WO2001066825A1

WO2001066825A1 - Coating compositions containing nickel and boron

Info

Publication number: WO2001066825A1
Application number: PCT/US2000/005955
Authority: WO
Original assignee: Mccomas, Edward; Mccomas Industries International, Inc.
Priority date: 2000-03-08
Filing date: 2000-03-08
Publication date: 2001-09-13
Also published as: AU2000235165A1

Abstract

The invention is directed to corrosion and wear resistant metallic coatings containing nickel, boron, and thallium. The coatings are preferably deposited on catalytically active substrates from an electroless coating bath containing nickel ions, a mixture of thallium nitrate and thallium sulfate as a stabilizer, a metal ion complexing agent, and a borohydride reducing agent, at a pH of about 10 to about 14.

Description

Coating compositions containing nickel and boron

BACKGROUND OF THE INVENTION

This invention relates to novel metal coatings, which exhibit exceptional hardness. More particularly this invention relates to metal coatings containing nickel, boron and thallium to the reductive deposition of said coatings on the surfaces of substrate articles from aqueous solutions at an alkaline pH.

The plating or deposition of metal alloys by chemical or electrochemical reduction of metal ions on t e surface of an article to modify its surface characteristics for both decorative and functional purposes is well known in the art. Of particular commercial significance is the deposition of metal/metal alloy coatings on both metal and activated non- metal substrates to enhance surface hardness and resistance to corrosion and wear. Nickel-boron and cobalt-boron alloy coatings are recognized in the art for their hardness and associated wear-resistance. The patent literature reflects an ongoing research and development effort in the area of nickel- boron coatings with the goal of producing still harder, more corrosion resistance coatings from a stable bath. For example, SΘΘ, U.S. Pat- Nos - 5,019-163; 3,-738,849; 3,674,447; 3,342,338; 3,378,400; 3,045,3342; and 726,710. The art has recognized that when a borohvdride reducing agent is used in a nickel/boron-plating bath a harder coating is achieved. However. borohvdride, is very unstable in the bath. The solution to the stability problem has been to add stabilizers such as thallium salts such as thallium sulfate, or lead chloride to control the instability of the borohvdride. To control the stability of the borohvdride requires balancing the need for a proper plating rate at the expense of stability. An over stabilized bath fends to plate slowly and co-deposit thallium m the coating. The addition of stabilizers created 3 new oroblem in the art by interfering with the formation of the nickel coating. D¹inner the foriπa on of the nickel coatincr the stabi1 zer wonlei co-deposit m the nickel coating thereby negatively impacting the hardness of the coating. In the case of thall um, the hardness of the coating begins to decrease as the concentration

crrOn-r- wi "'"he m "'k°1 coatmcr,

7 c; h Ka h qrrpς +- i γ~ o a _.c-,H

rTinf i minn c l aHH cτ7on additional th lliu to achieve stabιlιt⁷ of the nickel/boron bath. During normal operation of the bath, boron and thallium sa1T^" -^r ^ d ever "*^~hιrt^r iriπ¹¹^⁰? As ^^~h° b^^h 3_cres the ^ oun^" of thallium needed to stabilize the borohvdride increases. nis increase m co c t t o OJ.

bath causes the concentration of the thallium in the nickel

uch as Bellis or Klien the amount of thall um m the nickel Γ S^IΠQ "* " p. : mnr c; RflSr r r ra "h Ti Vinnr ~ i

production. As the thallium concentration m the coating aooroaches 4% the hardness of the coatmcr will be reduced b approximately 25% .

