U.S. patent number 3,881,999 [Application Number 05/364,173] was granted by the patent office on 1975-05-06 for method of making abrasion resistant coating for aluminum base alloy.
This patent grant is currently assigned to Westinghouse Electric Corporation. Invention is credited to Julius Toth, Edward M. Walker.
United States Patent |
3,881,999 |
Toth , et al. |
May 6, 1975 |
Method of making abrasion resistant coating for aluminum base
alloy
Abstract
The method for applying an abrasion resistant coating on the
surface of an aluminum or aluminum alloy conductor. After cleaning
the conductor surface to remove dirt, grease, and oxides and to
make the surface uniformly active, a plurality of coatings of
metals are applied including an inner coating of tin, intermediate
coatings of bronze and copper, and an outer coating of tin or
silver.
Inventors: |
Toth; Julius (Beaver, PA),
Walker; Edward M. (Industry, PA) |
Assignee: |
Westinghouse Electric
Corporation (Pittsburgh, PA)
|
Family
ID: |
23433371 |
Appl.
No.: |
05/364,173 |
Filed: |
May 25, 1973 |
Current U.S.
Class: |
205/176; 205/181;
205/185; 205/213; 205/220; 428/673; 428/935; 205/182; 205/210;
428/647; 428/675 |
Current CPC
Class: |
C25D
5/10 (20130101); C25D 5/44 (20130101); Y10S
428/935 (20130101); Y10T 428/12715 (20150115); Y10T
428/1291 (20150115); Y10T 428/12896 (20150115) |
Current International
Class: |
C25D
5/34 (20060101); C25D 5/10 (20060101); C25D
5/44 (20060101); C23b 005/50 (); C23f 017/00 () |
Field of
Search: |
;204/40,38B,33,35R
;29/197 ;117/71M |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Kaplan; G. L.
Attorney, Agent or Firm: Johns; L. P.
Claims
What is claimed is:
1. A method for applying an abrasion resistant coating on the
surface of an aluminum-base alloy member comprising the steps
of:
1. cleaning the surface of the member;
2. rinsing the surface of the member;
3. applying an aqueous deoxidizing solution to the surface of the
member;
4. rinsing the surface of the member;
5. applying a coating of tin by immersing the member in an aqueous
solution consisting essentially of, for each gallon of water, from
about 8 to about 14 ounces of at least one tin-containing compound
selected from the group consisting of sodium stannate and potassium
stannate, and of from about 1 to 10 ounces of a chelating
agent;
6. electroplating a coating of a copperbase alloy on the tin
coating by immersing the member in an electrolyte consisting
essentially of, for each gallon of water, from about 3.5 to about
5.5 ounces of at least one compound selected from the group
consisting of sodium stannate and potassium stannate, from about
1.5 to about 2.5 ounces of copper cyanide, from about 2.5 to about
3.5 ounces of potassium cyanide, and from about 0.5 to about 1.3
ounces of potassium hydroxide;
7. rinsing the surface of the member;
8. electroplating a first coating of copper on the copper-base
alloy coating by immersing the member in an electrolyte consisting
essentially of, for each gallon of water, from about 3 to about 4
ounces of copper cyanide, of from about 6 to about 7 ounces of at
least one compound selected from the group consisting of sodium
cyanide and potassium cyanide, and of from about 4 to about 6% of
potassium-sodium tartrate;
9. electroplating a second coating of copper on the first coating
of copper by immersing the member in an electrolyte consisting
essentially of, for each gallon of water, from about 8 to about 10
ounces of copper cyanide, of from about 14 to about 16 ounces of at
least one compound selected from the group consisting of sodium
cyanide and potassium cyanide; and
10. electroplating an outer coating of a metal selected from a
group consisting of silver and tin to the second coating of
copper.
2. The method of claim 1 wherein between steps 9 and 10 the member
is rinsed and in step 10 the outer coating is tin.
3. The method of claim 2 wherein in step 10 the electrolyte is an
aqueous solution consisting essentially of, for each gallon of
water, from about 1 to 4 ounces of potassium hydroxide, from about
26 to 28 ounces of potassium stannate, and about 10 ounces of tin
metal.
