WO2011089933A1 - Liquide de placage composite avec dispersion de fines particules de diamant, et procédé de fabrication associé - Google Patents

Liquide de placage composite avec dispersion de fines particules de diamant, et procédé de fabrication associé Download PDF

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WO2011089933A1
WO2011089933A1 PCT/JP2011/050156 JP2011050156W WO2011089933A1 WO 2011089933 A1 WO2011089933 A1 WO 2011089933A1 JP 2011050156 W JP2011050156 W JP 2011050156W WO 2011089933 A1 WO2011089933 A1 WO 2011089933A1
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plating solution
fine particles
composite plating
diamond fine
ions
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PCT/JP2011/050156
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English (en)
Japanese (ja)
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将治 小泉
肇 佐々木
寛 鈴木
紀夫 坪川
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アイテック株式会社
国立大学法人 新潟大学
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Priority to CN201180006904.XA priority Critical patent/CN102753734B/zh
Publication of WO2011089933A1 publication Critical patent/WO2011089933A1/fr

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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
    • 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
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/25—Diamond
    • C01B32/28—After-treatment, e.g. purification, irradiation, separation or recovery

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  • the present invention relates to a composite plating solution in which diamond fine particles are uniformly dispersed and a method for producing the same. More specifically, the present invention relates to a composite plating solution in which diamond fine particles introduced with a hydrophilic polymer or an ionic functional group are dispersed together with a surfactant in a metal plating solution, and a method for producing the same.
  • Nanodiamond which is a fine diamond particle, is artificially produced by the impact compression method or the static pressure method, and the form obtained by the production method is different.
  • Different types of nanodiamond such as polycrystal, single crystal, and cluster are known. Yes.
  • Polycrystalline nanodiamond has a spherical structure and is therefore considered a material suitable for a sliding surface between solids.
  • the polycrystalline nanodiamond is a sintered body having a primary particle size of 5 to 20 nm, but it is difficult to stably exist as a primary particle, and a large aggregate of about 50 to 7,500 nm It exists. Therefore, such nanodiamond has been used by being dispersed in a liquid when used industrially.
  • a method in which fine particles are dispersed in an aqueous solvent is generally used.
  • a composite plating bath in which fine particles such as fluororesin, nylon, polyethylene, graphite, fluorinated graphite, molybdenum disulfide, and boron nitride are dispersed in a metal plating bath is known.
  • a metal film is chemically deposited on the surface of the object to be plated, and fine particles are co-deposited in the metal film, and the fine particles are deposited in the metal matrix.
  • a dispersed composite plating film can be formed.
  • the formed composite plating film will have the properties of dispersed fine particles as well as various physical properties of the plated metal. Depending on the type of fine particles to be dispersed and co-deposited, various excellent properties such as low friction, wear resistance, hardness, etc. Properties can be imparted to the plating film.
  • Patent Document 1 describes that composite plating is performed by adding a nonionic dispersant to a plating solution mixed with diamond powder and dispersing the diamond powder in the plating solution.
  • Patent Document 2 As a method that does not use a surfactant, for example, in Patent Document 2, a plating film in which diamond fine particles are dispersed by immersing a substrate while stirring with a gas containing oxygen in a plating bath in which diamond fine particles are suspended is used. A method of forming is described. Patent Document 3 describes a method of performing composite plating with a dispersion liquid in which a cationic functional group is introduced and dispersed in nanodiamond using a polyethylene glycol unit-containing polymer azo polymerizer (AZOPEG) as an introduction agent. Has been. *
  • AZOPEG polyethylene glycol unit-containing polymer azo polymerizer
  • the polycrystalline nanodiamond obtained by the impact compression method has a very small primary particle of 5 to 20 nm, but non-graphitic and graphitic films are fused on the nanodiamond surface, and the particle size is 50 to 50 nm. It is manufactured and sold as a secondary or tertiary aggregate of 7,500 nm.