This invention solves "^h¹¹-¹ orobl°m m fh^Ω ar"^ of controlling the amount of thallium code osited m the nickel coatin^^1" as the bath acres while -*- the sam° "*^~ι llowmcr for an a -'ι"C--7^mι-h

haf

seleot ncr a mixture of th llium sulfate and thallium nitrate the co-deposition of thallium m the nickel coating can be less than 4 ^ as the bath ag s. Pr f rabl thai1m i the nickel coatincr can be les than 3% as the bath acre . A"*- the same time the olatincr rate can be maintained at 1 mill ^ r hour, It is therefore a general obj ect of this invention to ΌΓOVI de a method of electroless "platmcr an article of

1 +-<3 cnrfaro ATΠ τ-^"h a harH due11le wea and corrosion resistant me al co -*-me

both nickel, boron, and thallium from a bath containing a rn i t"< "I "> "P l ^"1 ^ ^TIl cπl f a o apH ha 1 1 l ϊ "h -r- ;a -j- -i cπ "I- I -n 4~ hc thallium, codeposited in the coatincr is below 4%. Preferably the thallium codeposited in the coating is below 3%. And at the same time the plating rate can be maintained at 1 mill per hour .

Z τ> π PP^ O "^ f "i s "i τt 7'--.-n"l- -i rι-rι ή cr - ^ rn^rϊ Hα l mrirn^TDH rriu-^ ] alloy coating composition containing both nickel and boron and a mixture of thallium sulfate and thallium nitrate. Another object of this invention is to provide coating

T.ioa -_-ιr-ι/-3

rαc ι c n coating can be deposited on at least a portion of the surface

_•

SUMMARY OF THE INVENTION

According to the present invention there is provided a novel metal coating composition containing both nickel and boron and a mixture of thallium sulfate and thallium nitrate. The coating composition can contain other metal ions. The coating composition is particularly useful for deposition on a surface of an article of manufacture, which is subject to exposure to corrosive conditions or one subject to sliding or rubbing contact with another surface under unusual wearing and bearing pressures. The metal coating of the present invention comprises about 85 to about 96.5 weight percent nickel, about 0.5 to about 10 weight percent boron and thallium not greater than about 4%. A preferred range for the nickel coating is 93-96 weight percent nickel and 2-5 weight percent boron and not greater than about 3% thallium. The coating is hard, yet ductile, and is highly corrosion and wear resistant.

It has now been surprisingly discovered that by using a mixture of thallium sulfate and thallium nitrate to stabilize a nickel-boron plating bath it becomes possible to control tne amount of thallium codeposited m the nickel/boron coating a^c the bath ages and at the same time maintain an acceptable plating rate. The present coating is preferably applied to a substrate electrolessly by contacting the substrate with a coating bath containing nickel ions, mixture of thallium sulfate and thallium nitrate, a metal ion complexmg agent, and a borohvdride reducing agent at pH about 10 to about 14 and at an elevated temperature of about 180 to about 210° F. The coating can be plated at lower temperatures after the plating has been initiated within a temperature range of about 180 to about 210 F

DETAILED DESCRIPTION OF THE INVENTION

Suitable substrates for electroless deposition are those with so-called catalytically active surfaces including those composed of nickel, cobalt, iron, steel, aluminum, zinc, palladium, platinum, copper, brass, chromium, tungsten, titanium, tin, silver carbon, graphite and alloys thereof. Those materials function catalytically to cause a reduction of the metal ions m the plating bath by the borohvdride and thereby result m deposition of the metal alloy on the surface of the substrate in contact with the plating bath. Aluminum usually requires a protective strike coat to prevent dissolution before plating. Non-metallic substrates such as glass, ceramics and plastics are m general, non-catalytic materials; however, such substances can be sensitized to be catalytically active by producing a film of one of the catalytic materials on its surface. This can be accomplished by a variety of techniques known to those skilled m the art. One preferred procedure involves dipping articles of glass, ceramic, or plastic m a solution of stannous chloride and ther contacting the treated surface with a solution of palladium chloride. A thin layer of palladium is thereby reduced on the treated surface. The article can then be plated or coated with the metallic composition m accordance with this invention by contact with a coating bath as detailed below. It is to be noted that magnesium, tungsten carbide and some plastics have exhibited some resistance to deposition of the present coatings .

A coating bath for deposition of the present coatings comprises

(1) Nickel ions, about 0.175 to about 2.10 moles per gallon. Calculations were based on a nickel chloride range of .05 to .6 pounds per gallon. A preferred range of nickel ions is about .35 to about 1.57 moles per gallon based on .1 to about .45 pound per gallon of nickel chloride.

