U.S. patent number 3,833,486 [Application Number 05/345,041] was granted by the patent office on 1974-09-03 for cyanide-free electroplating.
This patent grant is currently assigned to Lea-Ronal, Inc.. Invention is credited to Fred I. Nobel, Lazaro C. Yoen.
United States Patent |
3,833,486 |
Nobel , et al. |
September 3, 1974 |
CYANIDE-FREE ELECTROPLATING
Abstract
Improved cyanide-free aqueous electroplating baths for plating
metals, the baths containing water soluble phosphonate chelating
agents combined with at least one chelatable metal ion and
containing as an additive at least one strong oxidizing agent, and
electroplating processes employing said baths. Additional materials
may also be added for further improvements.
Inventors: |
Nobel; Fred I. (Roslyn, NY),
Yoen; Lazaro C. (Brooklyn, NY) |
Assignee: |
Lea-Ronal, Inc. (Freeport,
NY)
|
Family
ID: |
23353213 |
Appl.
No.: |
05/345,041 |
Filed: |
March 26, 1973 |
Current U.S.
Class: |
205/291; 205/238;
205/240; 205/242; 205/245; 205/252; 205/263; 205/271; 205/277;
205/281; 205/297; 205/300; 205/305; 205/313; 205/239; 205/241;
205/244; 205/246; 205/255; 205/269; 205/270; 205/274; 205/279;
205/296; 205/298; 205/302; 205/311 |
Current CPC
Class: |
C25D
3/38 (20130101); C25D 3/02 (20130101) |
Current International
Class: |
C25D
3/38 (20060101); C25D 3/02 (20060101); C23b
005/02 (); C23b 005/18 (); C23b 005/46 () |
Field of
Search: |
;204/43,44,45R,46,47,48,49,5R,51,52R,53,54R,54L,55R |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Other References
Frederick A. Lowenheim, "Modern Electroplating," pp. 178-185 &
293-294, (1968), TS 670 E46 C.2..
|
Primary Examiner: Kaplan; G. L.
Attorney, Agent or Firm: Rosen; Lawrence Berry; E. Janet
Claims
What is claimed is:
1. In a process for producing deposits of metal which comprises
electrodepositing metal from a cyanide-free aqueous solution
containing an effective amount of a complex formed of a water
soluble phosphonate chelating agent and at least one chelatable
metal ion of a metal to be electrodeposited and capable of
producing electrodeposits, the improvement which comprises
including in the electroplating solution from about 0.01 to about
5.0 g/l of at least one oxidizing agent selected from the group
consisting of peroxides, chlorites, perchlorates, hypochlorites,
permanganates and sulfoxides.
2. The process according to claim 1 in which the metal undergoing
electrodeposition is selected from the group consisting of iron,
cobalt, nickel, zinc, silver, copper, cadmium and tin.
3. The process of claim 2 in which the metal undergoing
electrodeposition is copper.
Description
This invention relates broadly to the electroplating of metals and
metal alloys from cyanide-free aqueous plating baths. More
specifically, this invention relates to improved cyanide-free
aqueous electroplating baths containing a stable metal chelate
formed from a water soluble phosphonate chelating agent combined
with at least one chelatable metal ion and containing as an
additional additive at least one strong oxidizing agent. It is also
contemplated to add certain other selected classes of materials to
the improved baths in order to achieve further advantageous
results.
It is one object of this invention to provide improvements in
cyanide-free plating baths for electroplating metals.
It is another object to add strong oxidizing agents to
electroplating baths to improve the brightness characteristics of
the metal deposits therefrom.
It is a further object to improve the life of phosphonate
chelate-containing, cyanide-free electroplating baths by the
addition thereto of at least one strong oxidizing agent and, as an
additional feature, other property-improving additives.
Other and further objects of the invention will become apparent
from the more detailed description of the invention set forth
below.
