MONTHLY REVIEW
Published
by the
American Electroplaters Society
Publication and Editorial Office
3040 Diversy Ave., Chicago
VOL.
XVII JULY, 1930 No. 7
EDITORIAL
To the members of the American Electro-Platers Society:
It gives me great pleasure to present to you the first issue of the Review
under jurisdiction of four new officers for term 1930-931.
It will be
our great aim to equal previous work of this publication, and to surpass
same as is expected of each succeeding administration
if progress is to be made by our Society.
We thank all past officers for
their kind assistance in trying to aid us in getting started off with
speed and accuracy, and hope for the same
courtesies afforded this office by the branch secretaries, officers
of branches, and the patience of our members, and I can assure you the
same
high standard of efficiency shall be maintained by the Monthly Review.
Page
2 contains full information on new officers. Kindly note these and
address all your communications to proper officers and this will promote
the efficiency of these new officers and avoid usual confusion in change
of officers.
The branch officers and members will also note that the
Society is now incorporated under the laws of New Jersey. Also that our
constitution
remains the same with such changes as are legally made at conventions
per provisions thereof. Also note that the 1st change is to strike
out of constitution Section 3, Article XII, page 23, by majority vote
of
delegates.
HYDROGEN PITTING AND PEALING OF NICKEL AND COPPER PLATED
DEPOSITS UPON HIGH CARBON AND OTHER STEELS
By Charles H. Proctor
Hydrogen pitting and
pealing of the copper and nickel plated deposits upon high carbon and
other steels at intervals, presents serious problems
under the present intensive production of such plated products previous
to chromium plating in the automotive and other allied industries.
Looking
backwards thirty years or more ago when the double nickel salt solution
(nickel and ammonium sulphate) was exclusively used and operated
under low current densities of not more than 5 amperes per square foot
of surface area, no pitting of the nickel plated finish occurred, but
as I review some of the problems I met with in the late eighties, 1888
to 1890 and 1892, I now know that hydrogen was then a problem as it
is today, but we did not know then its detrimental influence as it is
known
today.
I have
talked with many of the old time platers in Connecticut, whose fathers
were
platers before them; men who knew the art of plating
in
every detail and had to produce every type of finish and in those early
years there were no elaborate colored lacquers of the Duco and other
types to assist in the production of contrasting effects in the production
of art metal goods. The plater had to produce his own colors, principally
with a so-called ”French Varnish” base which consisted of
grain alcohol in which was dissolved gum copal and other hard gums. Such
men never mentioned hydrogen pitting or pealing of their nickel plated
deposits. If such problems occurred then the problem was always laid
at the door of defective cleaning or other chemical treatment of the
basic steel or cast or malleable iron products, but there is no question
that hydrogen has always been a disturbing factor in nickel plating operations
even as it is today, but upon a more extensive and more serious basic
due to intensive production from high density nickel and copper plating
solutions.
Going
back to the years 1888 to 1890, I was employed by the Ansonia Brass
and Copper
Company, Ansonia, Conn. This firm is now
a part
of the Anaconda
Copper & Brass Corporation, who succeeded the American Brass Corporation.
I then had charge of all plating and polishing and also lacquering departments
and we produced about every type of finish that it was possible to produce
and this means all the antique finishes that are produced today on electric
fixtures and art goods in general. We had problems then and they had
to be overcome because we had to produce acceptable goods even as platers
must produce today. This was in the days before volt and ampere meters,
before chemical control had become a recognized factor in the operation
of modern electroplating solutions, and before chemistry had become a
recognized factor. Still we did produce results. How we did it is still
a great problem but we carried the art along even as our fathers, who
were platers, did before us.
It was in 1881889 when I ran into the greatest
problem of all my extensive plating experience. We had to plate highly
polished copper- sheets some
22 inches by 54 inches in size, and 1/16 inch thick, on both sides
with an adherent deposit of nickel that would not strip or peal and that
would
withstand temperatures of three hundred degrees F. or more; beneath
a hydraulic pressure of 20,000 pounds or more. Such sheets as outlined
were used in the manufacture of polished celluloid in Arlington and
Newark,
N. J. The former plant is now controlled by the DuPont Corporation.
Matt finished celluloid had to be produced as well as the polished material,
so the nickel plated copper sheets had to be sand blasted after nickel
plating and steam pressure was used for the purpose instead of compressed
air as now used.
When we first started operations in the nickel plating
of such sheets all seemed to go along well. The sheets were trimmed
on the extreme ends
and sides to conform with the exact size required. The sheets were
then polished to a very high lustre with buff wheels with a face surface
area
wider than the sheets themselves. After polishing the sheets were packed
with canton flannel sheets and blotting paper pads between, to avoid
any possible scratching or abrasion of the sheets in transit. Such
defects would always show up in the polished celluloid sheet having been
transmitted
from the nickel plated surface.
Later on problems developed at intervals.
Nickel plated copper sheets were apparently perfect when leaving our
plant. The nickel did not peal
from the sheared strips when bent at right angles until crystallization
occurred and the strip broken in two nor in the final polishing operation
did the nickel separate from the sheets, yet at intervals when the
sheets were placed in production due to heat expansion and high pressure,
the
nickel would be found to separate from the base metal and adhere to
the celluloid sheets when removed from the hydraulic presses.
Every operation
was carefully gone over in detail when such problems occurred because
it was a very costly one for my firm as they had to
replace such sheets and stand for every incidental expense connected
with their failure, so each shipment that failed ran into thousands
of dollars.
Cleansing was thoroughly studied, removal of any oxide
even of a superficial nature was carefully gone into. The current was
carefully
controlled
under then existing conditions, but the problem still continued at
intervals. We had a metallurgical laboratory in charge of my late and
lamented friend,
Dr. George Grower. He went deeply into the solutions and made a check-up
to prove that there was nothing wrong with them but to no avail. Finally
the dawn came out of the darkness and I saw the true basis of my problem;
we did not know how to control it but I did in my own way. I decided
to add nothing to the solution contained in a tank 24 feet long, 36
inches deep and 24 inches wide, except commercially pure ammonium sulphate
and
water and keep the nickel solution exclusively for plating the copper
sheets.
It is strange, however, that before I discovered the probable
cause of my problem, I had plated hundreds of thousands of nickel plated
brass
clock cases in the same solution and never had the least trouble of
pealing of the nickel deposit.
We still meet with similar problems and some still
think that the cleansing, or the pH of the solution, or the current
control is the cause of pitting
or pealing, but I do not. If this theory was true then my firm would
never have developed the extensive business for sodium perborate I
first advocated for hydrogen control and 25 to 100 volume hydrogen peroxide
for the same purpose of hydrogen control in nickel plating solutions.