(2) An effective amount of a chemical agent for adjusting the pH of the bath to between about 10 and about 14;

(3) about 2.26 to about 6.795 moles per gallon of metal ion complexmg agent, preferably 3.3 to 3.8 moles per gallon

(4) about 0.03 to about .1 moles per gallon of coating bath of a borohvdride reducing agent based on BH4 preferably .045 to .08 moles per gallon of bath;

(5) 0.0508 grams per gallon and 0.11872 grams per gallon, preferably, between about 0.06784 grams per gallon and 0.10176 grams per gallon, and more preferably between about 0.075 grams per gal and 0.092 grams per gal of a mixture containing thallium sulfate and thallium nitrate. The best results falling between about 0.0806 and 0.0858 grams per gallon of the mixture containing thallium sulfate and thallium nitrate of as a stabilizer. The percentage of thallium nitrate the mixture is less than 50°- of the combined weight of the thallium nitrate and thallium sulfate; preferably between about 3% to about 38% thallium nitrate of the

weight of the thallium nitrate and thallium sulfate; and more preferably between about 3% to about 10% thallium nitrate of the combined weight of the thalliu_™ nitrate and thallium sulfate; and the best result between about 5% to about 7% thallium nitrate of the combined weight of the thallium nitrate and thallium sulfate;

The borohydride reducing agent can be selected from among the known borohydrides having a good degree of water solub¹ lity and stability aqueous solutions. Sodium borohydride is preferred. Ir addition, substituted borohydrides m which not more than three of the hydrogen atoms of the borohydride ion have been replaced can be utilized. Sodium trimethoxyborohydπde [NaB (OCH3) 3H] is illustrative of that type of compound.

The coating bath is prepared to have a pH of about 12 to about 14. Best results have been observed when the pH of the bath is maintained during the coating process within that range and more preferably at about pH 13.5. Adjustment of bath pH can be accomplished by addition of any of a wide variety of alkaline salts or solutions thereof. Preferred chemical agents for establishing and maintaining bath pH are the alkali metal hydroxides, particularly sodium and potassium hydroxide, and ammonium hydroxide. Ammonium hydroxide offers an additional advantage in that the ammonium ion can function to assist metal ion complexmg the coating bath. Due to the high alkalinity of the coating bath, a metal ion complexmg or sequestering agent is required in the bath to prevent precipitation of the metal ions such as nickel and other metal hydroxides or other basic salts. Importantly, too, the metal ion complexmg agent functions t^ lower metal ion reactivity; the complexed or sequestered metal ions have minimal reactivity with the borohydride ion« m the bulk solution but do react at the catalytic surfaces of substrates m contact with the solution. The term catalytic surface _refers to the surface any article composed of the aforementioned catalytic materials or to the surface of a non-catalytic material which has been sensitized by application of a film of said catalytic materials on its surface. The complexmg or sequestering agents suitable for use this invention include ammonia and organic complex-forming agents containing one or more of the following functional groups: primary ammo, secondary ammo, ternary ammo, lmmmo, carboxy and hydroxy. Many metal ion complexmg agents are knowr in the art. Preferred complexmg agent^c are ethylenediamme, diethylene tπamme, triethylene tetramme, the organic acids, oxalic acid, citric acid, tartaric acid and ethylene diamme tetraacetic acid, and the water soluble salts thereof. The most preferred is ethylene diamme. About 2.26 to about 6.795 moles per gallon of complexmg agent are used per gallon of coating bath. This calculation was based on .3 to about .9 pound per gallon of ethylenediamme. Best results have been obtained when about 3.39 to about 3.77 moles per gallon of coating bath. This calculation was based on about 0.45 t^ about 0.5 pound per gallon of ethylenediamme for each gallon of coating bath.

The metal ions, like nickel, m the coating bath are provided by the addition to the bath by the respective water soluble salts. Any salts of those metals having an anion component which is not antagonistic to the subject coating process is suitable. For example salts of oxidizing acid such as chlorate salts are not desirable since they will react with the borohydride reducing agent the bath. Nickel

sulfates, formates, acetates, and other salts whose anions are substantially inert with respect to the other ingredients the alkaline coating bath are satisfactory.

