US3904490A - Method of promoting the dispersion of solid particles in an electrolytic bath for composite electroplating of metals - Google Patents

Method of promoting the dispersion of solid particles in an electrolytic bath for composite electroplating of metals Download PDF

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Publication number
US3904490A
US3904490A US511096A US51109674A US3904490A US 3904490 A US3904490 A US 3904490A US 511096 A US511096 A US 511096A US 51109674 A US51109674 A US 51109674A US 3904490 A US3904490 A US 3904490A
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bath
component
sericite
silicon carbide
nickel
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US511096A
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Ishimori Shigeru
Otsuka Shinjiro
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Suzuki Motor Corp
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Suzuki Motor Corp
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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

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  • This invention relates generally to the art of electroplating, and in particular to the formation of plated coatings on metallic articles by composite or joint electrodeposition thereon ofa metal and finely divided particles of an insoluble solid in such a fashion that the solid particles are evenly dispersed throughout the bath and hence coatings. More specifically, the invention is directed to a method of promoting the formation and stabilization of a dispersion of the solid particles in an electrolytic bath containing a soluble compound of the metal.
  • plated nickel coatings have silicon carbide particles dispersed therein, for example, have markedly improved wear resistance, so that the coatings of this character are being adopted advantageously for lining the cylinders of internal combustion engines, among other applications.
  • An article to be plated is connected as the cathode in the bath, and the anode disposed in opposed relationship to the cathode is formed of nickel.
  • nickel deposits on the article along with the silicon carbide particles.
  • the silicon carbide particles must be held evenly dispersed in the bath in order to obtain plated coatings of unfluctuating quality.
  • this requirement has been met by: (1) agitating the bath by mechanical means; (2) imparting vibratory motion to the article to be plated; or (3) introducing air bubbles into the bath through perforated pipes laid out at the bottom of the cell. All these conventional means are not entirely satisfactory because, upon cessation of their operation, the particles of silicon carbide and the like settle to the cell bottom in several hours. Preparatory to each run of electroplating operation. therefore, the bath must be sufficiently agitated to cause even dispersion of the solid particles therein. Time and labor conventionally expanded to this end has presented a serious bar to the increase in the productivity of the plating plant. It should also be taken into consideration that the listed mechanical means are relatively bulky and require unnecessarily large space for installation.
  • an object of this invention to provide. in the plating of metallic articles by composite or joint electrodeposition thereon of nickel and finely divided particles of an insoluble solid, a novel method of causing the even dispersion of the solid particles in the plated coatings by use of a high efficacious dispersant to be added to an electrolytic bath, whereby the need for provision of mechanical means for agitating the bath is substantially eliminated.
  • Another object of the invention is to provide a method of the character described wherein the dispersant in use is effective not only to cause the even dispersion of the solid particles but to improve the wearresistance. heat-resistance, hardness, lubricity, and other properties of the resulting plated coatings. whereby these coatings are made extremely suitable for surface protection of various metal-made articles including internal combustion engine cylinders.
  • this invention provides, in the art of plating metallic articles by joint electrodeposition of first and second components, wherein the first component is nickel and the second component a powder insoluble inv an electrolytic bath containing a soluble compound of nickel, an improved method which comprises adding sericite to the bath for promoting the formation and stabilization of a dispersion of the second component therein.
  • Sericite is also effective in imparting wear resistance and lubricity to the plated coatings.
  • sericite itself can be used as the second component.
  • FIG. I is agraph in which is plotted a curve (i) of the sedimentation volume in cubic centimeters per gram of silicon carbide particles (second component) in an electrolytic bath additionally containing a first component and a dispersant according to the invention against the standing time in hours of the bath and. by way of comparison, a curve (ii) of the sedimentation volume of silicon carbide particles in an electrolytic bath additionally containing the first component but no dispersant against the standing time of the bath;
  • FIG. 2 is a photomicrograph of a section of a coating plated on an iron casting by joint clectrodcposition thereon of nickel and sericite;
  • FIG. 3 is also a photomicrograph of a section of an other plated coating formed by joint electrodeposition of nickel, silicon carbide, and sericite;
  • FIG. 4 is a graph indicating the results of wear tests of a nickel-silicon carbide plated coating (indicated by the solid line) according to the prior art and of a nickelsilicon carbide-scricite plated coating (dotted line) ac cording to the invention in relation to the silicon carbide contents of the coatings.
