WO1984002149A1 - Cosedimentation electrolytique de zinc et de graphite, ainsi que le produit resultant - Google Patents

Cosedimentation electrolytique de zinc et de graphite, ainsi que le produit resultant Download PDF

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Publication number
WO1984002149A1
WO1984002149A1 PCT/US1982/001689 US8201689W WO8402149A1 WO 1984002149 A1 WO1984002149 A1 WO 1984002149A1 US 8201689 W US8201689 W US 8201689W WO 8402149 A1 WO8402149 A1 WO 8402149A1
Authority
WO
WIPO (PCT)
Prior art keywords
zinc
graphite
codeposit
electrolyte
coating
Prior art date
Application number
PCT/US1982/001689
Other languages
English (en)
Inventor
William A Donakowski
John R Morgan
Original Assignee
Ford Motor Co
Ford Werke Ag
Ford France
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
Application filed by Ford Motor Co, Ford Werke Ag, Ford France filed Critical Ford Motor Co
Priority to EP19830900525 priority Critical patent/EP0127620B1/fr
Priority to JP83500658A priority patent/JPS59502108A/ja
Priority to PCT/US1982/001689 priority patent/WO1984002149A1/fr
Priority to DE8383900525T priority patent/DE3277378D1/de
Priority to BR8208101A priority patent/BR8208101A/pt
Publication of WO1984002149A1 publication Critical patent/WO1984002149A1/fr

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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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/24—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing hexavalent chromium compounds
    • 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
    • C25D5/48—After-treatment of electroplated surfaces