The stabilizer s added to the bath from of a concentrate. The concentrate contains about 28 to about 37 grams per gallon of the mixture containing thallium sulfate and thallium nitrate as a stabilizer. The preferred range of a mixture is about 31 to about 33 grams per gallon. The percentage of thallium nitrate m the mixture is less than 50° of the combined weight of the thallium nitrate and thallium sulfate; preferably between about 3% to about 38% of the combined weight of the thallium nitrate and thallium sulfate; and more preferably between about 3% to about 10% of t^he combined weight of the thallium nitrate and thallium sulfate; and the best result is between about 5% to about 7% of the combined weight of the thallium nitrate and thallium sulfate;

The pH of the concentrate is usually above 7, preferably at 10.5. A pH modifier is added to the concentrate to adjust the pH. The pH modifier is selected from those bases such as sodium hydroxide, that are not harmful to the plating bath.

The concentrate is added to the bath so that upon dilution the concentration of the mixture containing thallium sulfate and thallium nitrate m the bath can range between 0.0508 grams per gallon and 0.11872 per gallon, preferably, between about 0.06784 grams per gallon and 0.10176 grams per gallon, and more preferably between about 0.075 grams per gallon and 0.092 grams per gallon of a mixture containing thallium sulfate and thallium nitrate. The best results falling between about 0.0806 and 0.0858 grams per gallon of the mixture containing thallium sulfate and thallium nitrate.

The coating bath is typically prepared by forming an aqueous solution of the appropriate amounts of metal salts, adding the complexmg agent (s) and stabilizer, adjusting the pH to about 12 to about 14, heating to about 195° F., filtering and finally, immediately before introducing the substrate into the bath, adding the required amounts of sodium borohydride (typically m aqueous alkaline solution) . The article to be coated or plated using a bath m accordance with this invention is prepared by mechanical cleaning, degreasmg, anode-alkalme cleaning, and finally pickling an acid bath m accordance with the standard practice the metal-platmg art. The substrate can be masked if necessary to allow deposition of the metal alloy coating only on selected surfaces. Although the present coatings m general exhibit excellent adhesion to properly prepared

r r i j — i r a l

-Ά r~-_ι α v α r i OTI Γ Q H coatmg-adhesion can often be enhanced by depositing a nickel strike electroche ically on the substrate surface prior to applying the present coating.

The cleaned or otherwise surface-prepared article is immersed m the hot (about 180 to about 210° F. ^ coating bath to initiate the coating process. The process is continued until deposition of the coating has progressed to the desired thickness or until the metal ions are depleted from solution. Deposition rates vary under the conditions of the present process from about 0.1 mil (1 mιl=one one-thousandth of an inch) to about 1.5 mil per hour. The preferred plating rate is about 1 mil per hour.

The preferred range of the ingredients of the plating bath comprises about .35 to about 1.57 moles per gallon nickel, about 0.0806 to about 0.0858 grams per gallon of a mixture containing thallium sulfate and thallium nitrate of as a stabilizer, preferably ions, about 0.045 to about 0.08 moles per gallon of borohydride. The ratio of nickel, boron and thallium m the present coatings can be adjusted by varying the relative amounts of the metal salt components and borohydride in the coating bath.

Under normal usage conditions of the coating baths in accordance with the present invention, a mixture containing thallium sulfate and thallium nitrate as a stabilizer, and a borohydride reducing agent are added to the coating bath every

T- ΓIΩI r nςprrfl π m flip initial preparation of the bath. The need to replenish the present coating baths with thallium salts and borohydride depends on the ratio of coating bath volume to the surface area beincr coated- Thus replenishment of thallium salts and

T- IΩ nrocpnt" r«ai — i nrr

nnl H nn+" d r~ O r i "i v ^n a11 urface areas ar^Q beincr tr^^te .