The
modern hydrogen pitting and pealing of nickel plated deposits which
has caused an endless amount of trouble in the automobile and accessory
industries had its origin with the introduction of the single nickel
salt solution. The resultant high metal content of such solutions and
high current densities carried upon the surface area which influenced
hydrogen deposition or occlusion such as pitting.
When pitting first occurred
with nickel pealing it was decided that heating of the concentrated
nickel solution to 120 deg. Fahr. would expand the
hydrogen gases or bubbles and they would rise to the surface of the
solution and pass into the atmosphere, but did not solve the problem.
The filtering
of the nickel solution prevented mechanical pitting but not hydrogen
pitting or pealing. Filtering and air agitation by compressed air did
not solve nickel plating problems.
The
author failed to find any true reference to any authentic work on electro-plating
written during the
interim between the years of 1880
and 1895 which gave any satisfactory explanation of hydrogen pitting
and pealing, its true cause and cure until Dr. Madsen of Madsenell Nickel
fame discovered the detrimental influence of hydrogen. Many presumed
authorities who should know better in the light of present day facts
still believe such problems are due to other causes’ cleansing
in particular or detrimental pH or current conditions.
Dr.
Oliver P. Watts of the University of Wisconsin, whom we’ all
know and admire, in his excellent address in Pitting of Nickel Plating
at the annual banquet of Chicago Branch (A. E. S.) in January, 1924,
summed up the causes of nickel pitting and pealing from the reports of
those members of the society who were so kind as to write to him and
cite their experiences with these problems, as follows:
(a) The nickel
solution too acid.
(b) It is too alkaline.
(c) Imperfections in the basic metal surface.
(d) Defective cleansing of the basic metal surface.
Dr.
Watts frankly admitted at the outset of his address as follows: ”Although
I have used all the time that I could beg borrow or steal, I am- still
unable to give you a true cure for pitting and pealing of nickel deposits.
F.
E. Halberttin his excellent article, ”The Pitting and Pealing
of Nickel Deposits,” published in the Brass World in October, 1907,
gave the most satisfactory explanation of the cause of- such problems,
but could offer no solution of the problem.
The
late Emmanuel Blassett, Jr., a well known author and former member
of the New York
Branch (A.
E. S.), wrote an excellent article in December,
1911, issue of The Metal Industry on ”The Cause and Prevention
of Pitted and Rough Nickel Plated Deposits.” Mr. Blassett, however,
did not solve the problem in his article.
The electrical wizard, Thomas
A. Edison, was the first to solve the problem of hydrogen control of
nickel plated deposits. He had found the very
detrimental influence of hydrogen deposition and occlusion when endeavoring
to produce perfectly malleable thin sheets of nickel by electrolysis.
He obtained a U. S. Patent No. 964,096 in 1910 covering the introduction
of chlorine gas into the nickel solution under pressure. The function
of the chlorine so injected into the solution was to combine with the
excess hydrogen and from hydrochloric acid. The free acid so formed
in the solution removed the excessive amounts of hydrogen that was the
cause
of defective malleable nickel deposits and became a factor in increased
anodic reduction in the formation of nickel chloride.
The
value of Edison’s
ideas have been amply proven during the past few years by automotive
product manufacturers who have used tremendous
amounts of nickel chloride which results in greater anodic reduction,
greater throwing power and to a great extent hydrogen control. It was
Edison’s theory of the value of chlorine which gave the writer
the cue several years ago to advocate the extensive use of nickel chloride.
It is not a new factor, for as early as 1880 I saw it in operation in
Birmingham, England, and known as ”Double Nickel Chloride Solutions” for
planting the old high bicycle parts made from steel and the cycle type
which was then called the safety bicycle.
It has proven its value in the
commercial plating industry in America and many serious cases of hydrogen
pitting or pealing of the nickel deposit
have been controlled by its aid. Nickel chloride sodium perborate or
its product, hydrogen peroxide, are the real factors. It has proven
to be true in a thousand plants during the past few years and has eliminated
a great source of trouble to the plater and a costly disturbing factor
in the plating industry as a whole. It is now possible to nickel plate
steel in high density solutions, either still, automatic conveyor or
mechanical barrel type, with nickel content as high as 12 ounces of
metallic
nickel per gallon of solution and obtain the very maximum results.
The
problem of hydrogen pitting and pealing from the basic steel is nut
only confined to nickel deposits but occurs when articles made from low
carbon steel such as auto radiator shells and high carbon steels, such
as used in the manufacture of automobile bumpers, etc., are copper
plated.
This has proven to be true in solving many problems I have met with
in recent years, especially in copper plating from copper cyanide solution.
The
copper cyanide solution that develops hydrogen pealing of the copper
deposit may be an entirely normal one so far as metal and free cyanide
is concerned and the inert factor as sodium carbonate may also be normal,
still pealing problems may result even with the most careful chemical
treatment of the steel articles to be plated. Such a condition developed
in a large automobile plant in Toledo, Ohio, three years ago. For nearly
a week the copper deposit was pealing from radiator shells when the
deposit was polished to a lustre finish as a basis for the final nickel
and chromium
deposit. In many instances the pealing would not show up until the
nickel deposit had been applied and buffed to a lustre finish, then again
only
when the chromium had been applied.
It was
first inferred that the cleansing of the steel previous to plating
was defective
although the same type
cleaner had previously given ideal
results and no plating problems. The cleaner is a well known product
of a Michigan firm, but the conclusions were that the cleaning was the
true cause of the pealing problem. So the cleaner expert was called in
and for nearly a week labored consistently to cleanse the product satisfactorily.
I happened to be in the Ohio city where the plant is located and as usual
called upon the firm which was having the trouble outlined. The matter
was brought to the writer’s attention and he at once diagnosed
the problem as due to hydrogen and the copper cyanide solution was treated
accordingly and it was also decided to treat the nickel solution for
a possibility of hydrogen occlusion, although no trouble had occurred.
The addition of sodium bisulphite to the copper cyanide solution up to
two ounces per gallon of solution was made in proportion of one-half
ounce at a time. The copper was thus reduced from the cupric to the cuprous
state and the hydrogen gas, which caused the trouble, was released, due
to the reaction of the sulphurous acid the salt contained and has never
re-occurred. The cleaner expert returned during the day and when told
that the problems had been overcome, stated he thought that the last
addition he made to the latest cleaner installed would do the trick,
but he was advised later of the true cause of the trouble
Within the past
two months friends of the author have in stalled in a plant in the
Pittsburgh, Pa., district, a complete automatic conveyor
unit for nickel, copper and nickel plating automobile bumpers. The
mechanical features of this unit are perfect in united operation and
capable, under
forced conditions, of plating 17 carloads of automobile bumpers per
day at the maximum current densities.