Definitions

  • Automotive metal fasteners are usually coated or plated to enhance various characteristics such as resistance to corrosion, resistance to seizing/galling, low fastening friction, economy, solderability, and resistance to the stick-slip phenomenon (which is a repeated sticking followed by repeated slipping during fastener tightening operations).
  • cadium is subject to two disadvantages: (a) it has a toxic effect during processing, and (b) it is significantly expensive.
  • codeposited particles can be considered nonconductive and normally would not respond to the normal electrolytic action, but it was found that even graphite would plate or codeposit under very strained and undesirable conditions with nickel.
  • the metal matrix and codeposited particles were viewed as to their antifriction, antiseizing, and dry lubrication properties and found them not lower than zinc or cadmium. No investigation was made of the mode of corrosion of such codeposits. Without exploring proper processing parameters, the author concluded that codeposition was feasible only at conventional metal plating parameters. Similar observations were made by Parker as to electroless nickel deposits, entitled “Hardness and Wear Resistance Tests of Electroless Nickel Deposits", Journal of Plating, Vol. 61, p. 834, September 1974.
  • the invention is, in a broad aspect, the discovery that a codeposit of zinc and graphite provides an unusually good combination of physical characteristics including a coefficient of friction comparable to cadmium and, in a more particular aspect, an improved method of effectively electrodepositing zinc and graphite onto at least a vertical conductive metal surface.
  • the codeposit is a high lubricity coating material consisting of electrocodeposited zinc and graphite uniformly distributed, the graphite being present in an amount of 30-48% by weight of the codeposit, and the coating having a coefficient of friction equal to or less than .130 at a plated thickness of about .0005" showing (a) no red rust in a salt spray environment for at least 72 hours, and (b) no destruction due to corrosion in an industrial environment containing sulphur dioxide after four months.
  • the material have a chemically applied layer of zinc chromate at a thickness of .00002" so that optimally the coated combination will exhibit consistent torque performance at a torque load of 40 pounds, a coefficient of friction of about .112 or less, and no red rust in a salt spray environment for at least 120 hours.
  • the fastener When the codeposited coating is applied to a threaded fastener, the fastener will preferably exhibit a consistent torque tension relationship during tightening and have good solderability characteristics using either a resin solder cord or a zinc chloride containing flux.
  • the method is carried out by the use of an electrolytic cell having a zinc anode and the metal substrate connected as a cathode.
  • the essential steps of the method comprise: (a) immersing the substrate, in a cleansed condition, into an acidic zinc plating electrolyte containing at least 40 g/1 zinc ions and 30-110 g/1 insoluble bulk graphite, the electrolyte having a pH of 5-5.7; (b) energizing the electrolytic cell at a sufficient current density to plate out zinc onto said surface without burning while continuously agitating said graphite into uniform suspension throughout said solution, said agitation being periodically interrupted to allow said graphite to settle and saturate said zinc interface as it is plating out on said cathode.
  • the conductive metal substrate is a metallic threaded fastener which may be comprised of steel, copper, nickel, brass, bronze, zinc and. aluminum.
  • the agitation is preferably interrupted for 15-60 seconds at intervals of 15-80 seconds.
  • the particle size of the graphite employed is of an extremely fine character, and preferably is of a colloidal nature having a particle size of 1-25 microns.
  • the electrolyte is of the acid chloride type, created by either mixing 70-85 g/1 zinc chloride with 100-150 g/1 of potassium chloride, or 45-110 g/1 of zinc chloride when dissolved with 100-200 g/1 of sodium chloride.
  • the acid chloride bath contains also boric acid in an amount of 26-40 g/1.
  • the electrolyte may be improved by incorporating a grain refiner in the form of gelatin in an amount of .4-1 g/1 of electrolyte, and a cationic surfactant in the form of cocamine acetate (having the formula C 12 H 25 NH 3 ) in an amount of .1-.4 g/1 of electrolyte.
  • a grain refiner in the form of gelatin in an amount of .4-1 g/1 of electrolyte
  • a cationic surfactant in the form of cocamine acetate (having the formula C 12 H 25 NH 3 ) in an amount of .1-.4 g/1 of electrolyte.
  • the codeposit may be subjected to an additional step of dipping into a chromate passivation solution for a period of about 10-30 seconds in order to form a conversion zinc chromate coating on the outer layer of said codeposit.
  • the cleaning of the substrate may include immersion in a caustic cleansing solution to remove oils and other organic materials followed by a clean water rinse, and then immersion in a pickling solution to remove any oxides thereon, again followed by water rinse.
  • the apparatus is comprised of a mechanically rotated barrel which is perforated and contains a metallic plate bolted to the bottom of the barrel which in turn is connected to a commutator ring on the outside of the barrel.
  • the barrels are made of inert material such as polypropylene.
