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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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  • Y10T428/12944—Ni-base component

Definitions

• This invention is for improvements in or relating to decorative nickel electroplating, and more particularly relates to (l) the electrodeposition of sub-microscopic satin-textured to macroscopic satin-textured fine-grained nickel plate from semi-bright and bright nickel plating baths containing dispersed therein fine bath-insoluble particles, and (2) to the exceptional corrosion resistance of these deposits when over-laid with a thin chromium plate.
• the decorative fine-grained nickel deposits of this invention have various degrees of brightness, or of uniform smokiness, or of uniform satin-sheen depending mainly on the concentration and particle size of the dispersed fine powders in the semi-bright or bright nickel electroplating baths, the concentration of the nickel brighteners, the degree of agitation of the cathode or the solution, the brightness and smoothness of the metal surface plated upon, and the thickness of the plate applied, and these decorative nickel plates of various degrees of sub-microscopic, micro scopic, and macroscopic satin texture and luster when overlaid with a final thin chromium plate provide exceptionally outstanding corrosion protection to the underlying metal.
• titanium and zir conium compounds comprise the class consisting of waterinsoluble titanates and zirconatcs of the metals including calcium, strontium, barium, magnesium, nickel, cobalt, iron, zinc, lead, cadmium, cerium, aluminum, antimony and bismuth, the zirconium and titanium silicates, mixtures and mixed compounds thereof, including, for example, the mixed compounds of the zirconates and titanates, the mixed zirconium and titanium silicates, such as the alkali metal titanium or zirconium silicates, the barium, strontium and calcium titanium and zirconium silicates, as for example, barium zirconium silicate and the mixed aluminates, titanates and zirconates, as for example, zirconium spinel, etc.
• the mixed compounds of the zirconates and titanates such as the alkali metal titanium or zirconium silicates, the barium, strontium and calcium titanium and zirconium silicates, as for example, barium zircon
• the plates be come more satiny up to a point where further increase in concentration of powder produces no further change in appearance of the nickel plate at a given nickel plate thickness on a given base and with a given brightener concentration in the nickel bath.
• concentrations of powder As high as about 500 grams per liter of fine powder can be dispersed in the bath, though in general about 250 grams/liter is the highest that is ever needed for the most macroscopic satin plates.
• the macroscopic satin-textured types of nickel plate which can be obtained by using the higher concentrations, e.g. about grams/liter or higher of the afore-mentioned powders in the semi-bright and bright nickel electroplating baths are fine-grained lustrous satin nickel deposits which not only have a very pleasing appearance, but which can also be high-lighted by buffing raised areas to give beautiful two-tone effects, and which when chromium plated with about 0.01 mil chromium plate will also provide exceptionally good corrosion protection to the basis metals such as ferrous, aluminum, magnesium, brass, copper, zinc and other metal articles.
• the average particle diameter (herein sometimes referred to as particle size”) of the finely powdered bathinsoluble materials should not be greater than 5 microns. As some roughness, especially on shelf areas where particles can settle, may result from the use of materials of particle size greater than about 5 microns, the use of material of particle sizes less than 5 microns are preferred and are advantageous, with the most preferred particle size averaging about 0.02 to about 3 microns as determined with the electron microscope. Some agglomerated particles may have larger particle size than 5 microns but with agitation in the nickel bath the larger agglomeratcs may be reduced to 5 microns and under. Agitation is usually necessary to keep the fine powder suspended in the baths during plating. Air agitation or mechanical agitation including ultra-sonic agitation of the baths can be used.
• This textured plate has excellent adhesion, for example, to nickel, ferrous, copper, and brass surfaces similar to that obtained when the nickel bath contains none of the powdered material.
• the leveling of the bright nickel plate is not decreased by the presence of the finely powdered additives.
• the throwing and covering power of the agitated bright nickel baths with the suspended powders is about the same as without the fine powders present.