  • nanodiamond having an average particle size of several nanometers to several hundred nanometers was dispersed in a plating solution to obtain a composite plating film. Since the concentration of dispersed nanodiamond was dilute, the content of nanodiamond co-deposited in the composite plating film was about several percent. Therefore, a composite plating film that sufficiently exhibits the characteristics of nanodiamonds cannot be obtained.
  • an object of the present invention is to provide a composite plating solution in which diamond fine particles are stably dispersed and a method for producing the same.
  • a dispersion in which diamond fine particles into which a hydrophilic polymer or an ionic functional group has been introduced is dispersed together with an ionic or nonionic surfactant is added to the metal plating solution.
  • an ionic or nonionic surfactant is added to the metal plating solution.
  • the diamond fine particles have an average particle size of 1 nm to 1000 nm.
  • the surfactant is a homopolymer or copolymer surfactant having a molecular weight of 30,000 to 200,000.
  • the metal plating solution contains one or more metal ions selected from the group consisting of nickel ions, cobalt ions, copper ions, gold ions, iron ions, palladium ions, platinum ions, tin ions and rhodium ions. It is characterized by including.
  • diamond fine particles having an average particle diameter of 1 nm to 1000 nm and an ionic or nonionic surfactant in which a hydrophilic polymer or an ionic functional group is introduced are uniformly contained in the metal plating solution. It is distributed. Further, the diamond fine particles have a concentration of 0.1 g / liter to 20 g / liter. Further, the surfactant is a homopolymer or copolymer surfactant having a molecular weight of 30,000 to 200,000.
  • the composite plating method according to the present invention is characterized by forming a composite plating film in which the diamond fine particles are uniformly dispersed in a metal matrix by performing a plating treatment on the substrate surface using the composite plating solution.
  • the present invention has the above-described configuration, whereby diamond fine particles into which a hydrophilic polymer or an ionic functional group is introduced are dispersed in a metal plating solution together with an ionic or nonionic surfactant, and diamond A composite plating solution in which fine particles are uniformly dispersed in a stable state can be obtained.
  • FIG. 2 is an enlarged SEM photograph of a cross section of the composite plating film of Example 1.
  • FIG. 4 is an enlarged SEM photograph of a cross section of the composite plating film of Example 2.
  • the metal plating solution used in the present invention is not particularly limited, but is selected from the group consisting of nickel ions, cobalt ions, copper ions, gold ions, iron ions, palladium ions, platinum ions, tin ions and rhodium ions.
  • species or 2 or more types of metal ions can be used,
  • the metal plating solution containing a nickel ion is mentioned as an especially preferable thing.
  • diamond fine particles used in the present invention those having an average particle diameter of 1 nm to 1000 nm, preferably 10 nm to 1000 nm, particularly preferably 10 nm to 200 nm may be used.
  • diamond fine particles those of a polycrystalline type, a single crystal type, and a cluster type that are usually available can be used.
  • a film having a small particle size may be used.
  • a hydrophilic polymer or an ionic functional group is introduced on the surface of the diamond particle.
  • a cationic functional group protons are easily generated in an acidic region.
  • An amino group, a thiol group, a hydroxyl group, a phosphine group and the like which are bonded to each other to form onium. Among these, an amino group that is most likely to form onium is preferable, and an amidine skeleton having two amino groups is more preferable.
  • the azo radical initiator to be reacted with the diamond fine particles preferably has an amidine skeleton.
  • Amidine may be hydrochloride or cyclic.
  • diamond fine particles are reacted with an azo radical initiator in an aqueous solvent. What is necessary is just to mix a diamond fine particle and an azo radical initiator in an aqueous solvent, and to start radical reaction by heating or light irradiation. In the case of heating, it is sufficient to heat to 50 ° C. or more, preferably 65 to 75 ° C., and the reaction is completed in several tens of hours.
