they survive heating to relatively high temperatures without the warping and compositional deterioration usually suffered by polymers.
  • the composite deposition process employed in this invention can utilize much of the published electroless plating art.
  • the electroless Ni-P processes which are the subjects of certain of the Patents cited supra utilize aqueous solutions containing H 2 PO 2 - ions, which act as the reducing agent, and nickel ions furnished by dissolved nickel salts.
  • the electroless Ni-B processes utilize aqueous solutions of nickel salts and a boron-containing reducing agent, such as BH 4 - ions or dimethylamine borane (DMAB).
  • workable electroless plating baths contain buffers, e.g., salts of weak carboxylic or dibasic acids, to prevent rapid changes in pH, plus at least one of a large variety of chemical compounds or metallic ions which act as stabilizers preventing spontaneous bath decomposition.
  • U.S. Pat. No. 3,140,188 teaches processes by which Ni and Co can be deposited from stable baths containing Zn or Fe, and that the coatings are smooth, adherent and constituted of alloys including: Ni-Zn, Ni-Co-Zn, Co-Fe, and Ni-Fe.
  • U.S. Pat. No. 3,062,666 teaches that a lead salt can be included in the plating bath as a stabilizer, and it has been verified that the Ni or Co plating from the bath of this Patent contains small quantities of Pb, without impairing the smoothness.
  • the instant invention is not limited to electroless deposits consisting solely of the metals Ni, Co, Cu and the non-metals P and B, but also comprises these elements singly and plurally, as well as other elements whose presences are tolerable or, indeed, beneficial, as far as bath stability and coating quality are concerned.
  • Electroless plating is an autocatalytic process, in the sense that the coating which is deposited serves as catalyst for continuation of the plating process. Once plating is initiated on the surface of a metallic, ceramic, polymeric or other substrate, it will continue as long as the article remains in contact with the periodically replenished plating solution. Since no electric current is required for the plating which occurs, the general adjectives "electroless” or "chemical” have been used to differentiate these processes from conventional electroplating.
  • the diamond particles utilized in this invention can have particulate sizes in the range of from less than about 0.1 to 50 ⁇ or even to 75 ⁇ .
  • the quantity of diamonds incorporated in our electroless alloy coatings can range from about 1 to about 50 volume percent.
  • the diamond particle shapes employed herein were approximately equi-axed and there appeared to be no optimum particle size distribution.
  • the diamonds employed in some of the Examples infra consisted of mixtures extending from about 1 to about 22 ⁇ size.
  • a dispersion of diamond particles is maintained throughout the plating bath, so that the particles constantly contact surfaces of the substrates being coated.
  • the plating baths must be properly formulated, controlled and operated as hereinafter described under conditions that prevent initiation of plating on the surfaces of the diamond particles suspended in the bath. Thus, if plating initiates on the surfaces of the suspended particles, the bath will decompose by rapid depletion of the metallic ions and the reducing agent, rendering the bath uncontrollable and useless for further plating.
  • the plated diamond particles which come into contact with the substrates being coated form rough, highly porous, nonadherent, unsightly deposits, which are totally unacceptable.
  • Metallic substrates are given a conventional preplating treatment, depending on the particular metal or alloy, prior to coating by this invention.
  • the steel specimens of the Examples infra were first solvent-degreased in trichlorethylene, followed by hot alkaline cleaning (e.g., Enbond S61) at 65° C. for about 5 minutes, after which they were water rinsed, acid-etched in a 50% by volume solution of HCl at room temperature for 30 to 60 sec., and water rinsed prior to immersion in the plating bath.
  • hot alkaline cleaning e.g., Enbond S61
  • Plating initiates spontaneously on metallic substrates which are catalysts for electroless plating processes.
  • catalytic metals include Co, Ni, Pt and Pd.
  • Plating also initiates spontaneously on metals which are noncatalytic but less noble than the bath metal, because a thin film of the dissolved metal rapidly forms through displacement, and the dissolved metal, being a catalyst, continues the plating process. Examples of this, for electroless nickel processes, are the plating of iron, aluminum, magnesium, beryllium and titanium.
  • Metallic substrates which do not initiate plating spontaneously can be initiated galvanically by brief application of a small negative potential to the substrate.
  • Nonconducting substrates such as polymeric organic materials
  • Pearlstein in Metal Finishing, Aug. 1955, pp. 59-61, outlines a two-step approach to surface activation using the hereinbefore described SnCl 2 predip and PdCl 2 activation solution.
  • ABS i.e., acrylonitrile-butadiene-styrene copolymers
  • glass fiber-reinforced ABS and acicular rutile fiber-reinforced ABS resins described in the examples infra, which were given a plate with diamond particles composited with electroless Ni and electroless Ni-Co alloy matrices, were first given the following preplating treatment.
  • Ceramic substrates are prepared for plating by first mechanical roughening, e.g., grit blasting, or by chemical roughening using an aqueous HF solution to develop anchoring points for the catalyst and for the wear-resistant electroless alloy strike that is subsequently applied.
  • first mechanical roughening e.g., grit blasting
  • chemical roughening using an aqueous HF solution to develop anchoring points for the catalyst and for the wear-resistant electroless alloy strike that is subsequently applied.
  • the strike bath was of the same composition as the composite plating bath, except that it contained no diamond powder.
  • the purpose of the plating strike is to insure that the adhesion of the initial electroless coating applied to the substrate is not adversely affected by abrasive or other action of the dispersed particles contained in the composite plating bath.
  • a plating strike is imperative in plating non-conductors such as polymers, ceramics, wood and glass, the surfaces of which are thereby covered with adsorbed layers or islands of a catalyst initiating electroless plating.
  • the strike can be omitted.
