Patent Grant
9376755
Described herein is a method and corresponding composition of matter for improved cobalt-boron and nickel-boron electroless plating baths.
Cobalt-boron and nickel-boron plating baths have been in use since Talivaldis Berzins filed the first U.S. patent application on this type of process on Oct. 1, 1958, which matured into U.S. Pat. No. 3,096,182, issued Jul. 2, 1963. Conventional plating baths are generally used for making depositions on iron and iron alloy substrates. Most of these plating baths use sodium borohydride (NaBH4) as the source of boron. The Berzins patent and others typically recite process temperatures of from 60° C. to 100° C., at pH's of about 12 to 13 or higher. Baths of this type deposit nickel-boron or cobalt-boron alloys with a boron content of 3.5% to 6.0%. As a result, the coatings are very hard. They are used extensively on gun barrels and in many applications requiring a hard, scratch-resistant surface. Since the Berzins patent, a number of improvements have been patented, but there has been a strict adherence to maintaining the bath at a pH of from 12 to 14, and at temperatures of no less than 60° C. These conventional reaction conditions are echoed in the standard text on electroless nickel deposition techniques, “Electroless Plating Fundamentals and Applications,” G.O. Mallory and J. B. Hajdu, eds., ©1991 William Andrew Press, ISBN 978-0815512776. The high pH is required to prevent the decomposition of the borohydride. The conventional elevated temperature range is required to achieve an acceptably fast deposition rate. Iron and its alloys exhibit passivity at a high pH which counteracts the deposition. Additionally, absent adding catalysis to the bath (such as thallium and/or organic sulfur compounds) the maximum observed deposition rate is only about 0.0001 inch (2.54 μm) per hour at over 90° C. (See Mallory & Hajdu, supra, at page 82.). Thallium, however, is quite toxic and also plates out with the deposited nickel or cobalt. The co-deposited thallium imparts undesirable physical and chemical properties to the ultimate coating, as lower hardness, increased brittleness, and lower corrosion resistance.
To obtain a higher rate of deposition and a coating free of impurities introduced via a catalyst, amine-boranes came into use in the late 1960's. See U.S. Pat. No. 3,338,726, issued Aug. 29, 1967 to Berzins. The resulting deposited coatings contain less than 3.5% boron, deposit at higher rates, rate, may be used at temperatures as low as 40° C. and are conventionally used at pH's of about 6.0 to 9.5. The more mild deposition conditions also allow these types of baths to deposit onto aluminum and aluminum alloy substrates. They are used extensively in the electronics industry because the deposits may be soldered. However, due to the high cost of the amine-boranes, the baths are much more expensive to use. There are also adverse environmental issues associated with their use.
Disclosed and claimed herein are methods and corresponding compositions for improved electroless nickel-cobalt-boron plating. In the method, any soluble borohydride salt may be used with the preferred salt being sodium borohydride. Other suitable salts include lithium borohydride, potassium borohydride, and the like.
More specifically, the method comprises operating the plating bath at temperatures in the range of from about 60° F. to about 110° F. (about 15.5° C. to about 43.3° C.) with the preferred temperature being about 70° F. (about 21.1° C.) and in a pH range of about 10.5 to about 11.5 with the preferred pH being about 11.2. This pH range significantly reduces the passivity of iron and iron alloy substrates. The low temperature range significantly increases the stability of the borohydride salt being used. The borohydride concentration is maintained in the range of from about 0.100 to about 1.5 grams per liter of water with the preferred initial concentration being about 0.700 grams per liter of water.
Stabilization agents to prevent the nickel or cobalt from forming boride or hydroxide precipitates include a sufficient amount ammonia to form the corresponding ammonia cobalt- and/or ammonia nickel-coordinated complexes (optional) and a sufficient amount of an amino acid as defined herein. The amount of added stabilization agent should be sufficient to coordinate with the cobalt and/or nickel present in the bath to prevent precipitation when the plating bath is adjusted to the final pH. (Typically, the pH is pushed upward by adding alkali metal hydroxides to the plating bath.)
Any soluble nickel-containing or cobalt-containing salt may be used as long as the salt has no adverse effect upon the operation of the plating bath. The preferred nickel or cobalt salt being a halide; chloride is most preferred. The preferred concentration of the salt preferably yields a metal concentration of between about 0.02 to about 10.0 grams of nickel or cobalt per liter of plating bath.