  • the reaction rate depends on the amount of the azo radical initiator, and it is preferable to use an azo initiator in an amount of 0.1 to 5 times the weight of the diamond fine particles. If the amount of the azo initiator exceeds 5 times, the amount of organic matter introduced into the diamond fine particles will not increase, and if it is less than 0.1 times the amount of organic matter introduced into the diamond fine particles is small and the dispersibility becomes insufficient. .
  • the aqueous solvent is water or a mixture of water and a water-soluble solvent, and usually water may be used.
  • a water-soluble solvent can be appropriately mixed and used.
  • the water-soluble solvent include alcohols such as methanol and ethanol, aliphatic polyols such as ethylene glycol, glycerin and low molecular weight polyethylene glycol, nitriles such as acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide.
  • Amides such as N-methyl-2-pyrrolidone, sulfur-containing solvents such as dimethyl sulfoxide, dimethyl sulfone and sulfolane, and phosphorus-containing solvents such as hexamethylphosphoric triamide.
  • the concentration of diamond fine particles during the reaction is preferably 1 to 20% by weight, more preferably 5 to 10% by weight.
  • concentration is higher than 20% by weight, the diamond fine particles aggregate, and the reaction between the aggregated diamond fine particles and the azo radical initiator becomes insufficient, making it difficult to introduce an ionic functional group. If it is less than 1% by weight, the concentration of diamond fine particles in the composite plating solution is lowered and the amount of diamond fine particles in the composite plating film is reduced.
  • the aqueous dispersion of diamond fine particles obtained by the above method can be added to the metal plating solution as it is, but a treatment such as separation and washing is performed to remove unreacted azo radical initiators and excess salts. Preferably it is done.
  • a separation method methods such as filtration and centrifugation are used.
  • the filter medium a membrane filter of about 0.1 ⁇ m is preferable because of little separation loss.
  • demineralized water is usually used, but a water-soluble organic solvent may be appropriately mixed so that the remaining organic substances such as the azo radical initiator can be easily removed.
  • various salts can also be dissolved and used.
  • the aqueous dispersion In order to suppress reagglomeration of diamond fine particles in the aqueous dispersion, it is preferable to adjust the aqueous dispersion to a pH range of 3-8. In the case of a strong acid or base liquid, the charge on the surface of the diamond fine particles is neutralized by a counter ion, and dispersion stability due to charge repulsion is inhibited.
  • the pH adjuster include monohydrogen phosphate, dihydrogen phosphate, hydrogen carbonate, carbonate, hydroxide, and the like, and alkali metal salts, alkaline earth metal salts, ammonium salts, and the like are used. You can also.
  • the functional group introduced to the surface of the diamond fine particles a hydrophilic polymer, the steric repulsion force due to the polymer chain on the surface of the fine particles can be increased, and the diamond fine particles can be stably dispersed.
  • both ends of the azo radical initiator can be converted from a hydroxyl group to a Cl (chlorine) end, and then a polymer chain can be imparted to the resulting compound.
  • a polyethylene glycol (PEG) residue, a polydimethylsiloxane (PDMS) residue, etc. are mentioned.
  • the conversion from a hydroxyl group to a Cl terminal can be widely applied to known reaction conditions for acid chloride reaction.
  • the subsequent reaction with the polymer is a general dehydrochlorination reaction, and it is usually advantageous to carry out the reaction in the presence of a basic compound.
  • PDMS residues include — [Si (CH 3 ) 2 —O] m — (m is an integer of about 3 or more, preferably 40 or more) (See JP 2006-219591 A).
  • diamond fine particles are surface treated under dry conditions with an amino group-containing silane coupling agent or amino group-containing silicone oil to introduce amino groups on the surface, and Michael addition of methyl acrylate is added to the introduced amino groups. It is also possible to form a polyamine dendrimer on the surface of the diamond fine particles by repeating the reaction and terminal amination with diamine by repeating under dry conditions (see JP 2001-106940 A).