• the fine bath-insoluble powders plate out as uniform dispersions in the semi-bright and bright nickel plate and thereby cause sub-microscopic (with the finest particles of 0.01 to about 0.05 micron size) to microscopic-inclusions and sub-microscopic to microscopic-pitting in the surface of the nickel plate. That is at any given instant the surface of the semi-bright or bright nickel plate has distributed over its surface multitudinous fine particles in various stages of being imbedded in the surface and causing sub-microscopic and microscopic pitting, and with the thinnest plates (flashes or strikes) the pitting is mostly submicroscopic becoming more microscopically visible with thicker plating.
• the penetration of the corrosion pits towards the underlying basis metal is very greatly diminished.
• There is also some evidence of extremely fine stress-cracking of the chromium around the micro-inclusions which is also favorable to forming micro cathodes and anodes.
• These textured nickel deposits give the best appearance and corrosion protection results when plated on top of semi-bright sulfur-free nickel or bright nickel deposits. It is best and also simpler to use the regular semi-bright nickel plating baths for most of the plate and to use the minimum of the textured nickel plate required to obtain the desired appearance and corrosion resistance, because the textured nickel plating bath requires added control due to the presence of the dispersed particles, and also because the best corrosion protection results are obtained in this way.
• the macroscopic satin nickel plate obtained from the agitated bright or semi-bright nickel plating baths containing the higher concentrations of these fine powders can as already mentioned be easily buffed to a high luster, without losing the exceptional corrosion resistance when chromium plated.
• the beautiful two-tone effects achieved by buffing accessible portions of the macroscopic satin nickel plated object still have the highest corrosion resistance after the final chromium plate.
• Another useful decorative effect can be obtained where brush or 4 polishing lines are desired in a satin finish, by using coarse polishing grit, for example, to emery on the basis metal.
• the original coarse polishing lines, although diminished by the high leveling satin nickel plate, are still visible. In this way, a highly corrosion resistant scratch brush finish satin nickel is obtained without having to resort to scratch brushing a final nickel plate and thus greatly decreasing its corrosion protection.
• bright or semi-bright nickel plating baths of the Watts, sulfate, high chloride, sulfamate or fluoborate type, or mixtures can be used. While boric acid is the buffer usually used, other buffers, such as formates. acetates, succinates or citrates may also be employed.
• the pH of the baths may be from about 2 to 6, though the preferred pH values are from about 3.5 to 5.2.
• the temperature of the baths can be from room temperature to at least 80 C., though in general a temperature of about 55 C. to about 65 C. is preferred.
• the best addition agents or brighteners to achieve the semi-bright and bright nickel plating conditions necessary to obtain the lustrous satin textured nickel after the addition to the bath of the afore-mentioned powders are the following: the sulfur-containing brighteners including aromatic and unsaturated aliphatic sulfonic acids, sulfonamides and sulfonimides, such as the benzeneor naphthalene-sulfonic acids, p-toluene sulfonimide, benzene sulfonamide, o-benzoyl sulfimide, vinyl sulfonic acid, allyl sulfonic acid, 2-butyne-1, 4-disulfonic acid, o-sulfobenzaldehyde, etc.; the addition agents which produce semi-bright sulfur-free nickel plate such as formaldehyde, chloral hydrate, bromal hydrate, coumarin, butyne diol, ad
• Cobalt and iron can be present in the nickel bath as cobalt or ferrous sulfates, chlorides, bromides, sulfamates or fiuoborates in concentrations as high as at least 40 grams/liter, yielding nickel alloy plates containing concentrations of cobalt and/or iron up to a total of about 50% and it is to be understood that, except when the context requires otherwise, the expression nickel plate" as used herein covers such nickel alloy plates.
• Surface active agents may be present in the baths, but are not usually necessary in the air agitated baths.
• the maximum increase in lustrous sheen is obtained when the fine powders are used in the agitated full bright nickel plating bath such as the air-agitated bright nickel plating baths possessing good leveling properties.