Alkaline electroplating baths containing cyanides are widely used
in industrial metal electroplating operations for the plating of
certain metals. For many applications these cyanide-containing
baths produce excellent results. The conventional electroplating
baths consist essentially of aqueous alkaline solutions of the
cyanide salt of the metal to be electrodeposited. In addition to
these salts, additives may be included to improve the quality of
the electro-deposits obtained therefrom. These additives can be
used to produce grain refining, brightness, improve the bright
plating range, or in general to impart desirable characteristics to
the deposit or the operation of the bath. Typical examples of
commonly employed additives are aromatic alkyl sulfonates which
improve the luster of the plated metal surface and increase the
uniformity of the plating baths to increase the amount of plating
current density -- and hence plating speed -- which may be utilized
without a roughening or "burning" of the plated surface. Further
additives are employed to improve the "throwing power" of the
electroplating bath, i.e., the ability of the bath to deposit a
uniform thickness of plating metal in the recesses of a base metal
object.
While excellent results can be obtained by using the above
described cyanide-containing baths, the extreme toxicity of these
solutions as the result of the presence of large quantities of
cyanide presents disadvantages and makes their use undesirable. In
addition to the inherent health hazards to personnel in the
vicinity of the plating solution, a further problem is created by
the need to destroy all of the cyanide before it is allowed to
enter any stream or sewer system. The presence of even trace
amounts of these chemicals in streams or sewers presents a severe
health hazard and highly dangerous pollution problem. The chemical
destruction of cyanides, on the other hand, is both cumbersome and
expensive. Also, if the pH of an alkaline cyanide plating bath
inadvertently becomes neutral or acidic, lethal hydrogen cyanide
gas may form, creating a distinct hazard to all those in the
vicinity.
Alkaline pyrophosphate electroplating baths are also in use today.
These baths, however, have been found to be extremely sensitive to
organic contamination and require periodic dilutions as the
concentration of orthophosphate in the bath increases due to the
hydrolysis of the pyrophosphate ion. Thus, the effective
concentrations in the bath at any one time may be somewhat
uncertain.
Attempts to overcome the difficulties described in cyanide
electroplating and other above mentioned plating baths while
retaining the advantages thereof have been made. For instance,
electroplating solutions have been developed which contain a salt
of the metal which is to be deposited and a phosphonic acid
derivative as the chelating agent for the metal to be plated. Such
plating solutions are described in French Pat. No. 1,458,492 to
Monsanto Co. and in U.S. Pat. No. 3,475,293 to Haynes and Langguth
assigned to Monsanto Co. as well as in copending U.S. application
Ser. No. 825,067 of Nobel and Ostrow, assigned to Lea-Ronal, Inc.,
now abandoned. These patents describe electroplating baths
containing a complex consisting of a divalent metal ion and an
organophosphorous ligand of the formula: ##SPC1##
where n is an integer of from 2 to 3, incl., M is a member selected
from the group consisting of a hydrogen ion, ammonium, lower alkyl
amine or an alkali metal cation and Z is a connecting radical equal
in valence to n and containing not more than about 12 carbon atoms
exclusive of hydrogen in chemical combination and is selected from
the group consisting of (1) an aliphatic radical (2) an
N-substituted aliphatic radical containing from 2 to 3 alkyl groups
in which the connecting radical has a carbon atom linked to a
phosphorus atom in the ligand.
In addition, polyamine phosphonate compounds are described in
aforementioned U.S. Pat. application Ser. No. 825,067 in
conjunction with electroplating baths containing in addition to the
polyamine phosphonate, a chelatable metal ion.
Initially, the cyanide-free baths prepared in accordance with these
improved processes of the prior art patents and the patent
application aforementioned are semibright to lustrous. However,
these so-called improved electroplating solutions are not
commercially practicable because as the electroplating process
proceeds, the metallic deposit tends to become continually duller
and more granular, particularly in the low current density
areas.
For example, 267 ml. of the following plating solution was prepared
1 - hydroxyethylidene diphosphonic acid 180 g/l Copper metal as the
hydroxide 15 g/l Ethylenediamine tetramethylphosphonic acid 4 g/l
Potassium hydroxide to pH 10.3
The resulting solution was electrolyzed for 5 minutes at 1 ampere.
The deposit was uniformly lustrous or semibright. However,
continued electrolysis for an additional 120 ampere minutes (1
ampere for 120 minutes) the deposit became dull and granular,
particularly in the low current density areas. This plating
solution is therefore entirely impractical for commercial
electroplating operations, since it has very short life for
producing satisfactory results in terms of the metallic films
deposited therefrom.