  • the electrolytic bath for use in composite electro plating of metals according to the invention is composed of: (I) at least one first component selectable from compounds of nickel; (2) at least one second component selectable from oxides, carbides, metallic substances, ceramics, anad other inorganic substances in the form of insoluble powders; and (3) a dispersant for causing uniform dispersion of the second component in the bath and hence in electroplated coatingsv As the dispersant sericitc can be used.
  • sericite While its properties and uses are well known in the art,- sericite may be described as a scaly variety of muscovite or white mica. Monoclinic in crystal system like muscovitc, sericite has a silky or pearly luster and imparts oilincss upon adhesion to the human skin. The crystalline grains of memoriite are no more than about 2 microns in size. Sericite can also be described as a natural hydrous aluminum silicate, with a composition close to that of museovite, and has a low potassium content and a high moisture content. The general formula of courseite is:
  • the settlement of the second component at the cell bottom has easily taken place if the bath (not containing the dispersant according to the invention, of course) is allowed to stand for a few hours.
  • this second component is silicon carbide, and if its particles are about 3 microns or more in size, then these particles will coagulate in the bath.
  • the expenditure of considerable physical effort, including the use of the listed mechanical means according to the prior art, is required to effect redispersion of the coagulated silicon carbide masses in the form of the initial sized particles.
  • the curve (i) represents variation in silicon carbide sedimentation volume in cubic centimers per gram with the standing time in hours of a composite electroplating bath containing. in addition to the said first component, grams per liter of silicon carbide as the second component and I0 grams per liter of memoriite as the dispersant.
  • the curve (ii) in the same graph similarly represents variation in silicon carbide sedimentation volume in cubic centimcters per gram with the standing time in hours of a bath containing, in addition to the first component. 100 grams per liter of silicon carbide as the second component but no dispersant.
  • the viscosity of the bath increased with increase in the amount of memoriite added, so that the bath required an increasingly greater degree of agitation by mechanical means. With the addition of more than 100 grams per liter of memoriite, the bath could no longer be properly agitated. The coatings produced from such bath tended to exhibit stickiness and irregularity in thickness.
  • Anode Electrolytic Nickel EXAMPLE ll A bath having a composition shown in Table 1, Le. consisting of nickel sulfamate, nickel chloride, boric acid and sodium saccharin was admixed with grams per liter of serieite. With the use of this bath, an iron casting that had been subjected to the usual pretreat ment was electroplated under the same plating conditions as shown in Table l in a cell in accordance with the prior art process, in which the bath was constantly I agitated by blowing air under pressure from a compressor into perforated vinyl chloride pipes laid out at the bottom of the cell. The iron casting being plated was also subjected to constant vibratory motion. The process was carried out for 1 hours, with a current density of 20 amperes per square decimeter. The resultantly plated coating exhibited oiliness and smoothness obviously due to the addition of sericite to the bath.
  • FIG. 2 A photomicrograph representation of a section of this composite electroplated coating is shown in FIG. 2. It will be clearly observed that the fine sericite particles are uniformly dispersed throughout the nickel layer on the iron casting. The average size of the sericite particles was found to be 0.3 microns.
  • Table 2 represents the results of chem ieal analyses of the various ingredients of the sericite used in the foregoing experiments.
  • Table 3 shows the distribution of particle size of sericite used.
  • the sedimentation velocity of the silicon carbide particles increases with the increase in their size and with the decrease in the silicon carbide amount added to the bath. Also. the greater the size of the silicon carbide particles that have settled at the bottom of the cell. the more easily will they coagulate.
  • Table 4 represents the relationship between the quantities in grams per liter of various sized silicon carbide particles to a nickel sulfamate bath and their sedimentation velocities in centimeters per hour.
  • the bath has no sericite content. It should be noted in connection with this table that even when 150 grams per liter of silicon carbide particles with an average size of 2.2 microns is added to the bath. in which case the lowest sedimentation velocity is exhibited. the particles will coagulate if the bath is allowed to stand for several Table 2 lngredi- SiO A1 0 Fe O; FeO TiO CaO MgO K 0 cm Weight 47.21 .62 0.36 0.l 0.14 0.l 1.45 6.70 ratio, 7r
  • sericite can be added to the bath in a quantity anywhere in the range of from about 5 to 100 grams per liter in the case of nickel-sericite plating.
  • the upper limit becomes considerably lower in the case of nickel-silicon carbidesericite plating. This is because, upon introduction of silicon carbide to a nickel solution, the viscosity of the resultant dispersant naturally becomes significantly higher than that of the nickel solution.
  • the amount of sericite to be added to the bath is therefore determined more or less by the amount of silicon carbide added.