  • the electroless alloy-diamond composite coatings of this invention can be deposited by a wide variety of plating techniques ranging from simple rack plating, wherein articles are supported by a rack, to barrel plating, wherein the articles are introduced as free bodies into a rotating bath container, which can have its axis horizontally disposed or somewhat inclined.
  • articles can be tumble-plated as taught in application Ser. No. 103,355 supra.
  • the diamond powder to be composited (0.5 to 100 gms. as desired) is first blended with about 200 to 400 ml. of the plating bath in a high-speed mixer to break up agglomerates, wet all of the particles and form a concentrated slurry containing a uniform dispersion of particles.
  • the slurry is then slowly added to the plating vessel, where the powder particles are kept in suspension by mechanical agitation and/or bath circulation.
  • the quantity of diamonds maintained in the suspension while most commonly in the range of 1 to 10 g. per liter of bath, can range up to as much as 40 g./liter, the upper limit being only that the bath must remain sufficiently fluid to be capable of ready agitation and circulation.
  • the plating vessel 10 was a glass jar of 9 liters capacity, about 22 cm. inside diameter, which was provided with two annular shelves 11 and 12, fabricated from polytetrafluoroethylene, these shelves being held horizontal by snug frictional through-bore mounting on three upstanding polytetrafluoroethylene posts 16, only two of which appear in the FIGURE.
  • Shelves 11 and 12 typically measured 13 cm. inside diameter, 20 cm. outside diameter and were 0.6 cm. thick.
  • Upper shelf 11 was apertured at four locations 17 spaced 90° apart circumferentially, each sized to snugly engage a sample approximately 0.635 cm. ⁇ 1.52 cm., so that the top and bottom faces were exposed to the plating solution for the simultaneous plating of these two surfaces.
  • Lower shelf 12 was provided on its upper face with a multiplicity of recesses 18, which did not extend all the way through the shelf, these recesses being dimensioned to closely fit the specimens 20, which were snugly set therein, so that only the upper exposed surfaces were plated.
  • An electric motor-driven stirrer (typically, 350 rpm) provided the bath agitation, the shaft 22 of which was disposed approximately concentric with the longitudinal axis of vessel 10, which stirrer was provided, at its horizontally bent lower end, with an upstanding elliptical paddle 23 having a major axis of 6.25 cm. and a minor axis of 2.5 cm.
  • the dimensions a, b and c denoted in FIG. IX are, typically, 1.90, 2.54 and 7.62 cms., respectively.
  • Example 1-5 The plating process utilized in Examples 1-5, inclusive, was identical, except that different types of powders were added to the bath as indicated in the foregoing Table 1D.
  • Example a number (typically, 15-19) of molded ABS, glass-reinforced ABS, and acicular rutile-reinforced ABS polymer articles were tumble-plated as taught in application Ser. No. 103,355 supra, which is incorporated herein by reference.
  • the acicular rutile is a powder produced by the Pigments Department, E. I. Du Pont de Nemours Co., which consists of single crystals of TiO 2 measuring about 0.2 ⁇ wide ⁇ 2 to 3 ⁇ long.
  • the plating was conducted in an inverted frustoconical funnel of included angle 46° measuring 24 cm.
  • plating solution in diameter across at the top end and 0.93 cm. across the lower spout end, 25 cm. high, plating solution being circulated continuously through the spout upwardly into the funnel portion with overflow out of the top collected in a surrounding sump.
  • the plating solution velocity was maintained at a high enough rate (typically 4,200 cm. 3/min.) to support the articles being plated and, at the same time, tumble them slowly in a random manner at a rate of 4 to 7 complete inversions per minute.
  • the tumble rate is a function of solution supply velocity, part size, weight, shape and other factors, so that it varied somewhat over the several Examples.
  • the strike bath was maintained at a temperature of 55° C.
  • the sample-containing basket was gently agitated.
  • the specimens, plated with a thin nickel strike, were then dumped from the basket into the plating chamber of a tumble plater of the general design described supra through which was flowed the same plating solution as was used for the strike at a rate of approximately 4,200 cm 3 /min. and plating was continued for about 1 hr. before any particulate diamond additions.
  • Examples 1 through 4 in which 8 and 9 ⁇ classified size grades of powder (nominal size range 6-12 ⁇ ) were used, the powder added was furnished in amount sufficient to establish a concentration of suspended particles of 2 gm./liter of plating bath.
  • Example 5 in which a rough 1 to 10 ⁇ size grade of ⁇ SiC powder was used, the concentration of powder added was increased to 3 gm./liter to establish a concentration of particles in the 6 to 10 ⁇ size range approximately equivalent to that of Examples 1 through 4.
  • a description of the type powder employed in each Example is reported in Table 2. The period of composite plating was approximately 3.5 hours.
  • the coated surface was ground flat on 600 grit SiC abrasive papers
  • diamond “A” is seen to have recessed growth ledges (1), craters (2), upstanding growth projections (3) and a multitude of other irregularities which appear to present optimum sites for the nucleation of Ni-B alloy grains (4) on the diamond surface per se.
  • the smooth, quite uniform Ni-B grain matrix existing outwards from the diamond particles is relatively continuous and depressed for all of the diamond particles, regardless of type.
  • Diamond “A” particles have a fine-grained polycrystalline structure, being made up of a multitude of contiguous diamond crystallites tightly bonded directly to one another in an essentially unoriented pattern.
  • the microstructure of diamond “A” is characterized by a bimodal crystallite size distribution, single coherent particles containing a population of very small, blocky, variously oriented crystallites, typically having diameters in the 10-40 A range, interspersed with much larger blocky, unoriented crystallites, typically having diameters in the 100-1600 A range, and mean diameters in the 200-600 A range, as described in Belgian Pat. No. 735,374 the Jl. Applied Physics, Vol. 42, pp. 503-510 (1971).
  • the surfaces of these particles are irregular and of relatively large area, e.g., a specific surface area of about 2 sq. meters/gm., ideal for promoting nucleation of the matrix metal thereon.