The plating baths are constructed by dissolving the nickel or cobalt salts in mineral-free water, adding the ammonia (if used), then dissolving the amino acid in the bath. The preferred amino acid is glycine. The pH is then adjusted to the desired level. This can be done by any means now known or developed in the future. Typically this is done by adding an alkali metal hydroxide to the plating bath. The preferred alkali metal is potassium. The solution is the stirred to dissolve any nickel or cobalt hydroxides initially generated by adding the alkali metal hydroxide. The solution is then filtered to remove any precipitates. The borohydride is dissolved in an alkaline, aqueous solution and added to the bath. This procedure is followed to inhibit any initial rapid decomposition of the borohydride. Over the course of the reaction, the borohydride is consumed. As the borohydride in the bath is consumed, more is added, again dissolved in an aqueous, alkaline solution. As a general proposition, more than about 1.5 grams of borohydride per liter of solution will cause decomposition of the bath. Borohydride concentrations less than about 0.1 gram per liter are generally too low to give economical reduction rates of the nickel and cobalt ions.
Thus, disclosed and claimed herein is an electroless plating bath composition. The composition comprising an an aqueous solution including an amino acid having at least one amino moiety and at least one carboxylic acid moiety or a polypeptide thereof, having a molar ratio of amino moieties to carboxylic acid moieties of 1 or greater; a nickel-containing or a cobalt-containing salt; and a boron-containing reducing agent.
The amino acid may be a molecule consisting of one (1) amino acid moiety and one (1) carboxylic acid moiety or the the amino acid may be is selected from the group consisting of alpha-amino acids and beta-amino acids. Preferred amino acids include, but are not limited to alanine, asparagine, arginine, cysteine, glutamine, glycine, histidine, isoleucine, lysine, leucine, phenylalanine, methionine, serine, proline, tryptophan, threonine, tyrosine, valine, pyrrolysine, and ornithine.
The boron-containing reducing agent preferably comprises a borohydride, such as sodium borohydride, lithium borohydride, or potassium borohydride.
Also disclosed herein is a process for depositing a nickel-boron or cobalt-boron coating on a substrate, typically a metallic substrate. The method comprises creating a galvanic cell on a surface of a metallic substrate and then contacting the metallic substrate with a plating bath as described hereinabove, wherein an electroless deposition reaction results, yielding a nickel-boron or cobalt-boron coating on the metallic substrate.
As used herein, the term “amino acid” means any compound, without limitation, that comprises at least one amino moiety and at least one carboxylic acid moiety, with the proviso that the molar quantity of amino moieties is equal to or greater than the molar quantity of carboxylic acid moieties, whether natural or unnatural, as well as polypeptides comprised of amino acids. That is, the molar ratio of amino groups to carboxylic acid groups in an “amino acid” as that phrase is defined herein must be 1 or greater. The amino moiety and carboxylic acid moiety need not be at the termini of the molecule. Thus, as used herein, the term “amino acid,” explicitly encompasses natural and unnatural alpha amino acids, such as alanine, asparagine, arginine, cysteine, glutamine, glycine, histidine, isoleucine, lysine, leucine, phenylalanine, methionine, serine, proline, tryptophan, threonine, tyrosine, valine, pyrrolysine, ornithine, N-alkyl derivatives of the foregoing, and the like. The term “amino acid” also includes beta, gamma, and delta amino acids, and longer derivatives (i.e., β3 and β2 amino acids), homo-amino acids, proline and pyruvic acid derivatives, 3-substituted alanine derivatives, glycine derivatives, ring-substituted phenylalanine and tyrosine derivatives, linear core amino acids, diamino acids, D-amino acids, etc. The term “amino acid” also includes polypeptides comprising one or more amino acids as that term is defined herein, linked by peptidic bonds. Monomeric amino acids are generally preferred. A huge number of amino acids, natural and unnatural, are available commercially from numerous suppliers, such as Sigma-Aldrich (St. Louis, Mo.). The phrase “amino acid” excludes aspartic acid and glutamic acid because they have a molar quantity of carboxylic acid moieties larger than the molar quantity of amino groups (i.e., two carboxylic acid moieties per each amino moiety).