One gallon of bath prepared in accordance with the nrαf o H

a rw ϊrna pl it 1 ΔΔ c narp i n_fh c +Ό 3 -hhi nVnpcc

1 mi ^"! O ~ this result to be achieved the bath is replenished with thallium salts and borohydride in accordance with the above description as those components are depleted from solution. The pH of the coating bath will tend to drop during the

„ Cπr-_ι that it is within the preferred pH range of about 12 to about

14 T+" l^aσ bee'"¹ foim^ f ^a "I" => " ^ nh 1 <_-m c rn -t-Vi nH main o an α throughout the use of a coating bath can be minimized simDlv bv using a highly alkaline (concentrated sodium hydroxide) solution of borohydride to replenish the borohydride content of the bath as required. The coating deposition rate from the

Prps nf p] ecfroless coat inr bath i s about 0 1

i R _mi i per hour and is dependent on bath temperature, pH, and metal ion concentration. The deposition rate on most metal U sf

hat- c a +- p ni-αfαrroH temperature of about 185 to about 195° F. is approximately 1 mil per hour. The practical aspects for carrying out electroless coating processes are well known in the art. Such processes are disclosed generally in U.S. Pat. Nos. 5,109,613 issued to McComas on May 28, 1991; 3,338,726 issued to Berzms on Aug. 19, 1967; 3,096,182 issued to Berzins on Jul . 2, 1963; 3,045,334 issued to Berzins on Oct. 1, 1958; 3,378,400 issued to Sickles on Apr. 16, 1968; and 2,658,841 issued to Gutzeit and Krieg on Nov. 10, 1953; the disclosures of which are hereby incorporated by reference. The electroless nickel coatings of the present invention exhibit excellent hardness and concomitant wear resistance. They are highly ductile allowing the coating to flex with the substrate while maintaining a strong bond to the coated material. The coatings appear to be amorphous, and nonporous. The coatings are usually heat-treated. The heat treatment is accomplished at a temperature of about 375 to about 750° F. for a period of about one to about 24 hours. Shorter times, about one to two hours, is preferred at higher temperatures of between about 550-750° F. Longer heat treatment times have been shown to be advantageous at the lower temperature ranges of between about 375 to about 450° F.

The structure of the nickel/boron coating changes during heat treatment. Before heat treatment the nickel and boron appear to combine to form a alloy. After heat treatment nickel boride is formed. The coating appears to be a nickel boride dispersion within the nickel/boron alloy.

The present coatings have a wide range of applications, which will be recognized by those skilled in the art. They have particular utility for coating surfaces of articles that under normal use are subjected to highly abrasive, rubbing, or sliding conditions under high temperatures/pressures. Such high wear conditions are found at many points in the construction of tools, internal combustion engines including gas turbine engines, transmissions and m a wide variety of heavy equipment construction applications.

The following example provide details of bath compositions, process conditions, and coating compositions and properties representative of the present invention. The example is illustrative of the invention and are not m any way to be taken as limiting the scope thereof.

EXAMPLE I

A one ( 1 ) gallon batch unit of coating bath was prepared as follows. For the purposes of this example, four solutions were prepared: A (the bath), B 'the reducer , C (the stabilizer), and D 'the bath replenished . First, one-gallon batches of each solution were prepared. Solution A was made as follows; 1) 114 grams of nickel chloride, was added to a 1 gallon beaker containing a half (.5 gallon of de-ionized water 2) 227 grams of ethylenediamme was added as a complexmg agent; and 3^ 150 grams of sodium hydroxide was added to the beaker and de- ionized water was added to fill the beaker to the one gallon mark.

Solution B (the reducer¹ was made as follows: I¹ adding 1135 grams of sodium hydroxide to a half of gallon of de- ionized water; 2) allowing the solution to cool then adding 363 grams of sodium borohydride. Additional water was added to increase the level to one gallon

Solution C (the stabilizer¹' consisted of one gallon of deionized water containing 32 grams of thallium nitrate an alkaline medium. Solution D ⁽the bath replemsher) consisted of deionized water, .75 lb. of nickel chloride, 1.5 lbs. of ethylenediamme and 1.0 lb. of sodium hydroxide. This solution is added to the bath when the nickel ions in the bath drops below 70% of the original concentration.