  • Ni-B grains on the diamond “A” surfaces are evidence that chemical bonds form between the diamond and the alloy grains.
  • the Ni-B alloy grains cover all, or at least a major portion of, the diamond surface, including under and around projections, and around ledges, affording enhanced keying retention of the diamond particles in the alloy.
  • nucleation and growth of electroless alloy grains on catalytic surfaces is completely different from that occurring with electrodeposited coatings. Since nucleation and growth of metal or metal alloy grains depends, in electroplating, upon the discharge of metal ions at a conductive surface and, since diamond is non-conductive, there can be no chemical bonding, only physical entrapment of diamond in an electrodeposited matrix. In addition, the inclusion of non-conductive diamond particles in an electrodeposited matrix results in shielding of some metallic areas from any applied potential. The shielded areas will either not plate at all, or will at least plate at a slower rate than non-shielded areas, depending upon the degree of shielding, which results in voids in the coating.
  • Voids do not occur in an electroless alloy/nonconductive particle coating as long as there is suitable solution agitation and movement of the article being plated. This movement and agitation affords fresh metallic ions and reducing agent ingress to all surfaces, at the same time voiding gaseous reaction products as deposition proceeds.
  • the stabilizer concentration must be high enough to prevent spontaneous decomposition of the plating bath as well as prevent nucleation of plating on the surfaces of the diamond particles suspended in the bath.
  • nucleation of plating on the diamond "A" particles that come into contact with, and are incorporated in, the coating being deposited will be stifled.
  • excessively high stabilizer concentrations poisons the electroless plating reaction completely, even on a metallic surface which is normally a catalyst for electroless plating, preventing the formation of any coating whatever.
  • plating variables which affect the nucleation of plating on all diamond types are pH, bath temperature and reducing agent concentration. For each electroless alloy process, these variables must be carefully controlled to achieve nucleation at multitudinous sites on the diamond particles as these are incorporated into the composite coating while, at the same time, preventing plating on the particles suspended in the bath.
  • the operating temperature limits within which the desired nucleation will occur are relatively broad, ranging from about 50° C. to about 80° C. At a temperature of above about 80° C., plating starts to initiate on the diamond particles suspended in the bath, causing it to decompose. On the other hand, at temperatures below about 50° C. nucleation of plating is substantially inhibited.
  • the effect of temperature on abrasive wear resistance is shown by Examples 1 and 15.
  • Example 15 in a highly accelerated yarn line wear test, an electroless Ni-B/9 ⁇ diamond "A" coating deposited at 40° C.
  • the specimens used in these tests consisted of coupons measuring about 0.5 mm. wide cut from plated rectangular blocks measuring about 8 mm. ⁇ 13 mm. in cross-section.
  • the front and back surfaces of the test pieces were so smooth and polished that 250X photomicrographs could be taken before and after testing in order to evaluate the amount of wear. Photomicrographs were also taken in plan of the surface of the coatings before and after wear testing to distinguish between a valid test, where the wear track extends across the entire width of the coating, and an invalid test, where corner notching occurring at the front and/or back edges is the result of localized edge cutting and the central part of the wear track remains essentially untouched.
  • Both Tests employed the same general apparatus, shown schematically in FIGS. IIIA-IIIC, except that only the Accelerated Test used the slurry nozzle denoted at 28.
  • Test specimens were clamped in position during testing in a holder, not shown, which was provided with sets of vertical ceramic pins in front of and back of the specimen, which pins defined a vertical slot normal to the width of the specimen about 0.25 mm. wide through which the yarn line 29 ran.
  • the yarn is drawn from a bobbin (not shown) on the left side of FIG. 111A and is trained through "pig tail" ceramic guides 30, through two sets of tensioning disks 31a and 31b, and thence under a 3.2 mm. diameter horizontal ceramic pin 32 located 35 mm. in front of the central axis of the specimen 33.
  • the yarn line next runs across the top coated surface 33a of the specimen and leaves at a slight downward angle by transit under 3.2 mm. diameter horizontal pin 35 located 35 mm. downstream from the central axis of the specimen.
  • the vertical position of the specimen can be adjusted by elevating screws or the like, not shown, to preselect the break angle between running yarn 29 and the horizontal plane of coated surface 33a.
  • Wear Rate in microns per hour was defined as the average depth of the normal wear groove N, i.e., the sum of the wear grooves measured in front, df, and back, db, respectively, divided by 2, the whole divided by the test time in hours, as diagrammed for the lower test track, FIG. IIIE.
  • Very accurate measurements of the wear tracks were made from leading and trailing side elevation (i.e., edge-on) photomicrographs under high magnification both before and after each wear test.) Under the test conditions described, the electroless Ni-P alloy with 9 ⁇ diamond "A" composite coatings exhibited surface polishing but no measurable wear even after 8 hours of continuous testing.
  • Applicator 28 was provided with an axial bore 28a a measuring 0.508 mm. dia. which opened into a vertical-sided end notch 28b 3.18 mm. long, as measured in a horizontal plane in the direction of yarn line travel.
  • the base surface of notch 28b was a convex arc of radius 1.58 mm. drawn from the vertical axis of the applicator.
  • the upper inner edges of notch 28b were beveled outwardly at slopes of 40° measured from the vertical.
  • the yarn line traversed the orifice 28a diametrically at zero break angle, making essentially tangent contact with the orifice lips.
  • An abrasive slurry of oxide particles dispersed in water was pumped through applicator 28 and metered onto the yarn line.
