U.S. patent number 3,816,185 [Application Number 05/216,268] was granted by the patent office on 1974-06-11 for protective coating on wire.
This patent grant is currently assigned to Raytheon Company. Invention is credited to Luke Dzwonczyk, Roger Shih-Yah Mo, Emil Toledo.
United States Patent |
3,816,185 |
Toledo , et al. |
June 11, 1974 |
PROTECTIVE COATING ON WIRE
Abstract
A chemical bath for applying a protective coating on
magnetically plated wire during in-line processing, the bath
comprising an aqueous alkaline solution including a 0.05 to 0.25
percent concentration of an adsorbable, organic corrosion inhibitor
from the class consisting of thiazole, urea and amine compounds;
and a 1 to 5 percent concentration of an inorganic, PH stabilizer
from the class consisting of borate, benzoate and phosphate salts
of sodium and potassium.
Inventors: |
Toledo; Emil (Natick, MA),
Dzwonczyk; Luke (Marlboro, MA), Shih-Yah Mo; Roger
(Redondo Beach, CA) |
Assignee: |
Raytheon Company (Lexington,
MA)
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Family
ID: |
26693961 |
Appl.
No.: |
05/216,268 |
Filed: |
January 7, 1972 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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20851 |
Mar 18, 1970 |
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Current U.S.
Class: |
428/624; 148/271;
148/260; 148/274; G9B/5.282 |
Current CPC
Class: |
G11B
5/722 (20130101); C23C 22/60 (20130101); Y10T
428/12556 (20150115) |
Current International
Class: |
C23C
22/05 (20060101); C23C 22/60 (20060101); G11B
5/72 (20060101); C23f 007/00 () |
Field of
Search: |
;117/239,240,237
;148/6.14R,6.24 ;29/191.6 ;179/1.2R ;274/41.4 |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
Mathias et al., IEEE Transactions on Magnetics, Vol. May 5 No. 4,
December 1969, p. 748. .
Danylchuk et al., Bell System Technical Journal, Vol. 47, October
1968, pp. 1539, 1550-1552. .
Abstract of Ser. No. 680,058, Official Gazette, July 19, 1949, p.
928..
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Primary Examiner: Kendall; Ralph S.
Attorney, Agent or Firm: Pannone; Joseph D. Murphy; Harold
A. Rost; Edgar O.
Parent Case Text
This application is a division of application Ser. No. 20,851 filed
Mar. 18, 1970, now abandoned.
Claims
What is claimed is:
1. In combination:
a protective coating on a body comprising a permalloy plated
conductor having a coating of magnetic material, said protective
coating being applied by a bath comprising an aqueous alkaline
solution including an adsorbable, organic corrosion inhibitor
comprising thiazole and an inorganic PH stabilizer from the group
consisting of borate, benzoate and phosphate salts of sodium and
potassium and combinations thereof.
2. The combination as set forth in claim 1 wherein the PH of the
bath is maintained at a value between 8 and 11.
3. The combination as set forth in claim 1 wherein the minimum
concentration of said organic corrosion inhibitor is about 0.05
percent, and the minimum concentration of said inorganic PH
stabilizer is about 1 percent.
4. The combination as set forth in claim 1 wherein the maximum
concentration of said corrosion inhibitor is about 0.25 percent and
the maximum concentration of said inorganic PH stabilizer is about
5 percent.
5. The combination as set forth in claim 4 wherein said organic
corrosion inhibitor is substantially entirely thiazole and said
inorganic PH stabilizer is a combination of sodium borate and
sodium benzoate.
6. The combination as set forth in claim 5 wherein the
concentration of thiazole is about 1 gram per liter, the
concentration of sodium borate is about 10 grams per liter, and the
concentration of sodium benzoate is about 10 grams per liter.
Description
BACKGROUND OF THE INVENTION
The invention herein described was made in the course of and under
a contract, or subcontract thereunder, with the U.S. Strategic
Systems Projects Office, Department of the Navy.
This invention is related, generally, to chemical solutions for
forming protective coatings on wire and is concerned, more
particularly, with a chemical bath for applying a protective
coating on plated memory wire during in-line processing.