Solution A was heated to 192°F. Two 2" x 2" X.032 panels of mild steel were degreased with a solvent (methyl ethyl ketone) The panels were grit blasted with aluminum oxide (140 grit) and placed in a solution of 35% HC1 in order to activate the parts. The panels were rinsed with de-ionized water and placed in Solution A. Just before the panels were placed into the bath for plating, 10 ml of Solution B mixed with 10 ml of Solution C were added to the heated Solution A. Ten ml of solution A is equal to .0832 grams of the thallium salt.

After 30 minutes, Solution A was titrated for the presence and amount of sodium borohydride. An additional 10 mis of

Solution B and 10 mis of Solution C, mixed together, and were added after every 30 minutes of plating. The plating continued for 3 hours .

To show the benefits of using a mixture of thallium nitrate and thallium sulfate in proper proportions, example one was repeated by replacing the thallium nitrate with different proportions of the thallium nitrate and thallium sulfate.

In example 2, 32 grams of TiSO was use as the stabilizer;

In example 3, 16 grams of TiSO, and 16 grams of TiN0₃ was used;

In example 4, 8 grams of TiS0 and 24 grams of TiNO-, was used;

In example 5, 4 grams of TiSO, and 30 grams of TiN0₃ was used; In example 6, 2 grams of TiSO, and 24 grams of TiNO; was used;

In example 7, 1 grams of TiN0₃ and 31 grams TiSO, of was used;

In example 8, 2 grams of TiN0₃ and 30 grams TiS0₄ of was used;

In example 9, 4 grams of TiN0₃ and 28 grams TiSO, of was used;

In example 10, 8 grams of TiN0₃ and 24 grams TiSO. of was used; The results of the examples show how bath stability is a function of the amounts of TiNO; and TiS0₄. Bath stability is defined as the ability to maintain a good plating rate such as

1 mill per hour and at the same time control the seeding in the

1 T bath and the thallium deposition the coating. The result of the examples are shown the table. (0) stable bath;

(-) bath slightly over stabilized, plating rate slow, about .8 m ll per hour bath, coating is acceptable.

(-) ( - ) bath over stabilized resulting m a slower plating rate about .6 mill per hour, thallium m coating increased, coating is acceptable. l - (_) ι - \ bath very over stabilized plating rate slows to about .5 mill, coating unacceptable, has little or no nodules . (^_1 (^_) ' - } { ~ unacceptable coating. (+) bath slightly under stabilized resulting m

increased plating rate of about .001 mill per hour, coating ι^c good.

(+ ) '+ ) bath slightly under stabilized resulting in slightly fast plating rate of about .0013 bath tends to decompose but can recover by adding more stabilizer, coating is acceptable. (+ ) ' + Ϊ '-<-) bath very under stabilized resulting m fast plating rate causing nickel to seed out, coating is unacceptable acceptable. * seed σ

TABLE

30MIN 60MIN 90MIN 120MIN 150MIN 180MIN

These examples were run with the. operator increasing or decreasing the amount of stabilizer in the bath to compensate for over stability or under stability. Example 2 illustrates the addition of stabilizer to adjust the stability of the bath. After 60 minutes the bath starts to become over stabilized requiring a cutback in the amount of stabilizer to be added. This causes the bath to become slightly under stabilized. After 150 minutes even with adjustments to the bath becomes so over stabilized that the coating become unstable. This example shows that the bath stability is difficult to maintain because of the tendency of the bath to swing back and forth. In contrast, examples 6-9 show a more stable bath. The tendency of the bath to have dramatic swings back and forth between over and under stability is minimized. Therefore the baths shown in examples 6-9 are more easily controlled and provide a more stable bath as the bath ages. ι ς The desired plating rate is 0.001 nch per hour. Achieving this optimum plating rate requires adjusting the amount of the stabilizer so that the bath does not seed out by plating too fast or becomes over stabilized thereby resulting too much thallium co-deposited m the nickel coat and a reduction m plating rate.