  • the diamond fine particles introduced with the hydrophilic polymer or ionic functional group described above are added to the metal plating solution as they are, they are affected by the strong ionic strength of electrolyte ions such as nickel ions in the metal plating solution. The electrostatic repulsive force acting between the fine particles is canceled out, causing aggregation and precipitation.
  • a surfactant as a dispersant in order to suppress such aggregation and precipitation of the diamond fine particles and to stably disperse the diamond fine particles in the metal plating solution.
  • the surfactant to be added include anionic surfactants such as anionic and cationic surfactants, and nonionic surfactants.
  • anionic surfactants such as anionic and cationic surfactants
  • nonionic surfactants such as anionic and cationic surfactants
  • alkylbenzene sulfonate, dialkyldimethylammonium salt, etc. there are alkylbenzene sulfonate, dialkyldimethylammonium salt, etc., and these may be appropriately selected depending on the ionic functional group introduced on the surface of the diamond fine particles.
  • the alkyl group used here is an integer of 1 to 6 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl and the like.
  • a nonionic surfactant for example, in the case of PEG, polyethylene glycol mono-4-octylphenyl ether or an alkylphenol surfactant is used.
  • the surfactant used as the dispersant is preferably a homopolymer or copolymer surfactant having a molecular weight of 30,000 to 200,000.
  • the molecular weight is larger than 200,000, it causes cross-linking between diamond fine particles, and acts as an aggregating agent rather than a dispersing agent.
  • the molecular weight is smaller than 30,000, desorption from the diamond fine particles is likely to occur even if the adsorption rate is high, and the effect as a dispersing agent becomes small.
  • the amount of diamond fine particles added may be 0.5 to 10 g / liter in the composition of the composite plating solution. preferable. If a plating treatment is performed using a composite plating solution in which the amount of added diamond fine particles is adjusted within this range, the diamond fine particles can be uniformly dispersed in the plating film, and the content of the diamond fine particles is 0.1 to 30 volumes. % Can also be adjusted.
  • examples of the reducing agent used in the composite plating solution include hypophosphites such as sodium hypophosphite, dimethylamine borane, and hydrazine, amine boranes, and hydrazine salts.
  • concentration of the reducing agent in the composite plating solution varies depending on the type of reducing agent used and the metal to be deposited, but is preferably 20 to 50 g / liter in the composition in the composite plating solution.
  • a complexing agent within a range that does not interfere with the dispersion state of the diamond fine particles.
  • complexing agents that can be used in the composite plating solution include organic acids such as citric acid, lactic acid, succinic acid, malonic acid, propionic acid, adipic acid, malic acid, glycolic acid, and water-soluble salts thereof. Of these, one or a combination of two or more can be used.
  • concentration of the complexing agent to be added is preferably 10 to 40 g / liter in the composition in the composite plating solution.
  • the substrate to be plated is immersed in the composite plating solution in which diamond fine particles are stably dispersed.
  • a composite plating film in which diamond fine particles are uniformly dispersed in the nano order in the metal matrix can be formed on the surface of the object to be plated.
  • an acidic solution such as hydrochloric acid, sulfuric acid or sulfamic acid, or an alkaline solution such as sodium hydroxide or ammonium hydroxide can be appropriately added as a regulator.
  • the bath temperature during the plating process it is preferable to adjust the bath temperature during the plating process to 85 to 90 ° C.
  • the plating efficiency can be improved by stirring the composite plating solution during the plating process or by shaking the object to be plated, and the appearance and thickness of the composite plating film can be kept constant. it can.
  • One preferred embodiment of the method for producing a composite plating solution described above and a composite plating method using the same is, for example, diamond fine particles (average particle size) introduced with a hydrophilic polymer or an ionic functional group as described above.
  • Ni-P electroless composite plating solution (see below composition) in which a surfactant is uniformly dispersed in the composite plating solution and a composite plating method using the same.