I was requested to write up the detailed
information covering all solutions, including: alkaline cleansing,
acid pickling, nickel strike, copper cyanide
and final nickel deposit. The detail included the several water washings,
both cold and hot, as required. The formula outlined for the plating
solutions were as follows:
Nickel Solution (Strike and Regular): |
Water |
1 gallon |
Single nickel salts |
50 ounces |
Nickel chloride |
4 ounces |
Boracic acid |
2 ounces |
Voltage, 6. Amperage, from 30 to 100 per square
foot of surface area.
Temperature, 110 to 120 deg. Fahr. pH, 5.4-5.6.
Copper Cyanide Solution: |
Water |
1 gallon |
Sodium cyanide 96/98% |
10 ounces |
Copper cyanide |
8 ounces |
Sodium sulphite |
4 ounces |
Sodium hyposulphite |
1/50 ounce |
Voltage, 5 to 6. Amperage, 25 to 100 per
square foot of surface area. Temperature, 120 deg. Fahr.
With absolute cleansing the high carbon steel
bumpers developed pitting and slight pealing in the nickel solution
and hydrogen pitting and pealing
of the copper deposit. Although cleaner experts and research chemists
had diagnosed the pitting and pealing problems as one of exclusive
defective cleansing, still the writer decided hydrogen gas was the true
cause of
the problem and treated them accordingly with sodium perborate, as
the hydrogen controlling factor in the two nickel solutions, and with
sodium
bisulphite additions in the copper cyanide solution, up to two ounces
per gallon. It required a minimum of one-fourth ounce of sodium perborate
administered under the procedure first outlined in this paper.
If, at
any time, you are confronted with similar problems first being absolutely
assured that your product is chemically clean, then the factors
I have outlined will solve your problems of pitting and pealing of
the nickel and copper plated deposits.
As previously stated, it was Dr. Madsen
who first proposed publicly the use of hydrogen peroxide as a controlling
factor for hydrogen in nickel
plating solutions. He advocated from 4 to 16 cc. of a 3 per cent solution
per gallon of solution, or 1 to 4 cc. per liter. The active oxygen
it contains and splitting off the hydrogen peroxide combined with the
hydrogen
as it is generated at the cathode, and thus prevents hydrogen pitting
or pealing.
Hydrogen peroxide is an unstable liquid, however, which
starts to decompose as soon as it is made. Moreover, it contains only
1 1/2 per
cent oxygen,
the rest being water. It is, therefore, bulky and causes a great deal
of expense in transportation.
It was, in order to overcome these disadvantages
that I cast about to find a better source of oxygen which could be
relied upon to retain its
valuable oxygen until required, which would not necessitate carrying
around an enormous bulk of dead matter and which would permit accurate
measurement and therefore uniform results. If, besides this, such a
chemical were slightly alkaline, its addition to the acid nickel solution
would
neutralize a part of the acid.
I found such a chemical in sodium perborate
(Na BO3 + HO) which is a powder contained 10 per cent available oxygen.
Its solution in water
is mildly alkaline. It can be kept indefinitely without loss of strength.
One pound is the equivalent of 6.7 pounds hydrogen peroxide. It costs
one-third less for the oxygen it contains. Instead of from 8.8 to 35
pounds of hydrogen peroxide per 1,000 gallons of nickel solution, we
take from 1 1/3 to 5 pounds of sodium perborate. The perborate should
first be dissolved in warm water (100 degrees Fahr.) at the rate of 1
pound
in 6 gallons. This solution is then added to the nickel bath in such
quantity as experience- teaches will take care of the hydrogen evolved.
In
most instances the slight alkalinity of the perborate solution is of
advantage in cutting down excessive acidity of the nickel bath, but
when the latter is finely regulated the perborate solution may first
he acidified with hydrochloric acid until it equals the acidity of
the nickel bath.
I may state that in every case I have met, the perborate
has acted as expected, and has prevented hydrogen pitting or pealing,
which would
appear to indicate that sodium perborate accomplishes all that hydrogen
peroxide does, but overcomes its disadvantages and is cheaper.
INTRODUCTION
OF IRON INTO
ALKALINE CLEANING AND PLATING SOLUTIONS
Read at Washington,
D. C., 1930, by F. J. Liscom Chicago Branch
How does iron
get into the bath?
In what form is it held in solution?
What effect does it have on the anode?
Effect on the steel tank and steel
anode rods of a silver solution?
Work
is pickled in sulphuric acid—hydrochloric acid?
Neutralizing
of pickling acid?
Rinse water as source of impurities in-plating
solutions?
Effect of ammonium
chloride in nickel solution?
Effect of ammonium chloride
in acid copper solution on the anode?
Effect
of chlorides in a silver bath—sodium chloride—ammonium
chloride—and mixture of both?
Why the addition of sal ammoniac to
cyanide solutions?
Introduction of
Iron Into Alkaline Cleaning and Plating Solutions
From
time to time a request for credit comes through the mail for a steel
plating tank that has failed, i. e., showed signs of corrosion or actually
perforated. Many tanks have been replaced with new ones only to have
a repeat request for another. There have been so many steel tanks that
have failed that it has become a hardship for the manufacturers. As
it was realized that all of the tanks could not be defective, an investigation
was started in an endeavor to find out the reason for the numerous
failures.
One has not far to go to find this reason if he happens to be a close
observer.
Steel tanks have been used for generations as containers
for cleaning solutions. We used weak solutions and low temperatures and
expended
much
arm power at the handle of a scrub brush, but all of this has been
changed, and now in this age of production we must resort to less laborious
methods
for cleaning the work to be plated. Therefore, we install electro-cleaners
and high current densities and do the work in a fraction of the time
consumed by the old method of hand scrubbing.
Now, electric cleaning is
a very proper method when it is performed in an intelligent manner,
but unfortunately the process has its-limitations.
In the first place the tank should never be made the anode of the circuit
because eventually corrosion is sure to follow. Caustic soda, soda
ash, or sodium cyanide, when used as a cleaner, will cause no trouble
so long
as there is no salt such as sodium sulphate, trisodium phosphate, sodium
chloride, or ammonium chloride present; even the sulphate and phosphate
may be neglected provided there is enough caustic soda present. However,
if the caustic soda has become destroyed by age, the sodium sulphate
and phosphate, if present, will commence to corrode the steel tank.