One exemplary magnetic plating line comprises a spaced, parallel
array of chemical cells in colinear alignment with a rotatable
spool of wire at one end of the array and a longitudinally
disposed, tubular furnace at the other end. The wire, usually, is
made of a resilient material having good electrical properties,
such as beryllium-copper, for example. In operation, wire feeds
continuously off the spool and is drawn longitudinally through the
respective cells of the array and the aligned, tubular furnace.
Generally, the surface of the wire is cleaned, etched and
electropolished while passing through the initial cell stages, and
receives a plating of copper, while passing through the
intermediate cell stages of the array. Usually, in the final cell
stages of the array, the wire is plated with a material having
desirable magnetic properties, such as permalloy, for example.
Permalloy is a nickel-iron compound having preferred percentage
compositions for plated memory wire which exhibit low
magnetostrictive properties when the plated wire is distorted.
Another reason permalloy is a preferred plating material for
magnetic memory wire is that it acquires uniaxial, anisotropic
magnetic properties when influenced by a coaxial magnetic field
during the plating process. As a result, an "easy" direction of
magnetication is established circumferentially in the plated
permalloy film; and an orthogonal "hard" direction of magnetization
is established parallel to the axis of the wire. Furthermore, each
discrete cylindrical portion of the plated permalloy film has a
nearly square hysteresis loop in the easy direction of
magnetization and an almost linear hysteresis loop in the hard
direction. Thus, any particular portion of the plated permalloy
film may be magnetized in the circumferential direction, either
clockwise or counterclockwise. Also, the magnetic vector of a
selected portion of the plated permalloy film may be switched from
one circumferential rest position to the other. Consequently, the
two oppositely directed rest positions, usually, are assigned the
respective digits, one and zero, of a binary logic system.
In order to avoid deterioration of the described magnetic
characteristics, the plated permalloy film is annealed while
exposed to the flux of an orienting magnetic field. Therefore,
after leaving the final permalloy plating cell in the magnetic
plating line, the plated wire, generally, passes through an
additional chemical cell containing a pool of conductive liquid,
such as mercury, for example. The mercury liquid provides a minimum
resistance means for making an electrical connection to the
continuously moving wire, without wetting the metallic components
of the plated permalloy film. By means of the mercury contact, an
orienting current is passed through the permalloy plated wire while
the wire is traveling through the subsequent furnace stage of the
magnetic plating line. In the furnace, the wire generally passes
through an inert or a reducing gas atmosphere which, usually, is
maintained at a temperature greater than 250.degree.C. Thus, the
plated permalloy film is annealed while the magnetic vectors of the
respective memory cells in the permalloy film are uniformly aligned
by a coaxial magnetic field established by the orienting current.
After passing through the heat treatment furnace, the wire,
generally, is tested as part of the continuous process and cut into
segments which, subsequently, are assembled into a memory
system.
The plated permalloy film is very thin, generally being about 1
micron in thickness. Consequently, minute holes occur in the film
along the length of the continuous wire. It has been found that,
when the permalloy plated wire passes through the liquid contact,
minute quantities of mercury enter these "pin" holes and amalgamate
with the exposed copper material. Consequently, when the permalloy
plated wire enters the elevated temperature environment of the heat
treatment furnace, the low melting temperature mercury-copper alloy
expands radially under the permalloy film. As a result, localized
cracking and peeling of the permalloy film were found, at a later
time, to have occurred around the respective pin holes and spread
radially outward therefrom. Thus, stored memory bits were destroyed
and sizable portions of the plated memory wire had become
inoperative.
Therefore, in order to ensure long term reliability for plated
memory systems, it is imperative that the plated memory wire be
protected from the described type of mercury-induced corrosion.
Protective coatings applied after the plated wire has been
processed and tested will not solve this problem, because the
mercury must be prevented from wetting any exposed copper material
during processing of the wire. Furthermore, it is essential that
the mercury liquid be in electrical contact with the continuously
moving wire in order to provide an orienting current during the
heat treatment process. Consequently, coatings of insulating
material, such as paints, varnishes, resins and the like, are
unsuitable for such protective coatings. Also, any coating of
protective material applied during processing of the wire must be
capable of withstanding the elevated temperature environment of the
heat treatment furnace without stressing or otherwise affecting the
magnetic properties of the plated permalloy film.