4. The method of claim 3 wherein the operating conditions comprise
a temperature of from about 130.degree. to 180.degree.F, a voltage
of from about 3 to 6 volts, a current density of from about 30 to
160 amperes per square foot, and an anode to cathode ratio of up to
1:2.
5. The method of claim 4 in which the temperature is about
140.degree.F and the current density is 75 amperes per square
foot.
6. The method of claim 3 wherein there are about 2 ounces of
potassium hydroxide, about 28 ounces of potassium stannate, and
about 10.6 ounces of tin metal.
7. The method of claim 2 wherein the tin applied by step 5 has a
weight of from about 0.1 to 0.3 mg/in.sup.2, the copper base alloy
coating has a thickness ranging from about 0.00001 to 0.00003 inch,
the first coating of copper has a thickness of from about 0.00001
to 0.00003 inch, the second coating of copper having a thickness
ranging from about 0.00018 to 0.00022, and the outer coating of tin
having a thickness of from about 0.0001 to 0.0003 inch.
8. The method of claim 1 wherein the outer coating is silver.
9. The method of claim 8 wherein the electrolyte in step 10
consists essentially of an aqueous solution of, for each gallon of
water, about 2.5 to 3.5 ounces of silver cyanide, from about 8 to 9
ounces of potassium cyanide, and from about 6 to 10 ounces of
potassium carbonate.
10. The method of claim 9 wherein a current density of 10 amperes
per square foot is provided.
11. The method of claim 1 wherein in step 6 the cathode current
density is from about 20 to 80 amperes per square foot, the anode
current density is from about 10 to 20 amperes per square foot, the
temperature range is from about 75.degree. to 85.degree.F, and the
time of exposure of the member is from about 3 to 10 minutes.
12. The method of claim 11 wherein the cathode current density is
about 30 amperes per square foot, the anode current density is
about 15 amperes per square foot, the temperature of the
electrolyte is about 80.degree.F, and the time of exposure of the
member is about 4 minutes.
13. The method of claim 1 wherein in step 8 the electrolyte
consists essentially of, for each gallon of water, about 3.5 ounces
of copper cyanide, about 6.4 ounces of at least one compound
selected from the group consisting of sodium cyanide and potassium
cyanide, and of about 5% by volume of potassium-sodium
tartrate.
14. The method of claim 13 wherein the operating conditions of the
electrolyte consists essentially of a pH of from about 9.8 to 10.2,
a temperature ranging from about 105.degree. to 115.degree.F, and a
voltage supply of about 9 volts.
15. The method of claim 1 wherein in step 9 the electrolyte
consists essentially of about 9 ounces of copper cyanide, about 15
ounces of at least one compound selected from the group consisting
of sodium cyanide and potassium cyanide, about 6% by volume of
potassium-sodium tartrate.
16. The method of claim 15 wherein the operating conditions of step
9 consist essentially of an electrolyte temperature of about
165.degree.F, a supply voltage of about 9 volts, and a plating time
of about 4 minutes at 25 amperes per square foot.
17. The method of claim 1 wherein in step (5) there is about 11
ounces of the tin-coating compound.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to an abrasion resistant coating for an
aluminum and aluminum alloy conductor and to a method for applying
the coating.
2. Description of the Prior Art
The application of protective coatings for various purposes on the
surface of members composed of aluminum and aluminum alloys is
well-known in the art such as disclosed in U.S. Pat. Nos.
2,377,606; 2,947,639; and 3,274,021. Generally, those patents
disclosed a method for providing a tightly adherent tin coating on
an aluminum surface.
Where specific environmental problems are incurred, additional
protection is necessary. In the past a coating consisting of layers
of zincate, copper, and silver plating on aluminum bus bars has
left much to be desired for environmental protection; improved
corrosion resistance in specialized areas has been indicated.