Chlorides, no matter what kind, will attack the steel even in the presence
of much
free cyanide and sodium hydroxide.
If the steel tank is the anode of the
electric cleaner, the plater should know if his cleaner solution is
attacking his steel tank. A simple test
will apprise him of the fact. All that is necessary to do is to take
a drinking glass, fill up the glass with the cleaning solution (preferably
filtered), then with two pieces of wire connected to the bus bars of
the dynamo place a steel nail on the other ends of the wires and dip
the ends of the nails into the cleaner solution. Let the electric current
flow through the solution and watch the anode nail. If the solution
contains chemicals that will cause corrosion, a heavy scum will form
on the anode
in a very few minutes.
Trouble often occurs when you have a lot of work
that must be pickled. This is done in sulphuric or muriatic acid, after
which you rinse, dry,
polish, and go to the cleaner. The iron or steel has iron sulphate
or chloride in the pores which the cleaner neutralizes. The iron in the
salt is precipitated and sodium chloride or sulphate is formed. Each
day increases the amount until at last the alkali is weakened and the
sodium chloride and sodium sulphate get into action, and eventually,
if used as an anode, the tank goes to the junk pile.
Again, we find that
some operators will take the work out of the pickle and neutralize
the acid in the cleaner even without a previous rinse.
Neutralizing solutions have been found that actually showed acid reaction
with blue litmus paper. The remedy is obvious, and it is within your
power to correct the evil.
Where work must
be pickled be sure to rinse the acid away by the use of several rinse
waters, neutralize the remaining
acid in a strong alkali ”her
than the electric cleaner, and again rinse well, and lastly take the
positive connection off of the cleaner tank and install anode rods insulated
from the tank and fitted with large, steel anodes. This last suggestion
does not cure the evil; it only delays the day when the tank is junked
unless care is taken to exclude the acid mentioned.
Acids are not the
only offenders, for, where only one rinse tank has been installed,
nickel sulphate gets into the cleaner and cyanide plating
solutions in steel tanks by being carried from the foul rinse water.
Nickel solutions also contain chlorides as well as sulphates, and these
too should be rinsed away.
Avoid the use of low percentage sodium cyanide,
as this often contains as much as 20 to 25 per cent sodium chloride.
This sodium cyanide is
satisfactory for heat treatment of steel but not for plating.
Just one
more thought—perhaps you use what is termed the reverse
current in the cleaner, and you think that because the work comes out
of the cleaner with a dirty color you are plating out the dirt. Well,
you are not. You are simply undoing what the polisher has done because
of the fact that the cleaner is low in caustic and high in sulphates
and chlorides of soda or ammonia, which means that you actually etch
the work you are about to plate, and, if the ”dirt which you plated
out” is not removed by an acid, then the plating may peel, blister,
or pit.
In the old days
electroplating was something of a mystery even of the best informed.
All formulae said to dissolve so much of such
and
such
chemicals and if the solution does not work then add so and so. Then
the more thoughtful ones began to investigate to try to find out the
why. Finally there came methods of analysis for plating solutions. These
data were based on the published methods of analysis of solutions which
contained only pure chemicals—at least they did when new.
However,
a plating solution that has been used for a long time may have gathered
some other ingredients not mentioned in the formula, such as
glue, salts of other metals such as zinc and copper, cadmium in nickel
solutions, iron which may appear as ferrocyanide in alkali baths, or
salts of the strong acids as chlorides and sulphates. Some of these
impurities exert a powerful influence even in microscopic quantities.
With this
thought in mind some experiments have been carried on, not necessarily
to a final conclusion but to a point that indicates that we are not
going into the chemical research as far as we should, which is an argument
in favor of more funds for the research committee. The results of these
experiments, as well as some observations, are here set down in the
hopes
that further work may be done by others more capable.
Some years ago
our attention was called to a large cyanide brass plating solution
which
was working badly. An effort was made to analyze the solution
for metals, carbonates, free cyanide, etc. As the analysis proceeded
it became evident that there was a metal present other than copper and
zinc. This metal proved to be iron. Since then solutions have come to
hand from time to time that contained iron. However, little attention
was paid to its presence; no attempt was made to ascertain in what form
the iron was held or what effect it may have had on the deposit of copper,
brass, or cadmium; or what, if any, action it had upon the anode. Very
recently three cyanide solutions have come to hand, one a cadmium. Here
it was noted that the steel supports of the cadmium anodes were gradually
disintegrated to such an extent that they fell apart, and at low temperature
(60° F. to 70° F.) small, transparent, sand-like crystals, which
gave no reaction for either sulphates or carbonates, formed on the steel.
Eventually they fell off and accumulated on the bottom of the tank. After
these crystals were gathered and lay in the air for several days they
lost their water of crystallization and a white powder resulted which
was still soluble in water. When hydrochloric acid was added a green
solution resulted. It was also noted that the tank was corroded at the
ends to such an extent that it had to be replaced by a new tank.
Two copper
solutions came to hand that contained a small amount of free cyanide—a
little metallic copper. The solutions had a peculiar color. The anodes
were coated over with a reddish brown, fur-like coating,
which much resembled copper ferrocyanide.
Experiments have
been carried on with sodium cyanide solutions to which iron salts have
been purposely
added in the presence of varying amounts
of free sodium cyanide. Both ferrous sulphate and ferric chlorides were
tried. The ”ous” salt seemed to be the most completely dissolved
in cyanide, especially when there was sodium hydrate present. All of
the iron salts, ”ous” or ”ic”, are not completely
soluble in cyanide sodium. No matter how strong or how hot the solution
is there still remains some undissolved iron precipitate in the cyanide
solution with either ”ic” or ”ous” iron in-solution.
When all of the iron salts have been dissolved that will dissolve there
is still free cyanide present. To these iron solutions was added enough
copper cyanide so that no free sodium cyanide remained. Then, when a
current of 6 to 7 amperes per square foot was passed, a good deposit
formed on the cathode, while the copper anode became covered with a thick
coating of a mixed, blue-green solid and a reddish-brown scum. Sodium
cyanide was added in quantities of 1/4 ounces per gallon until at about
ounces per gallon only the reddish-brown scum was apparent on the anode.
At approximately 1/4 ounces per gallon of sodium cyanide the anodes did
not coat heavily at 6 to 7 amperes per square foot. To find what would
be the effect of a greater current density with the same amount of free
sodium cyanide, the current was increased to approximately 15 amperes
per square foot, and it was found that in 15 minutes there formed on
the anode a thick, heavy, reddish-brown coating, which corresponded to
the color of copper ferrocyanide.