SUMMARY OF THE INVENTION
Accordingly, this invention provides a chemical bath for forming a
protective coating on plated memory wire while the wire is moving
longitudinally through the bath at plating line velocity. The
chemical bath of this invention comprises an aqueous, alkaline
solution including 0.05 to 0.25 percent concentration of an
adsorbable corrosion inhibitor, and 1 to 5 percent concentration of
a PH stabilizer. It was found that members of the thiazole group of
compounds, such as thiazole, mercaptothiazole, benzothiazole, for
examples, are the most effective adsorbable, corrosion inhibiting
agents. However, members of the urea group of compounds, such as
thiourea, monotolylthiourea, ditolylthiourea, for examples, and
members of the amine group of compounds, such as dibenzlamine,
tribenzlamine, hexodecylamine, for examples, also are acceptable as
adsorbable, corrosion inhibiting agents in the chemical bath of
this invention. Sodium borate, sodium benzoate and sodium phosphate
are preferred stabilizing agents, although potassium borate,
potassium benzoate and potassium phosphate also are acceptable as
PH stabilizing agents for this bath.
Since the chemical bath of this invention was developed,
specifically, for protecting plated memory wire during in-line
processing, it was evaluated in a typical magnetic plating line.
The inventive aqueous, alkaline solution was contained in a
chemical cell which was disposed between the final cell of the
permalloy plating stage and the mercury contact cell. The chemical
cell, so disposed, was 3 inches high, 6 inches long, 5 inches wide
and contained 750 milliliters of the inventive alkaline solution.
During the evaluation tests, the described bath was maintained at a
temperature between 20.degree. and 30.degree.C.
The wire used for evaluating this chemical bath was a commercial
grade, No. 125 beryllium-copper wire having an initial diameter of
about 5.5 mils and a surface finish of about 16 microinches.
However, after passing through the etching and electro-polishing
cell stages of the magnetic plating line, the diameter of the wire
was reduced to about 4.9 mils and the resulting surface finish was
about 4 microinches. In the intermediate cell stages of the line,
the polished wire received a plating of copper, about 3 microns
thick. In the magnetic plating stage of the line, the copper-plated
wire received a plating of permalloy material about 1 micron in
thickness.
After passing through the chemical bath of this invention, the
plated wire passes through the mercury contact cell and then
through the heat treatment furnace. One suitable furnace was 4 feet
long and was maintained at a temperature between 300.degree. and
400.degree.C. In order to test the quality of the protective
coating applied by the chemical bath, an inert or reducing gas
atmosphere was not used in the heat treatment stage. Thus, the
plated wire was exposed to an air atmosphere at high temperature.
Under these conditions, any areas left uncovered by the protective
coating will be covered with a black oxide coating. It has been
found that wire coated with this black oxide film will not pass
electrical test at the end of the plating line. When a portion of
the wire fails electrical test, an automatic cutter is triggered
which then removes the rejectable portion from the continuous
wire.
The compositions of the inventive baths tested under the described
conditions are listed below.
Chemical Bath No. 1 ______________________________________
Constituent Conc. Range Preferable Conc.
______________________________________ Thiazole .5-2.5 gm/liter 1
gm/liter Sodium borate 10-50 gm/liter 10 gm/liter Sodium benzoate
10-50 gm/liter 10 gm/liter Distilled water balance balance Chemical
Bath No. 2 Constituent Conc. Range Preferable Conc.
Mercaptothiazole .5-2.5 gm/liter 1 gm/liter Sodium benzoate 10-50
gm/liter 10 gm/liter Chemical Bath No. 3 Constituent Conc. Range
Preferable Conc. Benzothiazole .5-2.5 gm/liter 1 gm/liter Sodium
phosphate 10-50 gm/liter 10 gm/liter
______________________________________
The function of the organic inhibitor, such as thiazole,
mercaptothiazole and benzothiazole in the inventive Chemical Baths
Nos. 1, 2 and 3, for example, is to coat any exposed copper on the
plated wire before it enters the mercury contact cell. These
organic inhibitors preferentially wet copper and are adsorbed onto
the copper surface, thereby forming an extremely thin layer of
organic material, only a few molecules in thickness. This molecular
thin layer of inert material is sufficient to prevent mercury
wetting of the copper and the resulting formation of low melting
mercury copper amalgamines. However, the adsorbed layer of organic
material does not interfere with the passage of current from the
mercury to the plated wire. Thus, the mercury liquid still retains
electrical contact with the surface of the plated wire.