Associated with the foregoing has been a problem of fretting due to
either mechanical wear or corrosion. In one form fretting is wear
resulting from oscillating or vibratory motion of a limited
amplitude. Another form of fretting results from actual wear,
frictional changes, variations in electrical resistances,
electrical noise, and fatigue failure. Aluminum is particularly
susceptible to fretting corrosion which is the formation of hard
abrasive oxides (Al.sub.2 O.sub.3) as debris and by an excessive
rate of oxygen absorption. As a result, there has been a problem of
providing aluminum members, such as bus bars or conductors, with a
protective coating of a suitable type by which abrasion and
corrosion are avoided.
SUMMARY OF THE INVENTION
Generally, it has been found in accordance with this invention that
the foregoing problems may be overcome by providing an aluminum
conductor or bus bar with a multiple layered coating of various
metals applied in a given sequence, which sequence consists
essentially of an inner layer of tin, intermediate layers of bronze
and copper, and an outer layer of either tin or silver.
The invention also comprises a method for applying the several
layers in the indicated sequence.
DESCRIPTION OF THE PREFERRED EMBODIMENT
According to the present invention in practice the new method is
carried out in the following sequential manner:
1. Preliminarily cleaning the surface of the member to be coated
with a caustic solution to remove oxides, dirt, grease, and the
like;
2. Rinsing the surface in water;
3. Cleaning the surface with an acid;
4. Rinsing the member in water;
5. Applying an inner coating of tin to the surface;
6. Applying a copper-base alloy coating on the tin coating;
7. Rinsing the member in water;
8. Applying a first coating of copper on the copper-base alloy
coating;
9. Applying a second coating of copper on the first coating of
copper;
10. Rinsing the member in water and
11. Applying an outer coating of tin or silver on the second
coating of copper.
The method is applicable to pure aluminum and a wide range of
aluminum alloys such as aluminum alloy numbers 6061, 6101, 2024,
5052, 7075, 356, 360, and 380.
The first step comprises cleaning the surface with a caustic
solution to remove oxides, dirt and the like, and removes about 1/2
to 1 mil of aluminum surface. The preferred solution for this
purpose is about 8 ounces of sodium hydroxide per gallon of water
at 180.degree.F which is applied to the aluminum surface for a time
of from about one-half to one minute. Other alkali metal hydroxides
such as potassium hydroxide may be used. A chelating agent is
preferably added to the solution to slow down the action. A common
chelating agent is ethylenediaminetetraacetic acid (EDTA). The
advantage of the chelating agent is to maintain the material
removed from the aluminum surface in solution.
The second step is a water rinse to remove all traces of the
caustic solution of the first step because the third step involves
an acid solution.
The third step is a surface cleaning operation with an acid
solution such as a 1:1 mixture of nitric acid (67%) in water for
the purpose of deoxidizing and removing impurities in aluminum such
as iron and manganese. Although it is not necessary, about 1 to 5%
hydrofluoric acid is preferably added to make the aluminum surface
more uniformly active and to prevent blistering of subsequently
deposited metal. The blistering often occurs due to poor metal
preparation.
The fourth step is another rinse in water to remove all traces of
acid of the previous rinse, because the next step involves an
alkaline bath.
The fith step has the dual purpose of activating the aluminum
surface and depositing a thin layer of tin. In this step the
aluminum member is immersed in an aqueous solution the primary
constituent of which is at least one tin-containing compound
selected from the group consisting of a stannate of an alkali metal
such as sodium stannate and potassium stannate, together with a
chelating agent such as EDTA. The composition of the solution is
shown in Table I as follows:
Table I ______________________________________ Activating & Tin
Plating Bath Constituent Preferred Range Composition* Composition*
______________________________________ Na.sub.2 SnO.sub.3.sup..
H.sub.2 O 11 8-14 and/or K.sub.2 SnO.sub.3.sup.. H.sub.2 O
Chelating Agent 6 1-10 (EDTA)
______________________________________ *Ounces per gallon of
water
The constituents sodium stannate and potassium stannate may be used
either alone or mixted to make up the required composition. Sodium
stannate and potassium stannate used here and in subsequent steps
may be used either in the anhydrous or the trihydrate form; it
being immaterial, because the operating conditions require the
solution to be maintained at an elevated temperature of from
75.degree. to 85.degree.F with a preferred temperature of
80.degree.F. The immersion time may range from 10 to 60 seconds
with a preferred time of 30 seconds. A partial or wholly substitute
chelating agent is preferably used for stabilizing the tin to
prevent it from settling to the bottom of the container. It is a
mixture of zinc acetate, Zn (C.sub.2 H.sub.3 O.sub.2).sub.2, in an
amount of about 2 ounces per gallon of water and m-cresolsulthonic
acid in the amount of about 4 ounces per gallon of water. Thus, by
step 5 the surface of the aluminum member is completely activated
and the protective layer of tin is deposited. The weight of tin
deposited varies from about 0.1 to 0.3 mg/in..sup.2.