• Less luster is obtained when the nickel baths contain only a carrier type brightener such as a benzene or naphthalene sulfonic acid, p-toluene sulfonamide, benzene sulfonamide or o-benzoyl sulfimide. In the latter cases the luster is flatter. This is also true when the semi-bright sulfur-free type of addition agent such as formaldehyde coumarin,
• chloral hydrate or bromal is used solely with the fine powders, and with these semi-bright addition agents it is usually best to use the ultra-fine particle size powders of less than 0.5 micron particle size, and preferably less than 0.5 micron particle size as determined with the electron microscope.
• the sub-microscopic to macroscopic satin-textured nickel plate accepts chromium plate like regular nickel plate, and in general only the usual thicknesses of final chromium layer need be used, that is 0.25 micron though thicknesses of 2.5 or 5 microns may be used.
• the decorative nickel finish as such, or with the usual final chromium finish the microscopic to marcoscopic satintextured nickel plate can be given a rhodium, silver, tin, brass, bronze, copper, gold, or tin-nickel (65-35) alloy or other final thin coating.
• Thin wax, resin, or soluble wax, films or clear lacquers greatly decrease finger marking of the final coatings, such as nickel, bronze, silver or brass coatings. Chromium, rhodium, and tin-nickel alloy plate do not need these organic coatings, at least not for tarnishing effects.
• baths of this invention in which one or more of the above described powdered materials may be used as described herein. It is to be understood that other inorganic bath compositions and other brighteners may be used, though one of the preferred class of brighteners is the organic sulfon-oompounds.
• Example I Grams/ liter Strontium titanate and/or zirconate (SrTiO SrZrO 0.05 to 3 micron av.
• Example II Barium titanate and/or zirconate 0.1 to 3 micron av. particle size 0.2-100 NiSO -6H O 200-300 NiCl '6H O 40-80 H BO 40 Benzene sulfonamide l-3 Allyl sulfonic acid 1-4 N-allyl quinaldinium bromide 0.003-0.0l
• pH 3.S-5.2, temp -0-70 C. Air agitation or mechanical agitation.
• Example III Zirconium silicate (ZrSiO Example IV Cerium titanate and/ or zirconate av. particle size 0.1 to 3 microns 0.2-150 NiSO -6H O 50-150 NiCl -6H O 200- H BO 40 o-Benzoyl sulfimide 2-4 N-allyl isoquinolinium bromide 0.003-0.01 pH::3.5-5.2, temp, 50-70 C. Air agitation.
• ZrSiO Example IV Cerium titanate and/ or zirconate av. particle size 0.1 to 3 microns 0.2-150 NiSO -6H O 50-150 NiCl -6H O 200- H BO 40 o-Benzoyl sulfimide 2-4 N-allyl isoquinolinium bromide 0.003-0.01 pH::3.5-5.2, temp, 50-70 C. Air agitation.
• Example V Strontium titanate and/or zirconate av. particle size 0.05-3 microns 0.2-100 NiSO -6H O 200-300 NiCl -6H O 30-60 H BO 40 Bromal and/0r chloral hydrate 0.05-0.1 Formaldehyde 0.02-0.08
• Example VI Strontium titanate and/or zirconate av. particle size of 0.05-3 microns 0.2-10 Ultra-fine silica powder (Quso) 1-50 NiSO -6H O 200-300 NiCl -6H O 30-100 H BO 40 o-Benzoyl sulfimide 0.1-3 Benzene sulfonamide 1-3 Allyl sulfonic acid 1-4 Z-butynoxy-l, 4-diethane sulfonic acid 0.05-0.2
• the ultra-fine particles of about 0.01 to 0.05 micron size particles When the ultra-fine particles of about 0.01 to 0.05 micron size particles are used in the semi-bright and bright nickel electroplating bath, it is diflicult to see the included particles in cross-section of the nickel plate even at the highest magnification of the light microscope. However, on the surface of the plate using strong light it is possible to just see the microscopic pitting effect of these sub-microscopic particles. The thinner the plate that is deposited on a bright surface, the more difiicult is it to distinguish any difference between the appearance of the textured deposit and the bright plate obtained without the particles present.