It has now been found that oxidizing agents may be used with the
water soluble phosphonate chelating agents to alleviate the problem
of poor luster. Their use results in a greatly improved deposit. In
general it has been found that the stronger oxidizing agents such
as the peroxides, chlorites, perchlorates, hypochlorites,
permanganates, sulfoxides, and the like are most beneficial. In
particular, it was found that chlorites are long lived as effective
additives to the solutions and give superior results. The
improvement caused by the addition and periodic replenishment of
the oxidizing agents makes the chlorite containing bath a practical
plating bath. Particularly useful compounds include:
N-bromosuccinamide Potassium peroxymonosulfate N-chlorosuccinamide
Ammonium persulfate Chloroperbenzoic acid Sodium or potassium
perborate Dimethyl sulfoxide Sodium chlorite Perbenzoic acid Sodium
hypochlorite Potassium periodate Hydrogen peroxide Peracetic acid
Potassium permanganate Permaleic acid Potassium perchlorate
Pyridine N-oxide Potassium peroxydiphosphate
Also useful are certain inorganic high energy oxidizers such as the
fluoronitrogen compounds examples of which are nitrogen
trifluoride, difluorodiazine, tetrafluorohydrazine, difluoramine,
chlorodifluoroamine, and fluorine and fluorohalogen compounds
including chlorine trifluoride and derivatives, chlorine
pentafluoride, chlorine fluoride oxides, oxygen fluorides and
related compounds, and chlorine oxides and related compounds.
The amount of the selected oxidizing agent required varies somewhat
with the particular oxidizing agent selected to be used and the
amount of electrolysis the bath has undergone. Sufficient oxidizing
agent is used to overcome the bad effects produced by continuation
of electrolysis. The amount of sodium chlorite, the preferred
material, required is about 0.25 g/l in most baths. The range of
use for the oxidizing agents is from about 0.01 g/l up to about 5
g/l, but in all cases the minimum amount necessary to produce good
results should be employed. The amount required can readily be
determined by a Hull cell test, which is a plating test cell used
by all plating laboratories.
Examples of chelating agents which may be used as the basic
ingredient of these baths include diethylene triamine
pentamethylphosphonate acid, triethylene tetramine
hexamethylphosphonate acid, tetraethylene pentamine
heptamethylphosphonate acid and their alkali metal or ammonium
salts. Further examples of useful chelating agents are ethylene
diamine tetramethylphosphonic acid, hexamethylene diamine
tetramethylphosphonic acid, aminoethyl ethanolamine
trimethylphosphonic acid, aminoethyl piperazine trimethylphosphonic
acid, diamino pyridine tetramethylphosphonic acid, and their alkali
metal or ammonium salts. Chelating agents also useful are hydrazine
tetramethylphosphonic acid and its alkali metal or ammonium
salts.
In the hereinbefore described formula I for the organophosphorus
ligand when Z is an aliphatic radical containing from one to 12
carbon atoms the ligand will preferably have the formula:
##SPC2##
wherein X is selected from hydrogen, hydroxyl or a lower alkyl
group containing from about one to about four carbon atoms and Y is
a member selected from the group consisting of hydrogen, hydroxyl
and lower alkyl containing from about one to about four carbon
atoms, and M is as hereinbefore described.
In the above formula I when Z is an N-substituted aliphatic
connecting radical containing 3 alkyl groups the organophosphorus
ligand will have the formula: ##SPC3##
where X, Y and M are as hereinbefore described.
Compounds falling within the scope of the foregoing general formula
include aminotri(lower alkylidene phosphonic acid) compounds and
specific compounds falling therein include, for example,
aminotri(methylene phosphonic acid), aminotri(ethylidene phosphonic
acid), aminotri(isopropylidene phosphonic acid), aminodi(methylene
phosphonic acid), mono(ethylidene phosphonic acid),
aminodi(methylene phosphonic acid) mono(isopropylidene phosphonic
acid), aminomono(methylene phosphonic acid) di(ethylidene
phosphonic acid), aminomono(methylene phosphonic acid)
diisopropylidene phosphonic acid and the like.
Lower alkylidene diphosphonic acid compounds falling within the
scope of the above general formula include methylene diphosphonic
acid, ethylidene diphosphonic acid, isopropylidene diphosphonic
acid, 1-hydroxyethylidene diphosphonic acid, 1-hydroxypropylidene
diphosphonic acid, butylidene diphosphonic acid and the like.