From this we gather that for a cold
copper cyanide solution, where the sodium cyanide content must be kept
down (in the interest of high cathode
efficiency), the presence of iron will be detrimental to good anode
corrosion due to the ferrocyanide formed. In warm solutions, where a
much larger
free sodium cyanide content can be maintained and we can still have
a good cathode efficiency as well as a higher current density, it is
predicted
that there would still be some difficulty unless care were taken to
offset the ferrocyanide with free cyanide, temperature, and current density.
Just
how the iron gets into the solution in the first place is a problem.
We know from experience that in some solutions (electric cleaning) when
the work is being cleaned electrically on the anode or positive pole,
the steel is attacked, showing the characteristic color changes peculiar
to ferrous hydroxide; viz., the first color noticed is white. This is
soon followed by a greenish color. Later this, when exposed to water
or air, becomes the color of iron rust (ferric hydroxide?). Since this
red color does not seem to go into sodium cyanide, at least not completely,
it is presumed that when the ferrous hydroxide is white or in the early
stage of the green color, and it is on the surface of the work, going
into the warm cyanide plating solution, it is probably soluble in sodium
cyanide’ at least to some extent, and forms sodium ferrocyanide.
Then, if this is so, it follows that if a piece of steel or iron is pickled
in an acid and not completely rinsed and neutralized the iron salts produced
do undergo a chemical change to form hydrates (ous), which seemingly
are soluble in cyanide and hydrate and do form sodium ferrocyanide.
Again,
even if the iron salts from the pickle solution were not converted
into ferrocyanide, there would at least be a chemical change between
the acid radical of the pickle acids and the alkali of the cleaner,
and there would form as a part of the reaction a sodium sulphate or sodium
chloride, depending upon the acids used in the pickle (sulphate distinct
from chloride). With these chemicals in the plating solutions in contact
with the iron heating coils and the steel tank, which may get into
the
path of the electric current, i. e., become cathode near the back of
the copper anode and anode at the end or bottom of the tank near the
true cathode proper, at that portion of the tank that became the anode
electro-chemical action is set up to such an extent that the steel
tank becomes corroded and even perforated, exactly as described above
in connection
with certain electric cleaners. If, then, the white or green (ous)
iron hydrate at the instant of formation is dissolved in the sodium cyanide
and hydroxide of the bath, the final result will be the same; namely,
the formation of sodium sulphate or sodium chloride and possibly sodium
ferrocyanide.
Therefore, the
obvious solution of the problem is to prevent mineral acids or salts
of strong mineral acid from getting into the alkali
plating
solution even in small quantities, because, even after’ they have
attacked the tank and at least a portion of the dissolved iron goes into
solution or is precipitated as hydrate, the salt of the acid is regenerated
and is free to act again, etc., ad lib. If, however, such salts are present,
and they are frequently added to the solutions intentionally in the form
of sodium sulphite, bisulphite, hyposulphite, sodium sulphate, ammonium
chloride, etc., some provision should be made to prevent the electric
current from coming into contact with the steel tank. Therefore, use
rubber-lined steel tanks, which will keep down the effect of sodium sulphate
or chloride on the steel tank and leave only the anodes in the solution
open to the action of the chloride or sodium ferrocyanide, if present.
As
it was realized that all mineral acid salts may not act the same, some
tests were run which would determine which acids were the most detrimental.
Then solutions of sodium cyanide with the additions were prepared, each
in a separate beaker. The electrodes were of steel and the electrodes
of the several cells were electrically connected in series. A current
of suitable strength was passed for a period of one hour. The presence
of Rochelle salts resulted in no corrosion of the steel anode. However,
in the presence of sodium chloride or ammonium chloride there was a very
heavy corrosion of the steel anode; yet the action of the sodium chloride
was different than that of the ammonium chloride. With ammonium chloride
there the iron seemed to go into solution momentarily. As this metal-charged
solution came in contact with the chemicals a precipitate formed around
the drops. The color of this precipitate, at first whitish, later turned
to a bluish-green color and eventually became very dark brown in spots
(ferric hydroxide). As the action continued a very fine example of that
chemical phenomenon known as ”chemical garden” formed. As
the solution filters through this precipitate or membrane to dissolve
more iron at the anode, the membrane will break and the iron bearing
solution will burst forth only to be confined by a new membrane at the
point of the rupture. Some of the branches were as fine as a hair and
extended upward for at least two inches.
In that solution where sodium
chloride was used, the action on the anode was as great as where the
ammonium chloride was used, but there was no
chemical garden formation.
In a silver solution
made from silver chloride and cyanide, to which was added some ammonium
chloride, there was still
another type of result
at the anode. (And from this it is gathered that there is really more
in this subject than appears on the face. Notwithstanding the fact that
such solutions have been used for years without complaint, it does not
follow that there was no reason for complaint. Probably the thought was
that these conditions just had to be, as was the case with the yellow
sludge in nickel solutions where 90 per cent nickel anodes were used—”it
wad just there, that’s all.”) Both ammonium chloride and
sodium chloride were present. The latter resulted from the reaction when
silver chloride was dissolved in sodium cyanide. There formed at the
anode a yellowish, ochre-like precipitate, which slipped off the anode
and fell to the bottom of the beaker. Later, when this solution was taken
out and stirred, it was noticed that the particles were very small (colloidal)
and that they did not settle rapidly. The solution was then boiler with
some sodium cyanide solution, after which it was cooled and placed back
in the line, and the action on a fresh steel anode was noted. On this
second run the anode scale was exactly the same as in a bath where sodium
chloride alone was used. Why the anode slime should change from yellow
before boiling the solution to brown after boiling it is not known, unless
the boiling drove off the ammonia to form additional sodium chloride.
It
begins to look as if there are certain plating solutions in which ammonium
chloride may be used, while in other solutions it may be -useful;
as for instance in nickel solutions where the ammonia complex seems
to cause an action on the anode whereby the anode efficiency is greater
than the cathode efficiency. At least the metal content of the solution
does increase. However, in an acid copper solution ammonium chloride
will cause a yellow copper chloride to form on the anode which is insoluble
in the acid copper solution. This may be gathered and washed and dissolved
in nitric acid, and with silver nitrate test solution it will react
for
chlorine. Again, with the presence of sodium chloride in certain types
of nickel solutions where high current densities are used, it has been
noticed that the sludge is rich in nickel hydrate which forms and settles
at the bottom of the tank. Later Experiments
It was noticed that in a solution known to contain ferrocyanide,
sal ammoniac, and sodium cyanide, and in a silver solution which contained
both sal ammoniac, sodium chloride, and sodium cyanide, the iron anode
scum was of a dark blue color upon being examined in a strong light
when dry (see above). When it was treated with ammonium chloride a portion
of it went into solution (Prussian blue).