When the amount of stabilizer is low the plating speed increases causing bath decomposition or seed out. The nicke] plates itself, forms small particles and drops to the bottom of the bath. Too much stabilizer slows the plating rate. This condition results m an unacceptable coating having nodules that are flat or nonexistent. By using a mixture containing thallium sulfate and thallium nitrate as the stabilizer one can maintain the desired plating rate over a longer time period as the bath ages m contrast to the prior art.

Example 7, which gave the best result, was used to establish a concentration range for the mixture containing thallium sulfate and thallium nitrate m the bath. Example 7 was modified by varying the number of ml of solution C added to the bath. Example 10, repeated example 7, using 8 ml of solution C. The bath was stable for the first 90 minutes and for the next 60 minutes the bath became less stable but was still able to produce an acceptable coating. After 150 minutes the bath became unstable and the coating became unacceptable. Example 11, repeated example 7, using 6 ml of solution C. The bath was stable for the first 30 minutes and for the next 30 minutes the bath became seedy and very dark. After 60 minutes the bath became too unstable.

Example 12, repeated example 7, using 12 ml of solution C. The coating was acceptable for 120 minutes but then the concentration of thallium in the coating became two high causing a significant decrease m the hardness of the coating. Plating stopped after 150 minutes, the bath had become over stabilized.

Example 13, repeated example 7, using 14 ml of solution C. After 30 minutes the concentration of thallium the coating became tv o high causing a significant decrease in the hardness of the coating. The plating rate dropped to 0.0002 inch per hour. A plating rate of 0.001 inch per hour was desired. Plating stopped after 90 minutes.

These examples show that the mixture containing thallium sulfate and thallium nitrate in the bath should range between about 19.2 grams per gal and 44.8 per gal, preferably, between about 25.6 grams per gal and 38 grams per gal, and more preferably between about 25.6 grams per gal and 34 grams per gal. The best results would most likely fall between about 0.0806 and .0858 grams per gallon of the mixture.

With respect to the above description then, it is to be realized that the optimum proportions, process steps, and ingredients of the invention, to include variations in size, materials, shape, form, function and manner of operation, assembly and use, are deemed readily apparent and obvious to one skilled in the art, and all equivalent relationships to those described in the specification are intended to be encompassed by the present invention.

Therefore, the foregoing is considered as illustrative only of the principles of the invention. Further, since numerous modifications and changes will readily occur to those skilled in the art, it is not desired to limit the invention to the exact construction and operation shown and described, and accordingly, all suitable modifications and equivalents may be resorted to, falling within the scope of the invention. Now that the invention has been described.

Claims

CLAIMS What is claime is:

1. A coating bath for providing a hard, wear and corrosion resistant, ductile coating on a substrate, said bath having a pH of about 10 to about 14 and comprising

(1) about 0.175 to about 2.10 moles per gallon of coating bath of nickel ions:

(2) about 0,0508 to about 0.11872 grams per gallon of a mixture containing thallium nitrate and thallium sulfate as a stabilizer wherein the percentage of thallium nitrate in the mixture is less than 50% of the combined weight of the thallium nitrate an thallium sulfate

(3) an effective amount of metal ion complexing agent in an amount sufficient to inhibit precipitation of said metal ions from the coating bath; and

(4) an effective amount of a borohydride reducing gent -

?. The coating bath of claim 1, wherein the metal ion complexing agent is selected from the group of water soluble salts of tartaric acid, citric acid, oxalic acid, ethyl enedi ami ne. di ethyl enetri mi ne, tri ethyl nefri ami ne, ethyl enedi ami ne tetraacetic acid and ammonia .

3. The coating bath of claim 1, wherein the metal ion complexing agent is ethyl enedi ami n .

4. The coating bath of claim 6 wherein the borohydride reducing agent is selected from the group consisting of sodium borohydride, potassium borohydride, sodium trimethoxvborohvdri e, and notassium fri ethoxvborohvdr i de .