  • test No. 3 were selected for the Accelerated Wear Test for quantitative evaluation of the electroless alloy diamond composite coatings. This test is severe enough to cut grooves, or at least leave visible traces, in diamond composite coatings which extend across the entire width of the test samples, thereby permitting valid quantitative wear rate determination. The test is also severe enough to rapidly cut grooves in high density bulk Al 2 O 3 .
  • the three electroless Ni-B diamond composite coatings are approximately a factor of 8 to 20 times more wear-resistant than the Ni-B Al 2 O 3 composite coating and approximately a factor of 20-55 times more wear-resistant than the Ni-B(SiC) composite coating.
  • the rate of abrasive wear for the electroless Ni-B 9 ⁇ diamond "A” is approximately a factor of two less than that of the comparable composites with natural diamond or diamond "B.”
  • the superior wear resistance of electroless alloy diamond "A” composite coatings demonstrated is attributable to the strong chemical bond formed between the diamond "A” particles and the electroless alloy matrix due to extensive nucleation of plating on the diamond as hereinbefore described.
  • the rate of abrasive wear increases from 6.2 ⁇ /hr. to 216 ⁇ /hr. as the average particle size decreased from 5 ⁇ to 1 ⁇ .
  • the wear resistance of the coatings with particles about 3 ⁇ diameter is very sensitive to volume loading, as indicated for Examples 11 and 13.
  • the yarnline resistance for other types of wear-resistant particles exhibit the same trends (directly proportional to the loadings) with respect to the effects of particle size and volume loading.
  • Examples 6 synthetic diamond “A”
  • 7 natural diamond
  • plain carbon steel blocks were rack-plated in the apparatus of FIG. IX hereinbefore described.
  • the fifteen steel blocks ranged in size from 6 mm. ⁇ 10 mm. ⁇ 15 mm. to 6 mm. ⁇ 6 mm. ⁇ 12 mm. These were given the conventional preplating treatment for steel supra, and then immersed for 30 mins. in a Cuposit NL-63 electroless Ni-P plating bath maintained at 85° C. contained in the apparatus 22 cm. dia. jar. The blocks were disposed on lower shelf 12, permitting coating of top and side surfaces; however, only the top coating was wear-tested.
  • Specimens rack-plated as described contain a higher volume percent of the diamond particulate phase in the horizontal top surface coating than on the sides, and this was the surface chosen for wear testing because the dispersion was most uniform.
  • Example 6 Comparison of Example 6 with Example 7 shows that diamond "A" in Ni-P matrix is superior to natural diamond in the same matrix.
  • the particulate diamond "A" (1 ⁇ size) was slowly added in an amount establishing the final diamond concentration of the bath at 4 gm./liter, and composite plating was conducted at 55° C. for 4 hrs.
  • Examples 9 and 10 were, respectively, Ni-P alloy/9 ⁇ diamond "A” and Ni-P alloy/9 ⁇ natural diamond composites laid down on polymeric substrates.
  • Example 1 For each Example, three blocks and five coupons were prepared from ABS polymer, and the same from fiber-reinforced ABS. The blocks measured 8 ⁇ 13 ⁇ 25 mm. and the coupons 3 ⁇ 10 ⁇ 19 mm. All pieces were tumble-plated as hereinbefore described for Example 1.
  • Rectangular blocks and coupons of molded ABS and fiber-reinforced (some glass fiber and some acicular rutile employed singly) ABS resins were given the polymer pretreatment hereinbefore described for ABS resins and were then coated by the following procedure:
  • FIGS. 9 and 10 of U.S. Pat. No. 3,279,164 there is shown a yarn processing jet which comprises two mating portions, a "cap” and a “body,” which are separable for convenience in stringing up yarn, disassembly taking place at approximately section 10--10, FIG. 9, with the cap itself resembling the design of FIG. 10.
  • the cap was machined from a block of ABS resin filled with 15% of acicular rutile.
  • the cap was tumble-plated to give an electroless Ni-B/3 ⁇ diamond "A" composite coating by the procedure employed in Example 11, except that, in order to obtain only a thin coat, the deposition time was decreased to 80 minutes. Upon inspection under a low power microscope, it was observed that the narrow passageways in the cap were plated similarly to the flat faces which, of course, is important, because the major wear occurs in the passageways.
  • Quantimet analysis of photomicrographs taken at 1000X magnification indicated that the coatings contained about 29 volume percent of particulate diamond. Scanning electron photomicrographs of the surfaces of the composite coatings showed evidence of nucleation of plating at multitudinous sites on individual incorporated diamond particles.
  • This example illustrates the unique attachment between explosively formed diamond "A” and an electroless Cu matrix deposited by McDermid, Inc.'s Metex RS Copper 9055 process.
  • Molded rectangular blocks of ABS and fiber-reinforced ABS resins were given the preplating treatment hereinbefore described for nonconducting substrates generally and were then immersed in an electroless Metex RS copper 9055 bath maintained at 50° C. in a 4-liter beaker.
  • the blocks, which were suspended from copper wires, were positioned about 5 cm. from the bottom of the beaker at locations spaced around the periphery.
  • Plating of electroless copper (free of diamond particles) ensued for about 1 hr.
  • a slurry of plating bath plus a sufficient quantity of 9 ⁇ dia. diamond "A" particles to establish a concentration of 2 gm. powder/liter of plating bath was added to the beaker.
  • the plating bath was agitated with a powered stirrer operated at a speed sufficient to keep the powder particles in suspension.
  • Composite plating in the presence of diamond particles was conducted for 5 hrs.
  • the resulting Cu/9 ⁇ diamond "A” composite showed moderate nucleation of copper grains with the diamond "A.”
  • the copper matrix was composed of 1 to 4 ⁇ grains which displayed a crystal-like growth mechanism, i.e., all surfaces intersected at the same angles, which appeared to be approximately 90°.
  • the nucleated copper grains on the 9 ⁇ diamond “A” particles displayed the same type of crystal-like growth mechanism as the copper grains in the matrix. Copper grains as small as 0.4 ⁇ were observed on the diamond "A” particles, thus being similar to Ni-B grains nucleated on 12 ⁇ diamond “A” particles (refer FIG. I).
  • This example illustrates the effect of plating bath temperature on the nucleation of plating on explosively formed diamond "A” particles incorporated into electroless alloy composite coatings, and on the wear resistance of these coatings.