The sixth step is the application of a coating of a copper-base
alloy, such as a bronze strike, applied directly on the tin
coating. A rinse between steps 5 and 6 is unnecessary because the
solutions of both steps are alkaline. The sixth step is
accomplished by immersing the aluminum member into an electrolyte
consisting essentially of a stannate of an alkali metal such as
sodium stannate and copper cyanide. A partial or complete
substitute for sodium stannate may be potassium stannate. The
constituents and the amounts used for the bronze strike are shown
in Table II as follows:
Table II ______________________________________ Bronze Strike
Ounces per gallon of water Constituent Preferred Range Composition
Composition ______________________________________ Na.sub.2
SnO.sub.3 4.5 3.5-5.5 and/or K.sub.2 SnO.sub.3 CuCN 2.0 1.5-2.5 KCN
(Free) 3.0 2.5-3.5 KOH (Free) 1.0 0.5-1.3
______________________________________
The electrolyte solution consisting of the constituents listed in
Table II includes potassium cyanide (KCN) and potassium hydroxide
(KOH) which increase the conductivity and efficiency of the
electrolyte and improve the erosion of the copper and tin anodes,
thereby reducing the current loss and maintaining the desired
electrolyte temperature. In addition, by improving anode corrosion,
the amount of makeup of the constituents sodium stannate and
potassium stannate as well as copper cyanide is reduced.
The operating conditions of the bronze strike step are shown in
Table III, as follows:
Table III ______________________________________ Operating
Conditions Condition Preferred Range
______________________________________ Time 4 mins. 3 to 10 mins.
Temperature 80.degree.F 75.degree. - 85.degree.F Cathode current
density 30 ASF* 20 to 80 ASF Anode current density 15 ASF 10 to 20
ASF ______________________________________ *Amperes per square
foot
The thickness of the bronze coating may vary from about 0.00001 to
0.00003 inch.
The seventh step is a water rinse for the purpose of removing the
bronze solution and for preventing contamination of the copper
strike solution which is the eighth step.
The eighth step, being a copper strike for the application of a
relatively thin layer of copper on the bronze strike, has a purpose
of providing better adhesion of the copper plate application of
step 9. The aluminum member is immersed in electrolyte having the
constituents listed in Table IV as follows:
Table IV ______________________________________ Copper Strike
Ounces per gallon of water Constituent Preferred Range
______________________________________ CuCN 3.5 3-4 KCN and/or NaCN
6.4 6-7 Additive (tartral) 5% by vol. 4-6% by vol.
______________________________________
The additive (tartral) is preferably a Rochelle salt such as
potassium-sodium tartrate, which serves to improve anode and
cathode characteristics. The thickness of the copper strike ranges
from about 0.00001 to 0.00003 inch, the preferred thickness being
0.00002 inch. The operating conditions for the electrolyte bath are
listed in Table V as follows:
Table V ______________________________________ Operating Conditions
pH 9.8-10.2 Free Potassium Cyanide 1.0 to 1.5 oz./gallon
Temperature .degree.F 105-115 Voltage 9 volt supply; approx. 6
volts across work Current 10-30 ASF
______________________________________
Although the current range is from 10 to 30 amperes per square foot
the preferred current is 25 amperes per square foot for 60 to 120
seconds to obtain the above-indicated coating thickness.