  • the object to be plated is immersed in the above electroless composite plating bath adjusted to a liquid temperature of 85 to 90 ° C. and pH 4 to 5 for about 30 to 60 minutes to perform electroless composite plating.
  • a composite plating film in which diamond fine particles are uniformly dispersed in the Ni—P matrix is formed on the surface of the substrate.
  • a composite plating film of 5 to 15 ⁇ m can be formed on the surface of the object to be plated, and diamond fine particles whose average particle diameter is adjusted to 1 nm to 1000 nm can be uniformly dispersed inside the film. It becomes.
  • the amount of diamond fine particles deposited can be 0.1 to 30% by volume, and it is possible to deposit a sufficient amount to exhibit the characteristics of the diamond fine particles.
  • the metal ions are reduced to the metal by the reducing agent by the progress of the plating process, and the diamond fine particles are co-deposited.
  • the metal ion concentration, the reducing agent concentration and the diamond fine particle concentration in the liquid are lowered, and the pH is also lowered.
  • a metal plating solution a reducing agent, diamond fine particles, and a pH adjuster in the composite plating solution continuously or at regular intervals, and maintain their concentrations in a bathing condition.
  • the amount of decrease in the concentration of metal ions, the reducing agent and the fine diamond particles, the amount of change in pH, and the amount of precipitation of the composite plating film are proportional to each other.
  • the deposition rate of the composite plating film is considered to be substantially constant under the same plating conditions if the concentration of the composite plating solution is the same as the initial concentration, a certain amount of metal salt, reducing agent, By supplying appropriate amounts of the diamond fine particles and the pH adjusting agent, the concentration in the composite plating solution can be maintained at an almost initial concentration.
  • the electroless composite plating solution can continue the composite plating process satisfactorily for at least 2 turns, generally 3-4 turns, by replenishing the metal salt consumed in the plating process. Even if the plating process is continuously performed, a composite plating film having a smooth surface and excellent uniformity can be stably formed, and the precipitation rate and the amount of eutectoid of the diamond fine particles are hardly decreased.
  • one turn represents the state of the composite plating solution when an amount of metal corresponding to the initial metal ion concentration in the electroless composite plating solution is deposited, and indicates the degree of wear of the composite plating solution.
  • Example 1 Preparation of anionic functional group-introduced diamond fine particles> SCM fine diamond (average particle diameter; 20 nm) manufactured by Sumiishi Materials Co., Ltd. was used as the diamond fine particles. Further, as a macroazo initiator for introducing an anionic functional group onto the surface of diamond fine particles, “V-501 (4,4′-azobis (4-cyanoantanoic acid))” (hereinafter “V”) manufactured by Wako Pure Chemical Industries, Ltd. -501 ").
  • Diamond fine particles (1.0 g) and V-501 (1.0 g) were added to a 100 ml round bottom flask equipped with a stirrer, a condenser, and a thermocouple, and then 100 ml of methanol solvent was added and stirred while adding nitrogen. The reaction was carried out for 24 hours by heating to 50 ° C. in an atmosphere. After reacting for 24 hours, in order to increase the amount of anionic functional group introduced to the surface of the diamond fine particles, V-501 (1 g) was dissolved in 10 ml of methanol and added to the solution reacted for 24 hours. The reaction was carried out for 24 hours by heating to 50 ° C. in an atmosphere.
  • the reaction solvent was removed to remove unreacted monomers.
  • 100 ml of methanol is added again, and the diamond fine particles are dispersed by ultrasonic treatment, and centrifuged at 1.5 ⁇ 104 rpm for about 60 minutes. went. After centrifugation, the diamond fine particles obtained by removing methanol were dried by suction drying.
  • the anionic functional group-introduced diamond fine particles thus prepared were dispersed in 100 ml of pure water to obtain a 1% by weight diamond fine particle dispersion.
  • the pH of the obtained dispersion was 6.8, the average particle size was about 12 nm, and the maximum particle size was about 30 nm.