With ammonium chloride and cyanide
and an electric current a yellow scum formed on the steel anode (see
remarks above on silver). Hot caustic
soda dissolved a portion of this precipitate. The solution then gave
a green color with hydrochloric acid (iron). When a copper anode was
put into action in this solution it gradually became covered with a
red copper ferrocyanide, indicating that the iron that had been removed
from
the steel anode due to the presence of the ammonium chloride had been
dissolved in the cyanide; or else this was done by some reaction that
did cause the formation of sodium ferrocyanide. This, of course, set
free the chlorine, which was then free to attack the steel tank or
other iron that got in the path of the electric current. (Series.)
In the solutions
of ferrocyanide, sodium cyanide, and sodium chloride, the anode scum
seemed to be wholly red iron hydroxide
In a solution of
sodium cyanide and sal ammoniac the copper anode gives off a green
color which is expelled by more cyanide, but when the sodium
cyanide becomes saturated the color of the solution and the slime from
the anode indicate the ammonia copper complex and the presence of ferrocyanide,
as the copper anode takes on a red color.
When only sodium cyanide is
run with a steel anode there is no visible action on the steel. Summary
Work which is pickled in hydrochloric acid, or other acid
for that matter, should be well neutralized and rinsed several times
in clean
water before
going to a plating solution.
Cleaning and alkali plating solutions should
be free from all chlorides, or
The tanks should be rubber lined.
Unlined steel tanks should not be used
as the positive or anode in any cleaning or plating solution.
All electric cleaning and alkali plating
solutions should be tested with steel electrodes to see if the solution
attacks the steel tank under
the influence of the electric current.
Seemingly sodium ferrocyanide does
not interfere with anode corrosion in alkali copper solutions except
where the free cyanide content is low
and the current density is high.
Sodium ferrocyanide in the presence of
sodium cyanide does not effect the steel anode seriously.
Rochelle salts added to cyanide solution did
not attack steel, but 76 per cent sodium cyanide, i. e., chloride mixture,
should not be used
for plating.
Ammonium chloride should not be used in acid copper solutions.
Steel tanks
should be rubber lined to prevent a metal deposit on the tank back of
the anode, i. e., false cathode. At some other point as
the end or bottom of the tank, i. e., false anode, of chlorides are present
in the solution the tank may be expected to be corroded or even perforated
due to this series connection. Moral—Line steel tanks.
The object
of this paper is not to tell you something but rather to start something.
Thanks are due to Dr. W. Blum and also to Mr. Harold Faint
for helpful hints.
CADMIUM PLATING
Read at Detroit 1929 Annual
by H. C. Pierce
This morning
you heard a specific talk on cadmium plating. This goes in the other
direction, and is entirely a general discussion on cadmium.
The
corrosion of metals and its prevention is daily receiving more and
more notice, and is today one of our major engineering problems. The
numerous works and publications of recent years show the activity of
the investigators in this field; a field of paramount importance, but
one of the most complicated and least known in all chemistry.
The goal
of the investigator in corrosion has been to thoroughly grasp the fundamental
laws of corrosion, which, however, has been very difficult,
as the possibilities of corrosion of industrial products are almost
unlimited. It can only be predicted to what influences a material will
be subjected,
so that all precautionary methods of protection are more or less one
sided. The progress made in this field shows that the engineer is not
as helpless in combating corrosion as in former times. Ways and means
can and will be found to combat this resistless attack.
An accurate estimate
of the loss resulting from corrosion of the metals in common use is
quite impossible. This yearly loss is known to amount to millions of
dollars.
Much of this loss is invisible to the casual observed, but it is only necessary
to observe a few of our junk yards to have this fact forcibly brought to mind.
Some part of the corroded metal is recovered as scrap, but the cost of replacing
such parts far exceeds this saving. Rusting and corrosion may also impair the
strength of structures and machines, thus endangering not only property, but
human lives.
Aside from the actual destruction of parts, and cost of
replacement, there is
still another factor of extreme importance. Roughly, the loss and replacement
of 1,000 tons of steel gives a depletion tons of coal, 500 tons of limestone,
together with magnesite, chromite, etc. The labor required also involves a
large number of man hours.
The more numerous the uses of a product, the more are the
kinds of corrosive attacks to which it is subjected. The best example is that
of iron and its alloys,
which are used in all branches of industry and technology. The widespread use
of iron has been the means of bringing forth almost countless methods for protecting
iron from corrosive attacks. The method of protecting the surface depends primarily
on the use to which the article will be subjected. Of the various methods used
in protecting metal surfaces, metal coatings and methods of their application
play a particularly important part. Various metals have been successfully used
as metal coatings on other metals. Gold, silver, lead, tin, nickel, copper,
brass, chromium, zinc and cadmium have all been used in an attempt to
stop or to retard
the resistless advance of corrosion. Each metal has its own specific properties,
so that each metal has its own particular field of usefulness in this relentless
battle against corrosion. Likewise, these same specific properties often limit
the value of a metal as a rust proofing agent.
One metal, however,
has been found to be of particular value in protecting ferrous metals
against corrosion under
a maximum of conditions. This metal is cadmium.
Cadmium was discovered by the German Chemist Stromeyer in 1817, while investigating
the peculiar yellow color of a zinc oxide. Although discovered in 1817, it
is a comparatively new metal industrially. Most metals, especially those
found of
value in the plating industry, occur naturally in ores and are more or less
easily obtained. Metallic cadmium does not occur naturally, and there
is no ore of cadmium
or mineral of which cadmium is the main constituent. Only certain compounds
of cadmium, mainly carbonates and sulphides—are found associated
in minute quantities with the ores of zinc, and in still lesser quantities
with the ores
of lead and copper. Actually, the presence of cadmium in lead and copper ores
is due solely to the presence in them of zinc compounds or minerals, in the
absence of which, the ores would be cadmium free.
The ratio of cadmium to zinc varies
greatly, and is often too small to be of any value whatever. The useful ratio
varies roughly from 1 to 160 to 1 to 400,
the latter ratio probably being nearer the average than the former. The production
of cadmium except as a by-product is of course unprofitable, so its extraction
is always associated with the metallurgy of the ore in which cadmium occurs.
Even
though cadmium is obtained only as a by-product, the purity of commercial cadmium
is extremely high, it usually containing less than 0.5% of foreign matter,
and usually approaches 99.9% purity. The impurities usually found are traces
of zinc, iron, lead, tin, copper, nickel, and very occasionally, traces of
thallium.