“Substrate” means any substrate, metallic or otherwise, susceptible to electroless plating as described herein, and explicitly including iron and its alloys, aluminum and its alloys, such as mild steel (i.e., low-carbon steels), carbon steels, aluminum alloys such as 6061 and other precipitation hardening aluminum alloys, titanium and its alloys, magnesium and its alloys, etc.
Numerical ranges as used herein are intended to include every number and subset of numbers contained within that range, whether specifically disclosed or not. Further, these numerical ranges should be construed as providing support for a claim directed to any number or subset of numbers in that range. For example, a disclosure of from 1 to 10 should be construed as supporting a range of from 2 to 8, from 3 to 7, from 1 to 9, from 3.6 to 4.6, from 3.5 to 9.9, and so forth.
All references to singular characteristics or limitations of the present invention shall include the corresponding plural characteristic or limitation, and vice-versa, unless otherwise specified or clearly implied to the contrary by the context in which the reference is made.
All combinations of method or process steps as used herein can be performed in any order, unless otherwise specified or clearly implied to the contrary by the context in which the referenced combination is made.
The methods of the present invention can comprise, consist of, or consist essentially of the essential elements and limitations of the method described herein, as well as any additional or optional ingredients, components, or limitations described herein or otherwise useful in synthetic organic chemistry.
The present inventor has found that amino acids having a ratio of amino moieties to carboxylic acid moieties of one (1) or greater are highly effective stabilization agents for nickel-boron and cobalt-boron electroless plating. Nickel-boron and cobalt-boron plating baths comprising an amino acid enable lower temperature electroless plating with excellent coating results and without the co-deposition of additional, unwanted metallic species. The method and plating baths disclosed are most easily described by representative examples. Note that the examples are representative and for illustrative purposes only. The examples do not limit the scope of the claims in any fashion.
The following examples illustrate the process when used on a steel substrate (i.e., an iron alloy substrate) and an aluminum substrate. In all of the examples using a steel substrate, mild steel pieces 1 inch×3 inch×0.125 inches thick (2.54 cm×7.62 cm×3.175 mm) was employed. Each substrate was first cleaned in a strong alkaline cleaner, rinsed in mineral-free water, and then dipped in a copper sulfate solution for few seconds to deposit a small amount of copper on the surface. The deposited copper creates a galvanic cell on the surface of the metal to initiate the electroless deposition process. The steel substrates were then rinsed in mineral-free water, then in an aqueous ammonia solution (pH 11.0), and immediately placed in the plating bath. Examples using aluminum substrates used 6061 aluminum. See the examples for additional details.
A mild steel sample, prepared as indicated above, was placed in a plating bath comprising:
A mild steel sample, prepared as indicated above, was placed in a plating bath comprising:
A mild steel sample prepared as indicated above was placed in a plating bath comprising:
A mild steel sample, prepared as indicated above, was placed in a plating bath comprising:
A mild steel sample, prepared as indicated above, was placed in a plating bath comprising:
A mild steel sample, prepared as indicated above, was placed in a plating bath comprising:
A mild steel sample, prepared as indicated above, was placed in a plating bath comprising:
A mild steel sample, prepared as indicated above, was placed in a plating bath comprising:
A mild steel sample, prepared as indicated above, was placed in a plating bath comprising:
A mild steel sample, prepared as indicated above, was placed in a plating bath comprising:
A mild steel sample, prepared as indicated above, was placed in a plating bath comprising:
The solution was maintained at 70° F. (21.11° C.) on a thermostat-controlled hot plate. Almost immediate decomposition of the sodium borohydride resulted.
A mild steel sample, prepared as indicated above, was placed in a plating bath comprising:
A mild steel sample, prepared as indicated above, was placed in a plating bath comprising:
A 1 inch×3 inch×0.125 inch (2.54 cm×7.62 cm×3.175 mm) piece of 6061 alloy aluminum was cleaned and prepared as per ASTM B253 (“Standard Guide for the Preparation of Aluminum Alloys for Electroplating”) for non-zincate electroless nickel applications and then placed in a bath comprising:
A 1 inch×3 inch×0.125 inch (2.54 cm×7.62 cm×3.175 mm) piece of 6061 alloy aluminum was cleaned and prepared as per ASTM B253 for non-zincate electroless nickel applications and then placed in a bath comprising:
In addition to aluminum and its alloys, other light metals may be plated with the cobalt-boron and nickel-boron compositions described herein.