  • aggregates of diamond fine particles were not observed.
  • the produced anionic functional group-introduced diamond fine particles were subjected to FT-IR spectrum measurement. As a result of the measurement, new absorption not found in the raw diamond fine particles was observed in the vicinity of 1750 cm ⁇ 1 , 1630 cm ⁇ 1 and 1390 cm ⁇ 1 , and the introduction of COOH groups to the surface of the diamond fine particles was confirmed.
  • the produced anionic functional group-introduced diamond fine particles are dispersed in pure water at a concentration of 1 g / liter and sufficiently dispersed by ultrasonic treatment, and then a cationic surfactant (poly (diallyldimethylammonium chloride) 1 It was added to a concentration of 0.0 g / liter, and further sufficiently dispersed by ultrasonic treatment.
  • a cationic surfactant poly (diallyldimethylammonium chloride) 1 It was added to a concentration of 0.0 g / liter, and further sufficiently dispersed by ultrasonic treatment.
  • the obtained dispersion liquid in which the diamond fine particles and the surfactant were uniformly dispersed was added to the metal plating solution to prepare a composite plating solution having the following composition.
  • a composite plating solution having the following composition.
  • the prepared composite plating solution was adjusted to pH 5.0 by appropriately adding sulfuric acid or ammonium hydroxide solution.
  • the temperature of the composite plating solution was raised to 90 ° C. (use temperature of the composite plating solution).
  • the fine diamond particles in the composite plating solution maintained a good dispersion state, and it was confirmed that the manufactured composite plating solution maintained a stable dispersion state even when the temperature was raised to the use temperature.
  • the dispersion state was confirmed to be a good dispersion state by visually checking the presence or absence of precipitation and the color of the composite plating solution.
  • Such evaluation of the dispersion state can also be quantitatively evaluated by measuring the zeta potential and the particle size distribution.
  • the stability of the dispersed state can be quantitatively evaluated by measuring the zeta potential and the particle size distribution in a state where the composite plating solution is heated to room temperature and then analyzing the change in the dispersed state.
  • quantitative evaluation becomes possible by measuring the prepared composite plating solution with a zeta potential particle size distribution measuring device (for example, manufactured by Beckman Coulter, Inc .; product name DelsaNano).
  • 1 and 2 are graphs showing examples of measurement results of zeta potential and particle size distribution of the composite plating solution, respectively. No significant change is observed between the measurement results before the treatment (measured in a heated state) and after the treatment (measured in a cooled state at room temperature), indicating that a stable dispersion state is realized.
  • a composite plating treatment was performed on a test piece (material; stainless steel (SUS304)) using the composite plating solution.
  • the test pieces subjected to the composite plating treatment were evaluated for the appearance of the composite plating film and the amount of eutectoid of the diamond fine particles.
  • the appearance of the test piece showed a uniform nickel gloss color, and the amount of eutectoid of diamond fine particles was about 10% by weight.
  • FIG. 3 is a magnified photograph of the SEM in which a cross section of the formed composite plating film is photographed. As a result of observing the enlarged photograph shown in FIG. 3, it was confirmed that the diamond fine particles in the composite plating film were uniformly dispersed and eutectoid with an average particle size of about 20 nm.
  • Example 2 ⁇ Preparation of PEG-introduced diamond fine particles> 0.05 g of diamond fine particles as in Example 1 and 2.0 g of “VPE-0201” manufactured by Wako Pure Chemical Industries, Ltd. as a PEG macroazo initiator were added to a test tube. Furthermore, 15 ml of o-dichlorobenzene was added as a reaction catalyst, and the mixture was reacted by heating to 70 ° C. in a nitrogen atmosphere while stirring with a magnetic stirrer.
  • methanol was added to the test tube to stop the reaction, and the product was washed using methanol as a washing solvent.