As stated hereinbefore M in the above formula may be among others,
a hydrogen ion or an alkali metal cation. It is preferred that M be
an alkali metal cation such as sodium, potassium and lithium.
Particularly preferred organophosphorus ligands employed in the
form of a divalent transitional metal ion complex include for
example, pentapotassium amino(trimethylene phosphonate),
tetrapotassium 1-hydroxyethylidene diphosphonate, pentasodium
aminotri(methylene phosphonate), tetrasodium 1-hydroxyethylidene
diphosphonate.
The plating baths of the present invention may be prepared for
instance by forming an aqueous solution of a suitable metal
compound and a phosphonate chelating agent of the present
invention. Another method for preparing the baths disclosed herein
is to form an aqueous mixture of a metal chelate salt which has
been previously prepared, e.g., by the reaction of a chelatable
metal carbonate, hydroxide or oxide with a phosphonic acid of the
present invention, then neutralizing and adjusting the pH with a
suitable alkaline compound such as sodium hydroxide, potassium
hydroxide, ammonium hydroxide, or the alkali metal carbonates.
The oxidizing agent of the invention is then added in the required
small but effective concentration quantity. It may be added
initially or only after the bath has reached a stage in which it is
not producing a satisfactory bright deposit.
Any water soluble metal compound which will form chelates with the
above-described chelating agents may be used for the plating
solutions of this invention including soluble compounds of iron,
cobalt, nickel, zinc, silver, copper, cadmium and tin. The metal
compounds employed in making up the baths may be (1) ionic metal
salts which when solubilized release a chelatable metal ion, e.g.,
copper sulfate, or (2) complex salts which, when solubilized, will
supply a chelatable metal ion, e.g., sodium zincate, or (3) metal
salts, such as the carbonates which will react with phosphonic acid
chelating agent to form a metal chelate salt. The plating of alloys
can be achieved by the invention through the use of two or more
different chelatable metals in the proper proportions. Examples of
alloys which have been plated by the present invention are
copper-nickel alloy, and copper-zinc "yellow brass" alloy and
copper-zinc "white brass" alloy.
For best results, essentially neutral electroplating solution of 6
to 9 pH is preferable, but higher pH ranges, up to 13 as well as
lower ranges to about 3 or 4 can also be used.
A number of other and further features have been discovered as
improvements in the invention. These generally are selected
metallic and non-metallic ions and organic compounds which can be
added to improve further the brightness obtained.
For example, it has been discovered that certain metallic
additives, when added to the plating baths of the invention,
improve significantly the brightness of the deposits, provided the
bath is stabilized with the oxidizing agent. These metals are
thallium, lead and cadmium. The amounts used is about 0.01 to 0.5
g/l or a sufficient amount to give the brightness desired. These
metals may be added as the soluble metal salt such sulfate,
acetate, tartrate, citrate, chloride, and the like. Other metallic
ions which can also be used include arsenic, antimony and bismuth
and the amounts used are about 0.01 to 1 g/l or a sufficient amount
to give the brightness desired. The ions can be added as the
soluble salt such as tartrate. Of the metallics above listed
bismuth has been found to be preferred.
It has also been found that selenium and tellurium can be
advantageously used in the stabilized bath. They may be added as
the sodium selenite or tellurite. The amounts that are useful are
about 0.1 g/l or an amount sufficient to improve brightness.
It has also been found that amino acids can be used to improve the
brightness of metallic deposits. Amino acids that are useful as
additives to the plating baths are lysine hydrochloride, cysteine
hydrochloride, alanine, methionine, glycine, 1-tyrosine, and the
like. The preferred amino acid additive is glycine. The amount
required is about 0.01 to 5 g/l or an amount sufficient to produce
the desired effect. Amino acids increase the ability of the plating
solution to withstand prolonged electrolysis without plating
dull.
It has been found that metal additives can be used with the amino
acids, i.e., bismuth ions with glycine with achievement of good
results.
In order to illustrate the novel electroplating baths of this
invention a series of baths are exemplified below. While particular
embodiments of the invention are specifically shown, it will be
understood that the invention is obviously subject to variations
and modifications without departing from its broader aspects.