5. The coating bath of claim 1 wherein the borohydride reducing agent is sodium borohydride.

6. The coating bath of claim 5 wherein the borohydride concentration is about .05 to about .1 moles per gallon.

7. The coating bath of claim 1 wherein from about 2.26 to abou+^~ 6.795 moles of metal ion complexing compound per gallon of coating bath.

8. Th^Q c aling ba+-p of claim 1 wherein the nickel ion concentration is about 0.35 to about 1.57 moles p^Qr gallon.

9. The

about 0.10176 grams per gallon of a mixture containing thallium and thallium sulfate as a stahi 1 i 7 i"

10. The coating bath of claim 9 containing about 0.0806 to about 0.0858 grams per gallon of a mixture containing thallium nitrate and thallium sulfate as a stabilizer.

11. The coating bath of claim 1 wherein the percentage of thallium nitrate the mixture is between about 3% to about 38% of me combined weight of thallium nitrate and thallium sulfate .

12. The coating bath of claim 11 wherein the percentage of thallium nitrate m the mixture is between about 3% to about 10% of the combined weight of thallium nitrate and thallium sulfate .

13. The coating bath of claim 12 wherein the percentage of thallium nitrate m the mixture is between about 5% to about 7% of the combined weight of thallium nitrate and thallium sulfate .

14. The coating ba+"h of claim 9 wherein the percentage of thallium nitrate m the mixture is between about 3% to about 38% the combined weight of thallium nitrate and thallium sulfate.

15. The coating bath of claim 9 wherein the percentage of thallium nitrate in the mixture is between about 3% to about 10% the combined weight of thallium nitrate and thallium sulfate .

16. The coating ba^h of claim 9 wherein the percentage of thallium nitrate m the mixture is between about 5% to about 7% of the combined weight of thallium nitrate and thallium sulfat .

17. The coating bath of claim 10 wherein the percentage of thallium nitrate m the mixture is between about 3% to about 38% of the combined weight of thallium nitrate and thallium sulfate.

18. The coating bath of claim 10 wherein the percentage of thallium nitrate the mixture is between about 3% to about 10% of the combined weight of thallium nitrate and thallium sulfate.

19. The coating bath of claim 10 wherein the percentage of thallium nitrate m the mixture is between about 5% to about 7% of the combined weight of thallium nitrate and thallium sulfate

20. A concentrate containing about 28 to about 37 grams per gallon of mixture containing thallium sulfate and thallium nitrate, wherein the percentage of thallium nitrate in the mixture is less than 50% of the combined weight of the thallium nitrate and thallium sulfate.

21. A concentrate according to claims 20 wherein the mixture contains about 31 to about 33 grams per gallon of a thallium nitrate and thallium sulfate.

22. A concentrate according to claims 20 wherein the percentage r> -f ^hallium. nitrate in the mix'*^~ι"^{, Ω} is between about 3% to about 38% of the combined weight of thallium nitrate and thallium sulfate -

23. A concentrate according to claim 22 wherein the percentage nf ^hallium. nitrate in the i "*^_'^,ιr is bet e n _^Hnn⁴- 3° ^^~~' about 10% of the combined weight of thallium nitrate and thallium sulfate -

24. A concentrate according to claim 22 wherein the percentage of thallium nitrate in the mixture is between about 5% to about 7% of the combined weight of thallium nitrate and thallium sulfate -

25. A concentrate according to c aims 21 wherein the percentage of thallium, nitrate in the mix''-^ιιr^Ω is hofuoαn aKnnt- ^2. +-r< about 38% of the combined weight of thallium nitrate and thallium sulfate -

26. A concentrate according to claims 21 wherein the percentage of thallium nitrate in the mixture is between about 3% to about 10% of the combined weight of thallium nitrate and thallium sulfate .

27. A concentrate according to claims 26 wherein the percentage of thallium nitrate the mixture is between about 5% to about 7% of the combined weight of thallium nitrate and thallium snlfatβ-

28. A concentrate according to claims 20 having a pH of at

1 a p ; ^^~

29. A process of electrolessly coating an article using the composition of claim 1.

30. The composition se^t- forth m claim 1 formed by mixing ingredients 1), 2), 3), and ^ .

01