  • the cathode contact with the fasteners is usually made by metal discs on the bottom of the cylinder .
  • the electrolyte permeates the barrel through the perforations and the anode is suspended just below the level of the solution.
  • Figures 2 and 3 are enlarged schematic illustrations of a portion of a coating showing inorganic particles embedded in the coating.
  • Figure 2 employing conductive particles and Figure 3 using nonconductive inorganic particles;
  • Figure 4 is a graphical illustration showing the variation of coefficient of friction as a function of the type of material employed in the coating, particularly the concentration of graphite in a codeposit of zinc and graphite;
  • Figure 5 is a graphical illustration of the deposition rate or volume of the codeposited materials of this invention as a function of the current density;
  • Figures 6-8 each respectively illustrate a graphical illustration of torque and tension as a function of the angle of rotation of a fastener coated respectively with phosphate and oil (Figure 6), zinc and graphite codeposit with a chromate outer coating (Figure 7), and a cadmium plate with a chromate outer coating (Figure 8);
  • Figures 9-11 each respectively illustrate a scanning electron microscope photograph (at 100X) of coatings prepared in accordance with the process teaching of this invention.
  • Figure 9 illustrating a coating prepared with a concentration of 120 g/1 of graphite in the electrolyte.
  • Figure 10 illustrating a coating prepared from a 75 g/1 concentration of graphite in the electrolyte, and Figure 11 illustrating a concentration of 50 g/1 graphite in the eletrolyte; and
  • Figure 12 is an electron scanning microscope photograph of a section of a coating prepared in accordance with this invention showing the various layers of the coating as labeled.
  • This invention has discovered that a codeposit of zinc and graphite with a critically high content of graphite will provide an unusually good combination of physical charactertistics, including an ultralow co- efficient of friction.
  • the physical characteristics may comprise anticorrosion properties, good solderability, economy of processing and little or no stick slip problem.
  • the prior art has never codeposited zinc/graphite and thus has failed to observe the most elementary threshold of improvement of this codeposited material.
  • the codeposit of zinc and graphite has particular utility in the coating of fasteners, pins and gears.
  • a preferred method mode for obtaining the codeposit of this invention is as follows. Apparatus Preparation
  • a processing and electrolytic plating system is prepared.
  • a barrel plating mode may be employed whereby rotatable cylinders 10, constructed of acid resistant, nonabsorbant material (such as polypropylene, resin bonded fiberglass, hard rubber, PVC, lucite, and phenolic laminates) are used to contain the parts to be plated while being tumbled.
  • the cylinders are perforated and are mounted for rotation upon a horizontal axis, the trunions 11 for the axis being supported in a carriage 12 which is moved from tank to tank and is lowered into each tank for treatment therein.
  • the series of tanks that may be employed with this method, and barrel plating apparatus include a series of cleaning and rinsing tanks (not shown, which are interposed between process tanks).
  • One or more of electrolytic plating tanks 13-14-15 are employed, followed by a suitable rinse tank 16. Only the electrolytic plating tanks are energized and contain an electrolyte.
  • the parts, such as metal fasteners, are loaded in a bulk fashion into the cylinder through an access door thereof; the parts are connected as a cathode in the electrolytic plating cell by use of a metal plate bolted to the bottom of the barrel for contact with the batch of parts.
  • the plate is connected by slip ring to an outside electrical supply.
  • the anode can comprise a plurality of zinc elements extending into the bath containing the electrolyte solution and into which the barrels are lowered.
  • the substrate or, in this case, a bulk quantity of metallic fasteners, is loaded into the barrel plating cylinder and carried through a series of cleaning tanks.
  • a series of cleaning tanks which may preferably comprise a first bath having a highly alkaline solution effective to remove oil and gum deposits on the metallic substrate.
  • the alkaline cleansed metal substrate is then rinsed by use of conventional tap water and then immersed in a pickling solution containing a concentration of about 30% hydrochloric acid, which is effective to remove oxides, followed by a conventional water rinse.
  • the parts Prior to immersing the cleansed substrate into an acid zinc plating electrolyte for depositing a codeposit, the parts may preferably be preplated with 0.0002" zinc in a conventional acid zinc plating electrolyte.
  • the electrolyte for the codeposit contains 40 g/1 zinc ions and 30-110 g/1 insoluble bulk graphite.
  • the zinc ions are obtained in the electrolyte by introducing a zinc anode into the bath solution; the bulk graphite is preferably introduced in a fine grade condition, optimally colloidal graphite, having a particle size in the range of 1-25 microns. Crude foundry grade graphite is operable within the scope of this invention, crude graphite having an average particle size of 25-100 microns. Utilizing the finer colloidal graphite will obtain a much smoother codeposit having typically an average particle size of 2 microns.