  • Electroless Ni-B alloy composite coating containing 9 ⁇ dia. diamond "A” particles were plated by the process of Example 1, except that the bath temperature was decreased from 55° to 40° C.
  • Rectangular blocks and coupons of molded ABS and fiber-reinforced ABS resins were first given the hereinbefore described pretreatment required for ABS resins and were then coated as follows:
  • Rectangular blocks and coupons of molded ABS and fiber-reinforced ABS resins were given the standard polymer ABS pretreatment hereinbefore described and then coated as follows:
  • Example 16 The coatings of Examples 16, 17 and 18 were possessed of a uniform dispersion of diamond particles in the electroless Ni-B alloy matrix, as determined by metallographic examination. Quantimet analysis showed approximately 20 volume percent of particulate phase in the composite layers.
  • the blocks were mounted on shelf 12 of the plating apparatus of FIG. IX, given a conventional preplating treatment for steel and then immersed in an electroless Ni-Co-B plating bath of the following composition:
  • the plating bath was maintained at 60° C. and the blocks were plated with an electroless Ni-Co-B strike for 20 mins. Then a slurry containing a sufficient quantity of 9 ⁇ dia. diamond "A" to establish a concentration of 2 gms/liter was introduced into the plating bath. The diamond particles were kept in suspension by a mechanically-driven, paddle-type stirrer rotating at about 350 rpm. Plating was conducted for 3 hours.
  • the composite top surface coatings obtained were given a metallographic examination and it was found that a uniform dispersion of diamond particles existed throughout the Ni-Co-B matrix.
  • Quantimet analysis of photomicrographs of the same surface disclosed that the coating contained about 11 volume percent of the particulate phase, and scanning electron photomicrographs revealed nucleation of plating at multitudinous sites on individual diamond particles incorporated into the surface.
  • a Ni-Co-B matrix/diamond “A” composite coating appears to be at least as wear-resistant as the Ni-B/diamond “A” composite coating of Example 1.
  • the steel blocks were mounted on shelf 12 of the apparatus of FIG. IX, given the conventional pretreatment for steel, and then immersed in an Enplate NI-415 bath and given a 30-min. strike at 85° C. Then a suspension of 9 ⁇ diameter diamond "A" particles was added to give 1 gm/liter and plating continued. The diamond powder was maintained in suspension by a mechanically driven, paddle type stirrer rotated at about 350 rpm. The blocks were removed from the bath after 1.5 hrs. of composite plating.
  • a second set of steel blocks was rack-plated as hereinbefore described for the first set of steel blocks of this Example, except that the 30-min. strike was omitted, and the appearance and diamond content obtained was the same. It is concluded that, with a metal substrate, a strike is not always necessary.
  • the bath employed had the following composition:
  • the blocks were first given an electroless Co-B strike for 25 mins. Then a slurry containing 6 ⁇ dia. diamond "A" was added to give a plating bath concentration of 1 g/l, the diamond particles being kept in suspension by a power-driven paddle-type stirrer. Composite plating in the presence of diamond was done for 105 mins. Approximately five minutes after the steel blocks were removed, the bath decomposed due to excessive plating on the diamond particles suspended therein.
  • a wear test specimen was sliced from a plated block using a wafering machine provided with a 10 cm. dia., 1.2 cm. thick SiC cutting disk driven at 6500 rpm by a 1/3 HP motor.
  • An aqueous solution of Johnson Wax Co's. T.L.-131 cutting fluid was sprayed on the disk as coolant. Portions of the coating became detached and flaked away from the substrate at several locations on the top horizontal surface of the steel substrate, indicating that the coating adhesion was unsatisfactory. None of the other plated steel specimens of the other Examples exhibited coating detachment when similarly cut, except for those specimens of Examples 27 and 28, which were also plated from an active bath which exhibited a tendency to decompose.
  • the blocks were first given the conventional preplating treatment for steel and then immersed in an electroless Co-P plating bath of the following composition:
  • the blocks were plated with an electroless Co-P strike for 50 mins. Then sufficient 9 ⁇ dia. diamond "A" was slowly added to establish a concentration of 0.5 g/l, the particles being kept in suspension by a power-driven paddle-type stirrer. Composite plating in the presence of diamonds was continued for 4 hours.
  • Rectangular blocks and coupons of molded ABS and fiber-reinforced ABS resins were given the polymer pretreatment hereinbefore described for ABS resins and were then coated by the following procedure:
  • Rectangular blocks and coupons of molded ABS and fiber-reinforced ABS resins were given the polymer pretreatment hereinbefore described for ABS resins and were then coated by the following procedure:
  • Metallographic examination of the composite coating showed it to be nonporous and possessed of a uniform dispersion of Al 2 O 3 particles throughout the electroless Ni-B alloy matrix.
  • the coating contained 11 volume percent of the particulate phase.
  • the size of the majority of the Al 2 O 3 particles observed in the photomicrographs ranged from about 6 ⁇ to about 21 ⁇ .
  • a steel block was rack-plated with an electroless Co-B alloy composite coating containing 6 ⁇ dia. diamond "A" particles in a 1-liter bath stored in a 2 liter glass beaker 12 cm. in diameter.
  • the block was suspended from a nickel wire, given a conventional preplating treatment for steel and then immersed in an electroless Co-B plating bath of the following composition:
  • the block was first plated with an electroless Co-B strike for 85 minutes. Then the bath temperature was increased to 95° C. and a slurry containing enough 6 ⁇ dia. diamond "A" particles to establish a concentration of 0.5 g/l was added to the plating bath and kept in suspension by a power-driven paddle-type stirrer. Composite plating in the presence of diamond particles was continued for 2.5 hrs. The bath showed no signs of decomposition.
  • bath composition can affect whether or not nucleation of electroless alloy grains will occur on diamond "A" particles.
  • Example 21 showed that a Co-B/6 ⁇ diamond "A” composite coating from a bath formulated with CoSO 4 .7H 2 O did have nucleation, whereas, in Example 25, the Co-B/6 ⁇ diamond coating formulated from a CoCl 2 .6H 2 O bath did not show nucleation, nor did the Co-P/9 ⁇ diamond "A" coating of Example 22.