A 1 inch×3 inch×0.125 inch (2.54 cm×7.62 cm×3.175 mm) piece of AZ91D magnesium alloy was lightly glass bead blasted to remove an outer layer of oxide. (AZ91D is a well known and widely used magnesium alloy; it is used extensively for die casting metallic parts.) The piece was then placed in an aqueous, boiling 5% potassium hydroxide solution for two minutes, rinsed in mineral-free water and then placed in a dispersion of various polyamines and polyamides and made the anode of an electrochemical cell with the cathode being a 316 alloy stainless steel plate at about 15 amps per square foot for about three seconds. The substrate was then rinsed in a 1% aqueous ammonia solution to remove any polyamines or polyamides not chemically bounded to the substrate, rinsed in mineral-free water, and then placed in the following bath:
A 1 inch×3 inch×0.125 inch (2.54 cm×7.62 cm×3.175 mm) piece of AZ91D magnesium alloy was lightly glass bead blasted to remove an outer layer of oxide. (AZ91D is a well known and widely used magnesium alloy; it is used extensively for die casting metallic parts.) The piece was then placed in an aqueous, boiling 5% potassium hydroxide solution for two minutes, rinsed in mineral-free water and then placed in a dispersion of various polyamines and polyamides and made the anode of an electrochemical cell with the cathode being a 316 alloy stainless steel plate at about 15 amps per square foot for about three seconds. The substrate was then rinsed in a 1% aqueous ammonia solution to remove any polyamines or polyamides not chemically bounded to the substrate, rinsed in mineral-free water, and then placed in the following bath.
A 1 inch×3 inch×0.063 inch (2.54 cm×7.62 cm×1.6 mm) piece of Ti-6V titanium alloy was lightly glass bead blasted to remove an outer layer of oxide. The substrarte was then placed in an aqueous, boiling 5% potassium hydroxide solution for two minutes, rinsed in mineral-free water, and acid etched to remove the titanium oxides. The substrate was then rinsed in mineral-free water and placed in a polyamine/polyamide dispersion and made the anode for about three seconds. Excess polyamines and polyamines not bonded to the metal substrate were removed by rinsing in a 1% aqueous ammonia solution. The substrate was rinsed again in mineral-free water and placed in the following bath:
A 1 inch×3 inch×0.063 inch (2.54 cm×7.62 cm×1.6 mm) piece of Ti-6V titanium alloy was lightly glass bead blasted to remove an outer layer of oxide. The substrarte was then placed in an aqueous, boiling 5% potassium hydroxide solution for two minutes, rinsed in mineral-free water, and acid etched to remove the titanium oxides. The substrate was then rinsed in mineral-free water and placed in a polyamine/polyamide dispersion and made the anode for about three seconds. Excess polyamines and polyamines not bonded to the metal substrate were removed by rinsing in a 1% aqueous ammonia solution. The substrate was rinsed again in mineral-free water and placed in the following bath:
| Number | Name | Date | Kind |
|---|---|---|---|
| 3096182 | Berzins | Jul 1963 | A |
| 3338726 | Berzins | Aug 1967 | A |
| 4407869 | Mallory | Oct 1983 | A |
| 5258061 | Martyak | Nov 1993 | A |
| 5269838 | Inoue | Dec 1993 | A |
| 5718745 | Itoh | Feb 1998 | A |
| 20040235237 | Inoue | Nov 2004 | A1 |
| 20070066059 | Chen | Mar 2007 | A1 |
| 20080254205 | Petrov | Oct 2008 | A1 |
| 20120156387 | Stark | Jun 2012 | A1 |
| Number | Date | Country |
|---|---|---|
| 2270255 | Jan 2011 | EP |
| 785695 | Nov 1957 | GB |
| WO 2011003116 | Jan 2011 | WO |
| Number | Date | Country | |
|---|---|---|---|
| 20140353160 A1 | Dec 2014 | US |