  • the graphite is added to the electrolyte in amounts less than 30 g/1, a noticeable increase in the coefficient of friction of the codeposit will result and make the coating less effective in performing as a low friction composite. If the graphite is added to the solution and maintained in a suspension quantity of greater than 110 g/1, the graphite will plate out in an amount which will be greater than 50% of the codeposit and thus substantially reduce the ability of the codeposit to have anticorrosion characteristics attributable to the presence of zinc.
  • the acid zinc electrolyte is prepared by adding to an aqueous solution 45-110 g/1 zinc chloride and 100-200 g/1 sodium chloride. The pH of such acid bath should be maintained in the range of 5-5.7 and optimally about 5.3.
  • the acid chloride bath may be prepared by using 70-85 g/1 zinc chloride and 100-150 g/1 of potassium chloride. Boric acid in the range of 26-40 g/1 may be added as a buffering agent.
  • .4-.1 g/1 of unflavored gelatin may be added to the electrolyte. Additionally, .1-4.0 g/1 cocamine acetate (having the molecular formula of C 12 H 25 NH 3 ) is added, which serves to facilitate the deposition of nonconductive particles.
  • the pH range should be regulated as given. If higher than such range, zinc hydroxide will form which is undesirably insoluble. If lower than 5, the acidity of the electrolyte will affect cohesion.
  • the electrolyte should be maintained in a temperature range of 75-90 °F.
  • the electrolytic cell is energized at a sufficient current density to plate the zinc onto the substrate without burning while continuously agitating the graphite into suspension throughout said electrolyte.
  • the agitation is periodically interrupted to allow the graphite to settle and comingle with the zinc as the plating takes place on the cathode.
  • the agitation is carried out by the use of air pulsing and is interrupted for periods of 15-60 seconds at intervals of 15-180 seconds. During all other times the air pulsing is on.
  • the current density is preferably employed in the low range of 1-20 amps per square foot (.1-2.0 amps/dm 2 ). If the current density is lower than this value, insufficient plating zinc will take place.
  • the rate of zinc metal deposition affects the entrapment rate of the graphite particles during the coating of the cathode.
  • the graphite deposition rate and graphite particle volume can be optimized (see Figure 5). If a current density of between .8-1.6 amps/dm 2 is employed, the best graphite rate as well as graphite volume deposition is obtained. This is.
  • Chromate Outer Coating It is desirable to dip the electroplated codeposit in a solution containing an acid chromate for a period of 10-45 seconds to form a very thin chromate outer coating on the metal substrate.
  • the chromate should typically have a thickness of 2 -5 inches thick.
  • the zinc/graphite plated part is dipped in a chromating solution consisting of 30 g/1 chromic acid, 10 cc/1 phosphoric acid, 5 cc/1 hydrochloric acid, 5 cc/1 nitric acid, and 5 cc/1 sulfuric acid for a period of about 30 seconds, followed by a warm rinse of about 30 seconds.
  • a chromating solution consisting of 30 g/1 chromic acid, 10 cc/1 phosphoric acid, 5 cc/1 hydrochloric acid, 5 cc/1 nitric acid, and 5 cc/1 sulfuric acid for a period of about 30 seconds, followed by a warm rinse of about 30 seconds.
  • a chromating solution consisting of 30 g/1 chromic acid, 10 cc/1 phosphoric acid, 5 cc/1 hydrochloric acid, 5 cc/1 nitric acid, and 5 cc/1 sulfuric acid for a period of about 30 seconds, followed by a warm rinse of about 30 seconds
  • the chromate conversion coating on the codeposit of this invention renders exceptionally good corrosion resistance because of (a) the corrosion inhibiting effect of hexavalent chromium contained in the chromate film, and (b) to the physical barrier presented by the chromate film itself.
  • the film is formed by the chemical reaction of the hexavalent chromium with the zinc metal surface in the presence of activators in the acid solution.
  • the hexavalent chromium is partially reduced to trivalent chromium during the reaction with a concurrent rise in pH, forming a complex mixture consisting largely of hydrated basic chromium chromate and hydrus oxides of both chromium and the zinc metal.
  • the activators useful in forming the conversion coating include acetate formate, sulphate, chloride, flouride, nitrate phosphate, and sulphamate ions.
  • the immersion time for a conversion coating herein is relatively short, a period of 20-30 seconds.
  • the zinc/graphite codeposit in some samples was passivated with a chromate film of a thickness of 0.00002".
  • the samples were subjected to a chemical content analysis to determine the content of graphite and the corresponding coefficient of friction at a torque load of 40 ft/lbs.
  • the solution was varied with a variety of graphite contents; the results of such analysis are shown in the following Table 1.
  • the codeposit of this invention is dry to the touch, which is often commercially difficult to consistently achieve with fasteners coated with phosphate and oil.
  • the shelf life of the codeposit is excellent, having a life of well over one year, and is economical to finish while presenting no hazards with respect to toxic processing considerations.
  • the raw materials for the system are relatively plentiful.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Electroplating Methods And Accessories (AREA)