• the micro-inclusions and micro-pitting can be more easily discerned, and an increasing degree of visible satin texture of the plate occurs.
• the lower concentrations of powder of 0.2 to about 20 grams/liter, and in some cases even to about 50 grams/liter are best for obtaining bright plate from the bright nickel baths, and can thus be used best for very thin plates of about 0.01 to 0.1 mil thickness on top of regular bright nickel or semibright nickel plate to obtain after the final chromium plate very high corrosion protecting bright plate.
• the textured plate of this invention is applied on top of regular nickel plate which can be dull, semi-bright or bright nickel plate depending on the decorative effect desired. That is, the degree of brightness, smokiness, or satin quality is dependent on the original brightness and smoothness of the surface plated upon, as well as the thickness of the plate applied, the concentration and type of brighteners present, the concentration of the powder in the bath, the particle size of the powder and the type of powder, that is, its chemical constitution.
• barium titanate at a given concentration for example, of 20 grams/liter and with an average particle size of, for example, 0.5 to 3 microns, will give a more macroscopic satin nickel plate than will strontium titanate at the same concentration and of the same average particle size and from the same bright nickel bath.
• concentration of the strontium titanate or by using lower concentrations of the brighteners then the degree of macroscopic satin texture will be more closely alike.
• magnesium titanate of the same average particle size will require even higher concentrations of the powder to produce the same degree of macroscopic satin texture as the strontium titanate, or conversely strontium titanate and even more so magnesium titanate will allow a full bright plate from the bright nickel bath at higher concentrations of powder than will barium titanate.
• the nickel brighteners that produce very high leveling and brilliance as, for example, those given in US. 2,647,866 (Aug. 4, 1953) and U.S. 2,800,440 and 2,- 800,443 (July 23, 1957) will produce the highest brilliance with the powders dispersed in these bright nickel baths. For less luster, either the higher concentrations of the powders can be used in the very bright plating baths or lower concentrations or with just the organic sulfoncompounds present as brighteners.
• These latter brighteners such as o-benzoyl sulfimide, oor p-toluene sulfonamide, naphthalene, mono-, di-, or tri-sulfonic acids, etc., can be used in concentrations ranging from about 0.1 gram/ liter to saturation.
• strontium titanate it is best to use about 5 to 50 grams per liter of very fine silica to about 0.05 to 1 gram per liter of 0.1 to 3 micron strontium titanate to obtain sub-microscopic to microscopic textured fully bright nickel plate from the bright nickel bath and for macroscopic textured semibright nickel to use 1 to grams per liter of the very fine silica powder to about 10 to 50 grams per liter of: the strontium titanate, or zirconate.
• the textured decorative nickel plate of this invention on complex shaped articles such as many zinc die-cast articles, for example, rear view mirror holders, intricate light housings, steel bumpers, hub caps, and grilles, it is best to use duplex or dual nickel underneath the textured nickel deposit.
• the total nickel deposit would consist of semi-bright sulfur-free nickel followed by regular bright nickel followed by a thin textured nickel deposit of this invention.
• the latter being used as thin plate (0.01 to about 0.1 mil) if the highest brilliance is desired, or as a thicker plate with more powder in the bath to obtain a more subdued brightness or satin type of finish if desired.
• the copper plate When ductile copper plate is used under nickel plate that has a final coating of the textured decorative nickel plate of this invention, then the copper plate also helps in the total corrosion resistance unlike the case when copper is used as a substitute for part of the bright nickel thickness in deposits of copper-bright nickel and the usual 0.01 mil thick final chromium. It is believed that this beneficial effect of copper is also due to the tiny cathode areas developed in the final thin chromium plate, which in turn is due to the fine favorable porosity pattern developed in the thin final chromium plate as a result of its being deposited over a decorative nickel surface containing multitudinous sub-micro to micro-inclusions and sub-micro to micro-pits of the order of 10 per sq. cm.