  • the product is dispersed in methanol, subjected to ultrasonic washing for about 5 minutes, and then centrifuged at 1.5 ⁇ 104 rpm for about 30 minutes to dissolve the non-grafted PEG. The supernatant was removed. This operation was repeated 3 times to remove non-grafted PEG. Thereafter, the precipitate was sufficiently dried by heating to 50 ° C. under reduced pressure.
  • the produced PEG-introduced diamond fine particles are dispersed at a concentration of 1 g / liter in pure water and sufficiently dispersed by ultrasonic treatment, and then a nonionic surfactant (polyethylene glycol mono-4-octylphenyl ether) is added to 1 It was added to a concentration of 0.0 g / liter, and further sufficiently dispersed by ultrasonic treatment.
  • a nonionic surfactant polyethylene glycol mono-4-octylphenyl ether
  • the obtained dispersion liquid in which the diamond fine particles and the surfactant were uniformly dispersed was added to the metal plating solution to prepare a composite plating solution having the following composition.
  • a composite plating solution having the following composition.
  • the prepared composite plating solution was adjusted to pH 5.0 by appropriately adding sulfuric acid or ammonium hydroxide solution. Next, the temperature of the composite plating solution was raised to 90 ° C. (use temperature of the composite plating solution). At this time, the fine diamond particles in the composite plating solution maintained a good dispersion state, and it was confirmed that the manufactured composite plating solution maintained a stable dispersion state even when the temperature was raised to the use temperature. . The dispersion state was confirmed by visual observation as in Example 1.
  • a composite plating treatment was performed on a test piece (material; stainless steel (SUS304)) using the composite plating solution.
  • the test pieces subjected to the composite plating treatment were evaluated for the appearance of the composite plating film and the amount of eutectoid of the diamond fine particles.
  • the appearance of the test piece showed a uniform nickel luster color, and the amount of eutectoid of the diamond fine particles was about 1% by weight.
  • FIG. 4 is an enlarged photograph of the SEM in which a cross section of the formed composite plating film is photographed. As a result of observing the enlarged photograph shown in FIG. 4, it was confirmed that the diamond fine particles in the composite plating film were uniformly dispersed and eutectoid with an average particle diameter of about 100 nm.

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Abstract

L'invention concerne le procédé de fabrication d'un liquide de placage composite au cours duquel de fines particules de diamant de diamètre de grain moyen de 1nm à 1000nm présentes dans un revêtement de placage métallique, sont uniformément dispersées et forment un eutectoïde; lequel procédé permet de conférer des fonctions de résistance à l'abrasion, d'autolubrification, ou similaire. Un liquide de dispersion obtenu par dispersion avec un tensioactif ionique ou non ionique de ces fines particules de diamant de diamètre de grain moyen de 1nm à 1000nm et dans lesquelles sont introduits un polymère hydrophile ou un groupe fonctionnel ionique, est ajouté à un liquide de placage métallique. Ainsi, est fabriqué le liquide de placage composite dans lequel les fines particules de diamant sont stabilisées et dispersées.
PCT/JP2011/050156 2010-01-22 2011-01-07 Liquide de placage composite avec dispersion de fines particules de diamant, et procédé de fabrication associé WO2011089933A1 (fr)

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WO2017061246A1 (fr) * 2015-10-08 2017-04-13 株式会社ダイセル Procédé pour la récupération de nanodiamant à partir d'une solution de placage
US9702045B2 (en) 2015-07-06 2017-07-11 Carbodeon Ltd Oy Metallic coating and a method for producing the same
JP2017201053A (ja) * 2016-05-06 2017-11-09 豊橋鍍金工業株式会社 複合めっき方法および親水性粒子
EP3725921A4 (fr) * 2017-12-15 2021-01-27 Takagi, Mikiharu Procédé de raffinage de grains cristallins dans un film de placage
CN113549990A (zh) * 2021-06-11 2021-10-26 洛阳吉瓦新材料科技有限公司 一种电镀金刚石线锯上砂镀液的处理方法

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