Abstract

Cosédiment de zinc et de graphite à haute lubricité, ainsi qu'un procédé amélioré de sédimentation du cosédiment. Le revêtement est caractérisé par un coefficient de friction égal ou inférieur à 0,130 et une forte résistance à la corrosion démontrée par l'absence de rouille rouge lorsqu'il reste pendant 72 heures dans un environnement de vapeur saline et l'absence de destruction due à la corrosion lorsqu'il reste pendant quatre mois dans un environnement industriel contenant de l'oxyde sulfureux. Lorsque le cosédiment possède en plus un revêtement extérieur de chromate, le système possède un coefficient de friction égal ou inférieur à 0,112 et est exempt de rouille rouge lorsqu'il reste pendant au moins 120 heures dans un environnement de vapeur saline. On applique le cosédiment en immergeant un substrat métallique nettoyé dans un électrolyte de revêtement de zinc acide contenant au moins 40g/l d'ions de zinc et 30 à 110g/l de graphite insoluble en vrac, avec un pH se situant entre 5 et 5,7. La cellule dont l'électrolyte est une partie est mise sous tension pour provoquer une cosédimentation; le graphite est agité continuellement lorsqu'il est en solution, l'agitation étant interrompue périodiquement pour permettre au graphite de se déposer et d'imprégner l'interface de zinc pendant la sédimentation.
PCT/US1982/001689 1982-12-01 1982-12-01 Cosedimentation electrolytique de zinc et de graphite, ainsi que le produit resultant WO1984002149A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP19830900525 EP0127620B1 (fr) 1982-12-01 1982-12-01 Cosedimentation electrolytique de zinc et de graphite, ainsi que le produit resultant
JP83500658A JPS59502108A (ja) 1982-12-01 1982-12-01 亜鉛と黒鉛の同時電着及びその生成物
PCT/US1982/001689 WO1984002149A1 (fr) 1982-12-01 1982-12-01 Cosedimentation electrolytique de zinc et de graphite, ainsi que le produit resultant
DE8383900525T DE3277378D1 (en) 1982-12-01 1982-12-01 Electrolytic codeposition of zinc and graphite and resulting product
BR8208101A BR8208101A (pt) 1982-12-01 1982-12-01 Codeposito eletrolitico de zinco e grafite;processo de eletro galvanizacao de zinco e grafite e de um lote de fechos roscados;material de revestimento de alta lubricidade;fecho roscado eletrogalvinizado

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1982/001689 WO1984002149A1 (fr) 1982-12-01 1982-12-01 Cosedimentation electrolytique de zinc et de graphite, ainsi que le produit resultant

Publications (1)

Publication Number Publication Date
WO1984002149A1 true WO1984002149A1 (fr) 1984-06-07

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PCT/US1982/001689 WO1984002149A1 (fr) 1982-12-01 1982-12-01 Cosedimentation electrolytique de zinc et de graphite, ainsi que le produit resultant

Country Status (5)