It has been found that if the organic inhibitor concentration is
below the specified minimum value, the exposed copper material will
not be completely coated with inert material. Consequently,
mercury-induced corrosion can take place at the still exposed
copper areas and result in damage to the surrounding permalloy
film, as previously described. On the other hand, if the organic
inhibitor concentration is above the specified maximum value,
organic inhibitor material, being solubility sensitive, will
precipitate out of the solution. Not all organic inhibitors perform
satisfactorily in the chemical bath of this invention. Some organic
inhibitors do not preferentially wet exposed copper material, and
others contaminate the mercury cell. Some organic inhibitors which
may be used, alternatively, in place of those disclosed in
respective Chemical Baths 1, 2 and 3 are: mercaptobenzothiazol, 1-2
thiazoldinethione, 2-4 thiazoldenione, 1-(2 thiazolylago-2
napthol), thiourea, monotolylthiourea, ditolylthiourea,
dibenzlamine, tribenzylamine and hexodecyclamine.
The function of the PH stabilizer in this novel chemical bath is to
maintain the PH value of the bath in the 8-11 alkaline range. Thus,
if the concentration of the PH stabilizer is below the specified
minimum value, the PH value of the bath will be in the acidic range
and will result in pitting of the plated permalloy film. When the
PH stabilizer concentration is within the specified limits, the
resulting alkaline solution reacts with the plated permalloy
material and renders it passive thereby forming an extremely thin
layer of nickel-iron oxide, only a few molecules thick, on the
surface of the permalloy film. This molecular thin layer of
nickel-iron oxide material is not thick enough to interfere with
the passage of current from the mercury liquid to the plated wire.
However, if the concentration of the PH stabilizer is above the
specified maximum value, the PH value of the bath will be above the
required 8-11 range. This highly alkaline solution will passivate
the surface of the plated permalloy material too deeply. The
resulting thick nickel-iron oxide layer will interfere
significantly with the passage of current from the mercury liquid
to the plated wire core. Consequently, the orienting current
required for the heat treatment stage will fluctuate and the
resulting magnetic properties of the annealed permalloy film will
be erratic. Therefore, the maximum concentration value specified
for the PH stabilizer in the bath is extremely critical.
In this chemical bath, sodium borate, sodium benzoate and sodium
phosphate are preferred PH stabilizing agents. However, potassium
borate, potassium benzoate and potassium phosphate also may be used
as PH stabilizers. Further, these PH stabilizing agents may be used
alone or in combination with another one of the designated PH
stabilizers to maintain the bath in the desired PH range of 8-11.
When at least one of the designated PH stabilizers is present,
within the concentration range specified, the resulting alkaline
solution reacts with the permalloy plated wire to produce a surface
film which, after passing through the subsequent furnace stage,
hardens into a characteristic light colored coating. Evaluation
studies disclose that a permalloy plated memory wire having this
light colored coating has a low failure rate in electrical test and
exhibits improved aging properties. It also has been found that the
coating action of this inventive bath is practically instantaneous
and, therefore, not dependent on the speed of the magnetic plating
line.
Thus, there has been disclosed herein a novel chemical bath for
applying a protective coating to plated magnetic memory wire during
processing of the wire. The bath comprises an aqueous alkaline
solution including an organic inhibitor which is adsorbed on the
surface of exposed copper material to form a molecular thin film
thereon which prevents the copper areas from being wetted by
mercury in the subsequent liquid contact cell. The solution also
includes at least one PH stabilizer which maintains the solution in
the PH range of 8-11. As a result, of passing through this alkaline
solution and the subsequent furnace stage, the permalloy plated
wire is coated with a protective film which prevents further
oxidation of the permalloy plated wire. This protective coating
does not adversely affect the magnetic properties of the permalloy
plated material but appears to ensure that the permalloy material
will retain the magnetic properties required for plated memory
systems.
From the foregoing, it will be apparent that various changes may be
made by those skilled in the art without departing from the spirit
of this invention as expressed in the appended claims. It is to be
understood, therefore, that all matter described herein is to be
interpreted as illustrative and not in a limiting sense.
* * * * *