  • the principal advantage of adding sericite to nickelsilicon carbide baths is that the silicon carbide particles are thereby rendered highly dispe'rsible and are further prevented from coagulating.
  • the particle size of silicon carbide is in the range of ll0 microns, preferably 2-4 persed by mechanical means.
  • the silicon carbide particles Upon introduction of sericite to this nickelsilicon carbide bath. the silicon carbide particles become uniformly dispersed and become materially reduced in sedimentation velocity. The silicon carbide particles will not coagulate if the bath is allowed to stand for several days. This obviously is because. since the sericite particles added to the bath are as fine as about 0.3 microns in average size. the coarser silicon carbide particles are carried, so to say. by those of sericite and are thereby held dispersed in the bath. More specifically. upon introduction of 10 grams per liter of sericite to the nickel-silicon carbide baths represented in Table 4. the sedimentation velocities of the silicon carbide particles drop to about l/2.5 through [/23 of those exhibited in the case of no sericite introduction to the baths.
  • the average size of the silicon carbide particles is 3.7 microns.
  • FIG. 3 is the photomierographic representation of a ground cross section of the electroplated coating. fromwhich it will be noted that the silicon carbide particles are uniformly dispersed throughout the coating.
  • This coating is also notable for its improved heat re- Table 6 Sericite Quantity added. g/] 0 l0 SiC Quantity added. g/l
  • the bath viscosity increases with increase in the quantity of sericite added. tending to cause stickiness in the plated coatings.
  • the viscosity of a liquid increases in substantial proportion with its content ofparticulatc matter. it is therefore appropriate for most practical purposes that no more than about 40 grams per liter of sericite be added to an electroplating bath with a large content of fine silicon carbide particles.
  • Table 7 below rc present typical examples of the relationship between the amount in grams per liter of sericite added and the resulting viscosity ijn eentipoiscs of nickel baths each containing 100 grams per liter of different sized silicon carbide particles.
  • Table 9 Tabulated below as Table 9 are the results of hardness testing of a coating electroplated from a nickel bath containing 100 grams per liter of silicon carbide only and of another coating electroplated from a nickel bath containing 100 grams per liter of silicon carbide and 20 grams per liter of sericitc. Prior to the hardness tests. the coating specimens were charged into an electric furnace which had been heated to the specified temperatures and were allowed to stand for 1 hour therein. The thus heated specimens were then allowed to cool in the atmosphere. and their hardness was then measured by means of a micro- Vickers hardness tester.
  • the surface of the coatings plated from the nickel-silicon carbide-sericite bath are just as smooth and oily as those of the coatings plated from the nickelsericite bath.
  • the anti-wear property of the former type of coating can thus be markedly improved as a result of the use of sericitc as the dispersant.
  • the plated coatings formed by the addition of sericite to the nickel-silicon carbide bath have improved hardness at temperatures of about 300C or more. While the coatings plated in a bath with no sericite content according to the prior art suffer a marked drop in hardness in a temperature range of from about 200 to 300C, those plated in the bath containing sericite according to the invention exhibit a similar drop in hard ness only in a temperature range of from about 300 to 400C.
  • the wear resistance of the coatings according to the invention is also materially improved due to the inherent lubricity of sericitc.
  • composition of the bath and the conditions of the electroplating operation as employed in this Example was the same as Table 8 shown hereinbefore.
  • FIG. 3 represents a section of the coating formed under the foregoing conditions.
  • the nickel-silicon carbide-sericite plated coatings according" to the invention and nickel-silicon carbide plated coatings according to the prior art were further subjected to Ohkoshi wear tests with the aim of determining the relationship between the wear resistance of the coatings and their silicon content.
  • the wear resistance of the two types of coatings thus ascertained was also evaluated in relation to the use of scricite as the dispersant.
  • the required variation in the silicon carbide content of the test specimens was caused by controlling the amount of silicon carbide introduced into the bath. Silicon carbide particles with an average size of 3.7 microns were used for the preparation of all the test specimens.
  • silicon carbide is used as the insoluble powder of the second component, similar effect may also be achieved when powders of other inorganic substances which are insoluble to the electrolyte are used.
  • the second component and the dispersant are chemically independent, and the sedimentation speed of the second component is madeslower simply by a physical phenomenon.
  • the differences between the specific gravities and the particle sizes of the second component and sericite are not so small (specific gravity 277-288), but the particle size is so small that the sedimentation speed becomes very small in the solution as compared with the second component.
  • said second component is a member selected from the group consisting of insoluble powders of oxides, carbides, metallic substances, and ceramics, said bath containing at least a soluble compound of said first component and said second component.