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EP (1) EP0127620B1 (fr)
JP (1) JPS59502108A (fr)
BR (1) BR8208101A (fr)
DE (1) DE3277378D1 (fr)
WO (1) WO1984002149A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2221921A (en) * 1988-07-29 1990-02-21 Baj Ltd Electrolytic or electroless codeposition of particles and metal
WO2011156676A3 (fr) * 2010-06-10 2012-01-26 Authentix, Inc. Matériaux métalliques à particules luminescentes incorporées
CN114597482A (zh) * 2022-03-14 2022-06-07 浙江大学温州研究院 一种用于锌电池负极的固态电解质界面的原位制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3061525A (en) * 1959-06-22 1962-10-30 Platecraft Of America Inc Method for electroforming and coating
US3640799A (en) * 1967-09-09 1972-02-08 Nsu Motorenwerke Ag Process for producing a wear-resistant surface on a workpiece
US3922208A (en) * 1973-11-05 1975-11-25 Ford Motor Co Method of improving the surface finish of as-plated elnisil coatings
US3932228A (en) * 1973-11-01 1976-01-13 Suzuki Jidosha Kogyo Kabushiki Kaisha Metal material for sliding surfaces
US4036600A (en) * 1975-06-05 1977-07-19 Kawasaki Steel Corporation Steel substrate electroplated with Al powder dispersed in Zn

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2325559A1 (de) * 1973-05-19 1974-11-28 Dietmar Loeffler Verfahren zur galvanischen herstellung von graphit enthaltenden metallueberzuegen
JPS5224941A (en) * 1975-08-21 1977-02-24 Kawasaki Steel Co Surface treated steel plate for molding and its production method

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3061525A (en) * 1959-06-22 1962-10-30 Platecraft Of America Inc Method for electroforming and coating
US3640799A (en) * 1967-09-09 1972-02-08 Nsu Motorenwerke Ag Process for producing a wear-resistant surface on a workpiece
US3932228A (en) * 1973-11-01 1976-01-13 Suzuki Jidosha Kogyo Kabushiki Kaisha Metal material for sliding surfaces
US3922208A (en) * 1973-11-05 1975-11-25 Ford Motor Co Method of improving the surface finish of as-plated elnisil coatings
US4036600A (en) * 1975-06-05 1977-07-19 Kawasaki Steel Corporation Steel substrate electroplated with Al powder dispersed in Zn

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Plating, issued November 1969, T.W. TOMASZEWSKI, et al., Codeposition of Finely Dispersed Particles with Metals, pp 1234-1239 *
See also references of EP0127620A4 *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2221921A (en) * 1988-07-29 1990-02-21 Baj Ltd Electrolytic or electroless codeposition of particles and metal
US5037513A (en) * 1988-07-29 1991-08-06 Baj Limited Production of coatings
GB2221921B (en) * 1988-07-29 1993-02-03 Baj Ltd Improvements relating to the production of coatings
WO2011156676A3 (fr) * 2010-06-10 2012-01-26 Authentix, Inc. Matériaux métalliques à particules luminescentes incorporées
CN103080376A (zh) * 2010-06-10 2013-05-01 奥森迪克斯公司 嵌有发光颗粒的金属材料
US20140302234A1 (en) * 2010-06-10 2014-10-09 The Royal Mint Limited Metallic materials with embedded luminescent particles
AU2011264736B2 (en) * 2010-06-10 2015-08-06 The Royal Mint Limited Metallic materials with embedded luminescent particles
US9175398B2 (en) 2010-06-10 2015-11-03 The Royal Mint Limited Metallic materials with embedded luminescent particles
US9567688B2 (en) 2010-06-10 2017-02-14 The Royal Mint Limited Metallic materials with embedded luminescent particles
EP3290542A1 (fr) * 2010-06-10 2018-03-07 The Royal Mint Limited Matériaux métalliques comportant des particules luminescentes incorporées
CN114597482A (zh) * 2022-03-14 2022-06-07 浙江大学温州研究院 一种用于锌电池负极的固态电解质界面的原位制备方法

Also Published As

Publication number Publication date
EP0127620A1 (fr) 1984-12-12
BR8208101A (pt) 1984-10-02
JPS59502108A (ja) 1984-12-20
EP0127620B1 (fr) 1987-09-23
EP0127620A4 (fr) 1985-07-01
DE3277378D1 (en) 1987-10-29

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