  • Scanning electron micrographs revealed nucleation of plating at a multitude of sites on individual diamond particles incorporated into the coating on the top horizontal surface of the blocks. This was the first indication of nucleation at numerous sites on natural diamond.
  • Example 1 Between Example 1, and Examples 19 and 26, two changes were made: (1) The temperature was raised from 55° C. to 60° C. and (2) 6 gm/liter of nickel acetate was replaced by 6 gm/liter of cobalt acetate. As a result of these two changes, nucleation took place on natural diamond as well as on diamond "A" during their incorporation into the coating.
  • TDGA concentration was increased from 0.10 to 0.14.
  • the Santomerse S wetting agent concentration was decreased from 0.1 g/l to zero.
  • the concentration of diamond "A" powder in the bath was decreased from 2 g/l to 1 g/l.
  • the temperature of the bath was increased from 60° C. to 65° C.
  • Example 28 The bath used in Example 28 decomposed after 5 hrs. of operation due to initiation of plating on the diamond "A" particles suspended in the plating bath.
  • Ni-Co-B baths hereinbefore described are excessively active, in the sense that they will readily initiate plating on powder particles added to them.
  • particles with high-energy surfaces such as diamond "A” are added to them, they can decompose due to initiation of plating on the suspended particles which rapidly depletes the bath of metallic ions and reducing agent.
  • particles with low-energy surfaces such as natural diamonds, are added to these "active" baths, plating initates on the particles as they are incorporated into a composite coating being deposited on a substrate.
  • Test Ring 4620 steel, Rockwell C (Rc) 62
  • Test Block 4620 steel, Rc 62 (also used as substrate for coated samples)
  • the “electroless” samples in the above list were prepared according to the same detailed manner as in Examples 6 and 7, supra.
  • the "electroplated” sample was prepared by a commercial nickel electroplating firm, using sample blocks of 4620 steel substrate and diamonds furnished.
  • the tungsten carbide sample was a piece of commercial material.
  • concomitant particulate solids-electroless plate coating according to this invention is not only effective for interrecess coating but also preserves the integrity of sharp edges in structures where sharp edges are essential for good operation.
  • one design of jet coated successfully according to this invention is the air jet utilized for interlacing multi-filament textile yarns, as taught in U.S. Pat. No. 3,115,691.
  • an interlacing apparatus can utilize two air jets 51 of typical diameters in the range of about 0.020 to about 0.10 inch inclined towards one another at an angle ⁇ of, typically, 60°, so that their center lines approximately intersect at a striker plate 49 disposed, typically, 0.008-0.120 inch from the jet housing.
  • a multi-filament yarn 56 is passed centrally of the jets and the inside face of striker plate 49a, as shown, and is interlaced by the action of air vortices created by the jets. It should be mentioned that interlacing whips the yarn about quite violently and there occur repeated yarn impacts with the face of jet body 50 as well as across the jet orifices.
  • the coating procedure was identical to that cited in Example 13 for plating jet venturi units, except that the total plating time was decreased from 230 to 104 min. The plating time was decreased to minimize coating thickness and thereby retain the edge sharpness at the exit orifices of the air holes in the jets. As hereinbefore stated, sharpness and uniformity of the air orifices are important parameters that affect jet performance and yarn quality.
  • Photomicrographs and scanning electron micrographs of the jet orifices revealed that they were well coated on the interior and uniform, with sharp edges free of defects.
  • the radius of the orifice edge was increased only by an amount comparable to the total coating thickness, which was about 0.4 mils.
  • the scanning electron micrographs also revealed that the coating consisted of a uniform dispersion of 3 ⁇ diameter diamond particles in an electroless Ni-B matrix.
  • the surface roughness in the as-plated condition ranged from 40 to 60 AA (i.e., arithmetic average).
  • a Vasco 7152 Tool Steel such as hereinbefore described with reference to Table 3, shows a relatively high wear rate.
  • the wear grooves of the electroless alloy/diamond composites were not only measured to determine wear rate but were also studied to determine the strength of bonding of the particulate diamond within the coating matrix for each of the three diamonds tested, i.e., diamond "A,” diamond “B” and natural diamond. Thus, the wear grooves were carefully examined by scanning electron microscopy and light microscopy to determine the types of wear suffered and, also, whether diamond pull-out occurred under thread-line abrasion.
  • FIG. VI a 250X microscopic plan view of the entire wear sample width, shows the wear groove (2) of the same diamond "A" composite shown in localized magnification in FIG. IV.
  • the corresponding views for the 9 ⁇ natural diamond particle composite (FIG. VII) and the diamond "B" composite of FIG. VIII show the extensive matrix metal-polishing action which occurs in both of these yarnline wear tracks during yarnline testing. This is due to the cutting action of the 0.3 ⁇ ⁇ Al 2 O 3 particles on the threadline, which removes the electroless alloy matrix. The majority of matrix removal occurs after particle pull-out.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Textile Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Chemically Coating (AREA)
US05/694,047 1971-12-15 1976-06-07 Method for concomitant particulate diamond deposition in electroless plating, and the product thereof Expired - Lifetime USRE29285E (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US05/694,047 USRE29285E (en) 1973-03-15 1976-06-07 Method for concomitant particulate diamond deposition in electroless plating, and the product thereof
US07/393,821 USRE33767E (en) 1971-12-15 1989-08-15 Method for concomitant particulate diamond deposition in electroless plating, and the product thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US05/341,529 US3936577A (en) 1971-12-15 1973-03-15 Method for concomitant particulate diamond deposition in electroless plating, and the product thereof
US05/694,047 USRE29285E (en) 1973-03-15 1976-06-07 Method for concomitant particulate diamond deposition in electroless plating, and the product thereof