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US511096A 1973-10-05 1974-10-01 Method of promoting the dispersion of solid particles in an electrolytic bath for composite electroplating of metals Expired - Lifetime US3904490A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4338215A (en) * 1979-09-24 1982-07-06 Kennecott Corporation Conversion of radioactive wastes to stable form for disposal
DE3245070A1 (de) * 1981-12-08 1983-06-16 Aluminium Pechiney, 69003 Lyon Verfahren und vorrichtung fuer die genaue einstellung der anodenebene einer elektrolysezelle fuer die herstellung von aluminium
US4601795A (en) * 1985-03-27 1986-07-22 The United States Of America As Represented By Secretary Of Interior Alloy coating method
US4892627A (en) * 1989-02-18 1990-01-09 Takada Laboratories, Inc. Method of nickel-tungsten-silicon carbide composite plating
US5342502A (en) * 1992-08-31 1994-08-30 Industrial Technology Research Institute Method of preparing silicon carbide particles dispersed in an electrolytic bath for composite electroplating of metals

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2925529B1 (fr) * 2007-12-19 2010-01-22 Luzenac Europ Sas Materiau composite constitue par une matrice metallique dans laquelle sont reparties des nanoparticules phyllosilicatees lamellaires synthetiques
JP6649018B2 (ja) * 2015-09-16 2020-02-19 日本電産サンキョー株式会社 ロータリエンコーダ、およびロータリエンコーダの絶対角度位置検出方法

Citations (3)

* 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
US3644183A (en) * 1963-01-09 1972-02-22 Res Holland Nv Process for coating an object with a bright nickel/chromium coatin
US3762882A (en) * 1971-06-23 1973-10-02 Di Coat Corp Wear resistant diamond coating and method of application

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE620811A (en)) * 1961-07-31

Patent Citations (3)

* 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
US3644183A (en) * 1963-01-09 1972-02-22 Res Holland Nv Process for coating an object with a bright nickel/chromium coatin
US3762882A (en) * 1971-06-23 1973-10-02 Di Coat Corp Wear resistant diamond coating and method of application

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4338215A (en) * 1979-09-24 1982-07-06 Kennecott Corporation Conversion of radioactive wastes to stable form for disposal
DE3245070A1 (de) * 1981-12-08 1983-06-16 Aluminium Pechiney, 69003 Lyon Verfahren und vorrichtung fuer die genaue einstellung der anodenebene einer elektrolysezelle fuer die herstellung von aluminium
US4601795A (en) * 1985-03-27 1986-07-22 The United States Of America As Represented By Secretary Of Interior Alloy coating method
US4892627A (en) * 1989-02-18 1990-01-09 Takada Laboratories, Inc. Method of nickel-tungsten-silicon carbide composite plating
US5342502A (en) * 1992-08-31 1994-08-30 Industrial Technology Research Institute Method of preparing silicon carbide particles dispersed in an electrolytic bath for composite electroplating of metals

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JPS5436578B2 (en)) 1979-11-09

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