• a particularly desirable and extremely corrosion resistant composite plate is formed by electroplating the nickel plate of this invention on the upper layer of the composite nickel coating described and claimed in copending application Serial No. 103,296, filed April 17, 1961, which is assigned to the assignee of this invention now US. Patent 3,090,733, issued May 21, 1963.
• This composite plate comprises a lower nickel plate having an average thickness of about 0.15 mil to about 1.5 mils and an average .sulfur content less than about 0.03%, a first overlying electroplate of nickel, or nickel-cobalt alloy containing at least about 50% nickel and having a thickness of about 0.005 mil to about 0.2 mil and an average sulfur content of about 0.05% to about 0.3%, a second overlying layer of nickel or nickel-cobalt alloy containing at least about 50% nickel having a thickness of about 0.15 mil to about 1.5 mils and an average sulfur content of about 0.02% to about 0.15%, the second overlying layer containing a lower percentage of sulfur than said first overlying nickel electroplate and a higher percentage of sulfur than said lower nickel plate, an overlying layer of the nickel plate of this invention, and a top or upper layer of chromium having a thickness less than about 5 microns.
• the fine grain nickel plate of this invention may vary from a thin flash layer to the thicker plate characterized as the macroscopic satin
• titanates tend to raise the pH of the nickel baths to pH values around 5.5, as for example, magnesium titanate, iron titanates, and it is therefore best to use these higher pH values with such powders.
• the copper, zinc, cadmium, lead, antimony and bismuth titanates and zirconates must be used with much more careful control than the other powders to avoid an excess of free copper, zinc, lead, etc., ions which are known to be harmful to the quality of the nickel deposit, and thus it is best to use these powders at the lowest concentrations (0.1 to 1 gram/liter) for the microscopic satin-textured lustrous nickel plate, and to use the higher pH values of the nickel bath to minimize solubilization.
• the preferred powders are the calcium, strontium, barium, magnesium, nickel, cobalt, iron, cerium and aluminum zirconates and titanates, zirconium silicate, and the calcium, strontium, magnesium, and barium zirconium silicates, and the best of these are the strontium and barium zirconates and titanates, zirconium silicate, and the strontium and barium zirconium silicates.
• These powders are by far the least critical to use from the standpoint of their concentrations in the baths, the pH values of the baths, e.g. 36, and give optimum results for both microscopic and macroscopic satin-textured lustrous nickel plate.
• a method for electrodepositing a decorative nickel plate which comprises the step of electrolyzing an aqueous acidic solution of at least one nickel salt selected from the group consisting of nickel sulfate, nickel chloride, nickel fluoborate and nickel sulfamate and at least one soluble organic addition agent capable of producing semibright to fully bright nickel plate, said solution containing dispersed therein about 0.1 to about 250 grams/liter of at least one material selected from the class consisting of the water-insoluble oxygen-containing titanium and zirconium compounds containing a total of at least three different elements, said material being in the form of a fine powder having an ultimate particle size less than about 5 microns average diameter, thereafter plating on said electrodeposited layer an overlayer of a metal se lected from the group consisting of chromium, rhodium, silver, tin, brass, bronze, copper, gold, and an alloy consisting of 65 tin and 35 nickel, said overlayer having a thickness less than about 5 microns.