The
production of metallic cadmium has increased more than ten fold in the last
ten years. In 1919, approximately 100,000 pounds of metallic cadmium
were produced
in the United States, while in 1927, 1,074,654 pounds of metallic cadmium were
produced. Figures for 1928 have not been obtained, but undoubtedly exceed those
of 1927.
The use of cadmium for electro-deposition has increased
even more rapidly. In
1922, with a cadmium production of approximately 131,000 pounds, most of which
was used in the manufacture of paints, chemicals, solders, etc., only a few
hundred pounds were used for electroplating purposes. From that time
on, the increase
was rapid. In 1928, the Udylite Process Company alone used approximately 650,000
pounds. In the first four months of 1929 the Udylite Process Company actually
sold and delivered to Udylite licensees 329,000 pounds of cadmium metal. This
means that during 1929 one company alone will handle approximately 1,000,000
pounds of cadmium metal for electroplating purposes exclusively.
When it is considered
that the average coating is only 0.0002” thick, the
volume of work covered assumes staggering proportions. This amount of cadmium
metal if spread on the earth’s surface to a thickness of 0.0002”,
would cover an area of approximately 4 square miles, or 2,500 acres.
The color
of cadmium metal itself is very often referred to as tin color, but it may
be described as having a silver white color with a blueish tinge, and
is more nearly the color of steel than of tin, which possesses a yellowish
cast.
Cadmium has a brilliant luster when freshly cut or polished, but becomes dull
when exposed to the air. Cadmium crystallizes in hexagonal pyramids. The metal
shows no cleavage, the fracture is brilliant and crystalline when pure, but
fine grained and dull when impure. Pure cadmium sticks, when bent, give
a sound very
familiar to the so-called ”tin cry.” Impure cadmium sticks do not
give this cry when bent, so in an emergency this test may be used as a rough
test of purity.
Cadmium is soluble in most acids. Strong alkalies, such
as caustic soda or caustic potash, which dissolve zinc very rapidly,
have little or no action
on cadmium.
Cadmium combines directly with chlorine, bromine and iodine when placed in
solutions of those elements. Cadmium is also soluble in ammonium nitrate.
Cadmium is harder
than tin and softer than zinc. It is malleable and ductile at ordinary temperatures.
Being soft, cadmium will not resist heavy mechanical
wear, nor the action of abrasives. On the other hand, its softness and ductility
make it more resistant than zinc or nickel to knocks or blows, just as a tough
elastic enamel will outlast a brittle enamel.
The electro-deposition of cadmium
has developed almost entirely in the last ten years. Acid and ammonicial solutions
have been proposed at various times, but
such solutions were found to be quite unstable, changing in composition quite
rapidly, and producing a crystalline or porous deposit. This latter evil could
only be partially remedied by the use of addition agents of various sorts.
Cyanide solutions, even without addition agents, produce finely crystalline,
though dull
deposits, while various well known addition agents not only reduce the crystalline
size still further, but impart a lustrous color very pleasing to the eye. Cyanide
solutions are relatively stable as compared to acid or ammonicial solutions,
requiring a minimum of care under severe conditions. As a consequence, cyanide
solutions are mainly used for the electrodeposition of cadmium.
A metallic coating
may protect the ferrous base either chemically or mechanically or both. Cadmium
protects both chemically and mechanically. To protect the ferrous
basic metal chemically, the coating metal must stand above iron in the electromotive
series, so that in case the underlying metal is exposed, and moisture is present,
which is almost invariably the case, the coating metal will function as anode
in the little galvanic battery so formed, and corrode in preference to the
basic metal. Some difficulty has been found in placing cadmium accurately
relative
to iron. Apparently, in the presence of moisture and corrosive substances,
the easily changing iron potential and the over-voltage of hydrogen on
iron, play
a decided role. Regardless of the difficulty of definitely establishing the
position of cadmium, practical experience has shown that cadmium undoubtedly
stands above
iron, and that it is now the best rust proofing agent, bar none.
Cadmium also
protects mechanically. Even though cadmium is electronegative to iron, and
porosity does not mean immediate rusting of the underlying iron, it
is essential that the plate be as free as possible from porosity, in order
that maximum benefit be derived from its properties. The ideal plate
must also have
perfect adherency, be free of blisters and irregularities, be ductile, dense
and preferably bright in color. Cadmium deposits with such characteristics
are obtained from most of the cadmium solutions in use today.
Efficient results
in cadmium plating, as in other types of plating, depend essentially
on three factors—the proper type of solution and means of controlling this
solution’ proper electrical conditions, and proper handling of work.
Under this latter may be included cleaning, pickling, rinsing before and after
plating,
handling, storage, etc.
The majority of solutions used today for the electrodeposition
of cadmium produce deposits of finest crystalline structure and a minimum of
porosity, as well as
maintaining a constant composition under a maximum of varied operating conditions.
Even with an ideal solution, work may often be spoiled by bad electrical connections.
All leads should be of sufficient size to carry the necessary current, and
all connections and contracts should be clean and tight. A source of
trouble which
is often overlooked are the contacts which the anode hooks make. All other
connections are made by means of clamps or bolts. Here, however, contact
is nearly always
made by mere suspension, so that even under ideal conditions, there is possibility
of electrical loss here. Corrosion products often form under the anode hooks,
thus increasing the electrical losses still further. Even with proper leads
and connections all the way from the generator to the solution, there
is a final
point often overlooked. Wires and racks for hanging work must be of a size
to carry the necessary current. Obviously a part which requires 30 amperes
for proper
plating, should not be suspended on a wire with a carrying capacity of only
15-20 amperes. This, however, is often done.
Even after work has been hung in the plating
bath, it may be spoiled by improper amperage, or current distribution. In the
matter of current distribution, best
results are naturally obtained with only one piece in the tank at a time. In
production, however, the tank must be loaded, and often loaded with pieces
of varied size. Current is free to pass through various channels, and
the amount
that does pass through a given piece is a function of the size of the piece;
contacts to anode and cathode, size of racks or wires; distance away from anode;
the solution itself, and finally the voltage impressed. Each time the tank
is loaded, the chief variables are the number, size and shape of the
pieces, and
the contacts. The operator should see to it that each piece is gassing as evenly
as possible, that the contacts do not become hot, and that the plate is as
evenly deposited as possible. Sharp edges always receive the most current,
consequently
they will brighten first. If the edges are dark, the work is burned, which
indicates too much current. It is best to strike a happy medium between
high and low current
density.