The plating baths were prepared by dissolving in water the
indicated quantity of the compound of the metal to be
electrodeposited and the indicated phosphonate chelating agent. An
alkali metal hydroxide was added to the solution to adjust the pH
to the selected value. The examples illustrate the different metal
compounds which can be used in the invention and which when
solubilized release a metallic ion. For each of the baths described
below, the electroplating of the metal was conducted in a 267 ml.
Hull cell, in a conventional manner at a temperature in the range
of from room temperature to 140.degree.F. and at a current of 1
ampere. Various brighteners which are described as further features
of this invention were added to the bath as specific embodiments of
the invention.
BATH A
Grams per liter ______________________________________
Ethylenediamine tetramethyl- phosphonic acid 120 Copper sulfate 60
______________________________________
The pH of the mixture was adjusted to 10.3 with potassium
hydroxide. The electroplating was conducted at 140.degree.F. The
resulting copper deposit was of overall dull appearance with a
burned portion in the high current area.
BATH B
Grams per liter ______________________________________
Ethylenediamine tetramethyl- phosphonic acid 120 Copper sulfate 60
Glycine 4 ______________________________________
This is Bath A with glycine added. One half the panel from the low
current density is bright.
BATH C
Grams per liter ______________________________________
Ethylenediamine tetramethyl- phosphonic acid 120 Copper sulfate 60
Sodium selenite 0.02 ______________________________________
The pH of the mixture was adjusted to 8.0 with potassium hydroxide
and the deposition temperature was 140.degree.F. The copper deposit
was uniformly bright with a narrow burn in the high current
area.
BATH D
Grams per liter ______________________________________
1-Hydroxyethylidene-diphosphonic acid 180 Copper hydroxide 24
Cysteine hydrochloride 0.04
______________________________________
Potassium hydroxide was used to adjust the pH to 10.3 and the metal
was deposited at a temperature of 140.degree.F. The resulting
deposit was completely bright except at the high current area.
BATH E
Grams per liter ______________________________________
1-Hydroxyethylidene-diphosphonic acid 180 Copper hydroxide 24
Sodium bismuth tartrate 0.12
______________________________________
The pH was adjusted to 10.3 with sodium hydroxide and the
temperature was 140.degree.F. The resulting deposit was completely
bright except in the area of high current.
BATH F
To Bath E there was added 2 g/l of glycine. The overall brightness
of the metal deposited was improved.
BATH G
Grams per liter ______________________________________
1-Hydroxyethylidene diphosphonic acid 180 Copper hydroxide 24
Ethylenediamine tetramethyl Phosphonic acid 4
______________________________________
The pH was adjusted to a pH of 10.3 with potassium hydroxide. The
temperature used was 140.degree.F. The resulting deposit was
uniformly semibright; however, after electrolysis for 120 ampere
minutes, the deposit became dull and granular.
BATH H
After the deposit became dull and granular, 0.5 g/l of sodium
chlorite was added to Bath G. The deposit remained uniformly
semibright throughout the entire period of electrolysis.
BATH I
After the deposit became dull and granular, 1 cc/l of dimethyl
sulfoxide was added to Bath G. The deposit remained uniformly
semibright throughout the entire period of electrolysis.
BATH J
Grams per liter ______________________________________
Ethylenediamine tetramethylphosphonic 180 acid Nickel sulfate 75
Sodium chlorite 0.05 ______________________________________
Potassium hydroxide was added to adjust the pH to 5.0. A
temperature of 140.degree.F. was used and the metal deposit was
uniformly bright even after electrolyzing for 180 ampere
minutes.
BATH K
To Bath G there was added 1 cc/l of 30 percent hydrogen peroxide. A
metal deposit of uniform brightness was obtained throughout the
entire period of electrolysis.
BATH L
To Bath G there was added 0.5 g/l of potassium permanganate. Good
results in brightness were obtained throughout the entire period of
electrolysis.
BATH M
8 ml/l of 7 % sodium hypochlorite solution was added to Bath G.
Similar good results were obtained with metal
electrodeposition.
The above data demonstrate that the addition of oxidizing agents to
the plating baths led to markedly improved deposition results.
* * * * *