• a method for electrodepositing a decorative nickel plate which comprises the step of clectrolyzing an aqueous acidic solution of at least one nickel salt selected from the group consisting of nickel sulfate, nickel chloride, nickel fluoborate and nickel sulfamate and at least one soluble organic addition agent capable of producing semibright to fully bright nickel plate, said solution containing dispersed therein about 0.1 to about 250 grams/liter of at least one material selected from the group consisting of the waterinsoluble titanates and zirconates of a metal selected from the group consisting of calcium, strontium, barium, magnesium, nickel, cobalt, iron, and aluminum, the zirconium and titanium silicates, and mixtures and mixed compounds thereof, said material being in the form of a fine powder having an ultimate particle size of less than about 5 microns average diameter, thereafter plating on said electrodeposited layer an overlayer of a metal selected from the group consisting of chromium, rhodium, silver, tin, brass, bronze, copper, gold
• a method for electrodepositing a decorative nickel plate which comprises the step of electrolyzing an aqueous acidic solution of at least one nickel salt selected from the group consisting of nickel sulfate, nickel chloride, nickel fluoborate and nickel sulfamate and at least one soluble organic addition agent capable of producing semi-bright to fully bright nickel plate, said solution containing dispersed therein about 0.1 to about 250 grams/ liter of a mixture of at least one material selected from the group consisting of the water-insoluble titanates and zirconates of a metal selected from the group consisting of calcium, strontium, barium, magnesium, nickel, cobalt, iron, and aluminum, the zirconium and titanium silicates, mixed compounds thereof and about 1 to about 50 gnams/ liter of finely divided silica powder, said materials being in the form of fine powders having an ultimate particle size of less than about 5 microns average diameter, thereafter plating on said electrodeposited layer an overlayer of a metal selected from the group consisting of chromium
• said dissolved organic nickel brightener is selected from the group consisting of aromatic and unsaturated sulfonic acids, sulfonamides and sulfonimides.
• a method in accordance with claim 2 wherein said dissolved organic nickel brightener is o-benzoyl sulfimide.
• a composite electroplate on a metal surface susceptible to atmospheric corrosion which comprises a nickel plate with chromium overplate, said nickel plate having been electrodeposited from an acidic nickel plating bath containing dissolved therein at least one organic nickel brightener capable of producing semi-bright to fully bright nickel plate, and having dispersed in said bath at least 0.1 gram/liter of at least one water-insoluble powder material selected from the class consisting of the waterinsoluble oxygen-containing titanium and zirconium compounds containing a total of at least three different elements, said powder material having particles of average ultimate particle size less than about 5 microns, and an electrodeposited chromium overlay plate on said nickel plate of less than about 5 microns thickness.
• a composite electroplate in accordance with claim 14 wherein said dissolved organic nickel brightener is selected from the group consisting of aromatic and unsaturated aliphatic sulfonic acids, sulfonamides and sulfonimides.
• a composite electroplate on a metal surface susceptible to atmospheric corrosion which comprises a lower nickel electroplate having a thickness of about 0.15 mil to about 1.5 mils and an average sulfur content less than about 0.03%, an overlying layer consisting essentially of an electroplate selected from the group consisting of nickel electroplate and nickel cobalt alloy electroplate containing at least about 50% nickel and having a thickness of about 0.005 mil to about 0.2 mil and an average sulfur content of about 0.05% to about 0.3%, an overlying layer consisting essentially of an electroplate selected from the group consisting of nickel electroplate and nickel-cobalt alloy electroplate containing at least about 50% nickel, and having a thickness of about 0.15 mil to about 1.5 mils and an average sulfur content of about 0.02% to about 0.15%, the second overlying layer containing a lower percentage of sulfur than the said first overlying nickel electroplate and a higher percentage of sulfur than said nickel plate, an overlying layer of nickel plate electrodeposited thereon from an acidic nickel plating bath containing dissolved therein at least one organic nickel

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  • GB GB1051685D patent/GB1051685A/en active Active
• 1963
  • 1963-03-01 US US262199A patent/US3268308A/en not_active Expired - Lifetime
  • 1963-03-01 US US262191A patent/US3268307A/en not_active Expired - Lifetime
  • 1963-03-01 US US262200A patent/US3268423A/en not_active Expired - Lifetime
  • 1963-08-16 US US302739A patent/US3268424A/en not_active Expired - Lifetime
• 1964
  • 1964-02-29 DE DE1521063A patent/DE1521063C3/de not_active Expired
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  • 1964-08-14 DE DE1521065A patent/DE1521065C3/de not_active Expired
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