The ninth step is the application of the second coating, or the
so-called copper plating. For that purpose the aluminum member is
immersed in an electrolyte for a period of 4 minutes at 100%
cathode efficiency to provide a copper plate thickness of from
about 0.00018 to 0.00022 inch, and a preferred thickness of 0.00020
inch. The formula of the electrolyte bath and the operating
condition for the bath are listed in the following Tables VI and
VII:
Table VI ______________________________________ Copper Plate Ounces
per gallon of water Constituent Preferred Range Composition
Composition ______________________________________ CuCN 9 8-10 KCN
and/or NaCN 15 14-16 Additive (tartral) 6% by vol. 5-7% by vol.
______________________________________
Table VII ______________________________________ Operating
Conditions Free KCN and/or 0.5-1.5 oz./gallon NaCN Temperature
165.degree.F Voltage 9 volts Current Density 15-35 ASF (Preferred
25 ASF) Plating Time for .0002" Cu 4 min. at 25 ASF Agitation
Filtered air Filtration Continuous and sufficient to turn over tank
volume approx. 3 times per hour.
______________________________________
Step 10: After the copper plate or coating has been applied, the
member is ready for the outer coating of tin or silver as
preferred. However, a rinse in two baths of cold water is required
before subsequent plating of tin or silver.
Step 11: Where the choice is tin, the copper plated aluminum member
is immersed into the plating solution having the formula and
operating conditions set forth in Tables VIII and IX as
follows:
Table VIII ______________________________________ Tin Plate Ounces
per gallon of water Constituent Preferred Range Composition
Composition ______________________________________ KOH 2 1-4
(K.sub.2 SnO.sub.3) and/or Sodium Stannate (Na.sub.2 SmO.sub.3) 28
26-28 Tin metal equivalent 10.6 10-11
______________________________________
Table IX ______________________________________ Operating
Conditions Range Preferred ______________________________________
Temperature .degree.F 130-180 140.degree.F Voltage 3-6 Current
density 30-160 ASF 75 Anode to Cathode ratio Never more than 1:2
Time to deposit .0001 to .0006 in. of plating at recommended
current 2-4 2 density, minutes
______________________________________
The thickness of the outer tin plate or coating may range from
0.0001 to 0.0003 inch, the preferred thickness being 0.0002
inch.
Where the outer plating or coating is silver instead of tin, the
copper-plated aluminum member is placed in the silver plating
electrolyte having a formula and control conditions as set forth in
Tables X and XI as follows:
Table X ______________________________________ Silver Plate Ounces
per gallon of water Constituent Range Composition
______________________________________ AgCN 2.5-3.5 KCN 8.0-9.0
KCO.sub.3 6.0-10.0 ______________________________________
Table XI ______________________________________ Operating
Conditions Range Preferred ______________________________________
Time 60-70 seconds Temperature 70.degree.-100.degree.F 85.degree.F
Voltage 2-6 volts Current Density 5-10 ASF Anode to Cathode ratio
1:1 ______________________________________
A silver plating or coating thickness of from 0.00003 to 0.00005
inch is normally deposited in about 70 seconds for the indicated
current density. As in the preceding deposition such as for the
copper and tin, the cathode is the aluminum member held stationary
in the electrolyte. The anode is composed of copper, tin, or silver
depending upon the metal being deposited.
The resulting protective coating provided in the method set forth
above provides a corrosion and abrasion resistant plating for stabs
for bus ducts when bus bars are subjected to 30,000 consecutive
abrasion tests, i.e., involving sliding wear. More specifically, a
prior art problem of wear through aluminum resulted in the
formation of high resistance due to globules of aluminum oxide
(Al.sub.2 O.sub.3) which resistance caused excess heating at the
contact points and resulted in plastic flow in the form of fretting
and mechanical weldings of the stab and the contact which in turn
resulted in arcing. The multiple layered coating of this invention
satisfies the foregoing problem of fretting with attendent
problems. The bronze plating provides a suitable substrate for the
copper strike which in turn sets up a bond for the copper plating.
The copper plating has a tri-fold advantage including the
establishment of a base for the silver or tin which is subsequently
applied, preventing corrosion, and providing a hard base for
sliding friction on the stab surface. The outer coating of tin
prevents oxidation of the copper. Silver likewise prevents copper
oxidation but in addition resists fretting better than tin and does
it with a thinner coating.
* * * * *