Related Parent Applications (2)

Application Number Title Priority Date Filing Date
US20823371A Continuation-In-Part 1971-12-15 1971-12-15
US05/341,529 Reissue US3936577A (en) 1971-12-15 1973-03-15 Method for concomitant particulate diamond deposition in electroless plating, and the product thereof

Publications (2)

Publication Number Publication Date
USRE29285E true USRE29285E (en) 1977-06-28
USRE29285F1 USRE29285F1 (enExample) 1983-07-05

Family

ID=26992553

Family Applications (1)

Application Number Title Priority Date Filing Date
US05/694,047 Expired - Lifetime USRE29285E (en) 1971-12-15 1976-06-07 Method for concomitant particulate diamond deposition in electroless plating, and the product thereof

Country Status (1)

Country Link
US (1) USRE29285E (enExample)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4219004A (en) 1978-11-20 1980-08-26 Chemet Research, Inc. Flexible, self-supporting blade for cutting electronic crystals and substrates or the like
US4484988A (en) 1981-12-09 1984-11-27 Richmond Metal Finishers, Inc. Process for providing metallic articles and the like with wear-resistant coatings
US4547407A (en) 1982-08-09 1985-10-15 Surface Technology, Inc. Electroless metal coatings incorporating particulate matter of varied nominal sizes
US4684550A (en) 1986-04-25 1987-08-04 Mine Safety Appliances Company Electroless copper plating and bath therefor
US4951953A (en) 1990-02-15 1990-08-28 Kim Dong S T Golf club
US5029865A (en) * 1990-02-15 1991-07-09 Dsk Diamond, Inc. Golf club
US5079813A (en) * 1990-02-21 1992-01-14 E. I. Du Pont De Nemours And Company Interlacing apparatus
US5183602A (en) * 1989-09-18 1993-02-02 Cornell Research Foundation, Inc. Infra red diamond composites
US5206083A (en) * 1989-09-18 1993-04-27 Cornell Research Foundation, Inc. Diamond and diamond-like films and coatings prepared by deposition on substrate that contain a dispersion of diamond particles
US5527734A (en) * 1990-10-05 1996-06-18 U.S. Philips Corporation Method of manufacturing a semiconductor device by forming pyramid shaped bumps using a stabilizer
US5614477A (en) * 1995-09-07 1997-03-25 Kompan; Vladimir Anti-friction additive and method for using same
US5897965A (en) 1994-11-29 1999-04-27 Zexel Corporation Electrolessly plated nickel/phosphorus/boron system coatings and machine parts utilizing the coatings
US6309583B1 (en) * 1999-08-02 2001-10-30 Surface Technology, Inc. Composite coatings for thermal properties
US7802376B2 (en) * 2003-09-19 2010-09-28 Huettlin Herbert Apparatus for treating particulate material
US20110162751A1 (en) * 2009-12-23 2011-07-07 Exxonmobil Research And Engineering Company Protective Coatings for Petrochemical and Chemical Industry Equipment and Devices

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2858256A (en) * 1953-10-26 1958-10-28 Vitro Corp Of America Electrophoretic method of making an abrasive article and article made thereby
US3061525A (en) * 1959-06-22 1962-10-30 Platecraft Of America Inc Method for electroforming and coating
US3212918A (en) * 1962-05-28 1965-10-19 Ibm Electroless plating process
US3379556A (en) * 1965-02-24 1968-04-23 Ampex Electroless plating system
BE709470A (enExample) * 1967-01-18 1968-07-17
US3484282A (en) * 1966-08-06 1969-12-16 Knapsack Ag Process for the chemical nickel-plating of non-metallic articles
US3644183A (en) * 1963-01-09 1972-02-22 Res Holland Nv Process for coating an object with a bright nickel/chromium coatin
US3674447A (en) * 1969-08-04 1972-07-04 Du Pont Nickel or cobalt wear-resistant compositions and coatings
US3753667A (en) * 1968-01-16 1973-08-21 Gen Am Transport Articles having electroless metal coatings incorporating wear-resisting particles therein

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2858256A (en) * 1953-10-26 1958-10-28 Vitro Corp Of America Electrophoretic method of making an abrasive article and article made thereby
US3061525A (en) * 1959-06-22 1962-10-30 Platecraft Of America Inc Method for electroforming and coating
US3212918A (en) * 1962-05-28 1965-10-19 Ibm Electroless plating process
US3644183A (en) * 1963-01-09 1972-02-22 Res Holland Nv Process for coating an object with a bright nickel/chromium coatin
US3379556A (en) * 1965-02-24 1968-04-23 Ampex Electroless plating system
US3484282A (en) * 1966-08-06 1969-12-16 Knapsack Ag Process for the chemical nickel-plating of non-metallic articles
BE709470A (enExample) * 1967-01-18 1968-07-17
US3617363A (en) * 1967-01-18 1971-11-02 Gen Am Transport Process for electroless metallizing incorporating wear-resisting particles
US3753667A (en) * 1968-01-16 1973-08-21 Gen Am Transport Articles having electroless metal coatings incorporating wear-resisting particles therein
US3674447A (en) * 1969-08-04 1972-07-04 Du Pont Nickel or cobalt wear-resistant compositions and coatings

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Translation of German Offen. 1621206.

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4219004A (en) 1978-11-20 1980-08-26 Chemet Research, Inc. Flexible, self-supporting blade for cutting electronic crystals and substrates or the like
US4484988A (en) 1981-12-09 1984-11-27 Richmond Metal Finishers, Inc. Process for providing metallic articles and the like with wear-resistant coatings
US4547407A (en) 1982-08-09 1985-10-15 Surface Technology, Inc. Electroless metal coatings incorporating particulate matter of varied nominal sizes
US4684550A (en) 1986-04-25 1987-08-04 Mine Safety Appliances Company Electroless copper plating and bath therefor
US5206083A (en) * 1989-09-18 1993-04-27 Cornell Research Foundation, Inc. Diamond and diamond-like films and coatings prepared by deposition on substrate that contain a dispersion of diamond particles
US5183602A (en) * 1989-09-18 1993-02-02 Cornell Research Foundation, Inc. Infra red diamond composites
US4951953A (en) 1990-02-15 1990-08-28 Kim Dong S T Golf club
US5029865A (en) * 1990-02-15 1991-07-09 Dsk Diamond, Inc. Golf club
US5079813A (en) * 1990-02-21 1992-01-14 E. I. Du Pont De Nemours And Company Interlacing apparatus
US5527734A (en) * 1990-10-05 1996-06-18 U.S. Philips Corporation Method of manufacturing a semiconductor device by forming pyramid shaped bumps using a stabilizer
US5897965A (en) 1994-11-29 1999-04-27 Zexel Corporation Electrolessly plated nickel/phosphorus/boron system coatings and machine parts utilizing the coatings
US5614477A (en) * 1995-09-07 1997-03-25 Kompan; Vladimir Anti-friction additive and method for using same
US6309583B1 (en) * 1999-08-02 2001-10-30 Surface Technology, Inc. Composite coatings for thermal properties
US7802376B2 (en) * 2003-09-19 2010-09-28 Huettlin Herbert Apparatus for treating particulate material
US20110162751A1 (en) * 2009-12-23 2011-07-07 Exxonmobil Research And Engineering Company Protective Coatings for Petrochemical and Chemical Industry Equipment and Devices

Also Published As

Publication number Publication date
USRE29285F1 (enExample) 1983-07-05

Similar Documents

Publication Publication Date Title
US3936577A (en) Method for concomitant particulate diamond deposition in electroless plating, and the product thereof
USRE33767E (en) Method for concomitant particulate diamond deposition in electroless plating, and the product thereof
USRE29285E (en) Method for concomitant particulate diamond deposition in electroless plating, and the product thereof
Schlesinger Electroless deposition of nickel
US4547407A (en) Electroless metal coatings incorporating particulate matter of varied nominal sizes
US3762882A (en) Wear resistant diamond coating and method of application
Shipley Historical highlights of electroless plating
US3753667A (en) Articles having electroless metal coatings incorporating wear-resisting particles therein
Watanabe Nano plating-microstructure formation theory of plated films and a database of plated films
EP0520776B1 (en) Method of applying metal coatings on diamond
Dumesic et al. The rate of electroless copper depositionby formaldehyde reduction
US6319308B1 (en) Coating compositions containing nickel and boron and particles
US4854196A (en) Method of forming turbine blades with abradable tips
US3853094A (en) Electroless plating apparatus
US20060251910A1 (en) Composite electroless plating
AU661610B2 (en) Electrodeposited composite coatings
CN102713003B (zh) 无电镀Ni-复合材料的基材和方法
US6106927A (en) Ultra-smooth as-deposited electroless nickel coatings
US20060024514A1 (en) Electroless plating with nanometer particles
US3940512A (en) Method and apparatus for concomitant particulate deposition in electroless plating, and the product thereof
US5707725A (en) Composite plating having a gradient in density of codeposited particles
Osaka et al. Effects of Activation and Acceleration on Magnetic Properties of Chemically Deposited Co‐P Thin Films
Feldstein Composite electroless plating
Vaškelis Electroless plating
Bozzini et al. Corrosion and erosion-corrosion of electrodeposited Ni–P/B4 C composites