Poor cleaning is responsible for a multitude of plating
ills. It is readily recognized and accepted, but it is very difficult
to remedy in many cases. Since
the cleaning
problem is usually an individual problem, and so many excellent articles have
been written on cleaning and pickling, which later may be considered a branch
of cleaning, that I will not go deeply into this subject. I will merely state,
that even though it is sometimes possible to obtain a good cadmium deposit
on dirty looking work, consistently efficient results can only be obtained
by perfect
cleanliness at every step in the plating department.
After the work
has been cadmium plated, it should be immediately rinsed” in
cold water and then in hot water at approximately boiling temperature. The
water should be clean to prevent staining. Where facilities permit,
small parts may
be dried in a centrifugal, which eliminates water staining.
The plated work should
be removed as soon as possible from the acid fumes and steam atmosphere of
the plating room; it should be stored in clean boxes, handled
by clean hands and placed upon clean work benches.
In this paper, I have endeavored
to show very briefly the necessity for such a metal as cadmium, its origin,
its development and rise to a most commanding
position in the electro-plating world, and finally a brief and general discussion
of the best plating room practice to insure successful cadmium plating.
A REPORT
OF THE POSSIBILITIES OF POISONING FROM CADMIUM PLATE
Read at Detroit
1929 Meeting
by George Dubpernell
The question of the possibilities of poisoning
from cadmium plate frequently comes up, but the published information on this
subject is very scarce. The possibilities
are often vastly overestimated, there being no definite evidence available
to the contrary. Under these circumstances it would appear advisable
to discuss
the possibilities in detail, in order to define them.
There appear
to be no cases on record of persons having died from cadmium poisoning
due to cadmium plate
or cadmium salts. An authoritative text book on ”Toxicology” states
that, ”So far as one may find, no deaths have been reported from employment
of cadmium salts and in man the acute effects are those of a gastrointestinal
irritant.”
A British engineer is said (Chemical Trade Journal, Volume
75, pages 3 to 5, 1924) to have died from the effects of cadmium vapor
which he inhaled
when some
cadmium was melted and overheated in an open crucible, instead of in the regular
furnace, which was out of order at the time, There is no danger of this kind
in the use of cadmium plated products, as the quantity of cadmium on them is
so small.
Only one article appears to have been published on the
use of cadmium as a coating metal for food containers, and that is German
(Zeit, fur Unters.
der Lebensmittol,
Volume 54, pages 392-6, May, 1927). Lead and zinc are prohibited in contact
with foods in Germany, and this article is mainly a plea for the inclusion
of cadmium
in the lead-zinc law.
Here in the United States, the Bureau of Animal Industry
of the Department of Agriculture has prohibited the use of both zinc and cadmium
in direct contact
with meat or meat food products for considerable periods of time. This does
not mean the complete prohibition of cadmium or zinc plating in the packing
houses,
however, and it is of course permissible to protect various parts of mechanical
equipment, etc., from rusting in this manner, as long as they do not come into
direct contact with meat or meat food products for a long time.
Cadmium salts
are not accurately described as poisons to the human system from the ordinary
person’s point of view. In some cases they have been prescribed
by physicians for use as an emetic. The government chemists have shown that
cadmium salts are 8 to 9 times as effective as zinc salts when used as an emetic.
The
same men, and also many other workers, have found no cumulative effects of
cadmium salts when fed to animals for long periods of time. (Journal of Pharm.
and Exp.
Therap., Volume 21, pages 1-22, 59-64, 1923, and Journal Pharmacol. Proc.,
Volume 13, pages 504-5, 1919.) That is quite different from the case of lead
salts.
If you get just a trace of lead, it continually stays in your system and eventually
it becomes badly poisoned by it, if you keep on getting a small quantity of
lead.
The
effect of cadmium salts when taken internally is to cause severe vomiting,
diarrhea, nausea, headaches, etc., and temporary local injury to certain
organs.
The most severe case on record was described by G. A. Wheeler in Boston Med. & Surg.
J., Vol. 95, P. 434-6, 1876, in which several women took from .25 to 1 grams
of cadmium bromide, each, accidentally; both were made violently ill; one recovered
in about 24 hours and the other in about 5 days.
Cadmium salts have valuable antiseptic
and bactericidal properties and have been recommended for various therapeutic
uses.
Cadmium is only very slightly soluble
in neutral or alkaline solutions, and in solutions of organic substances in
general. It is, however, slightly soluble
in weakly acid solutions, which sometimes occur in connection with foodstuffs.
Zinc, on the contrary, is soluble in both acid and alkaline media and generally
at a greater rate owing to its higher solution pressure. The difference between
zinc and cadmium salts considered as poisons is one of degree only, the cadmium
salts being stronger in their action.
Cadmium metal is fairly rapidly attacked
by any foodstuffs of an acid character, such as vinegar, hard cider, fruit
acids, etc. Fresh meat, blood, milk, etc.,
have practically no action upon metallic cadmium when they are fresh and edible,
because they are slightly alkaline in reaction. However, when these protein
containing foodstuffs decompose or turn sour, they generate acids or
amino compounds which
may have an action on cadmium, and when the cadmium is then dissolved, it causes
sickness for a few hours or a day if sufficient quantities are ingested into
the human system. We have actually encountered at least several such cases
of sickness caused by cadmium getting into foodstuffs; the results in
these cases
were rather unpleasant, and painful internal disturbances, frequent vomiting,
etc., occurred.
The situation can probably be summarized as follows: Cadmium
in its dissolved state is a powerful emetic and its general use in contact
with
foods is to be
avoided. It is only possible to use it in specific cases where the conditions
are definitely known and do not vary, where the foodstuffs in question is neutral
or alkaline in reaction, and will not turn acid.
Acid food products such as vinegar,
lemon juice, and other fruit juices, sour milk, etc., may attack cadmium plate
quite readily and cause illness to persons
who eat the foodstuffs.
CHAIRMAN VAN DERAU: Have any of you any questions to ask
of Mr. Dubpernell?
MR.
JOHN E. STERLING: I would like to ask Mr. Dubpernell a question. In the event
of knives cutting into salt meat, and so forth, you think the cadmium plate
would be affected?
MR. DUBPERNELL:
No, I certainly don’t. That was where this
question first came up, in the packing houses. I have here some shroud pins that
were tested
for use. (Shows pins.) These had been immersed in fresh meat over night while
it was cooled. You see, they kill the animal and then pin a shroud on it with
these pins. They are put in the meat when the meat is warm and fresh, and then
the meat is cooled in the refrigerator over night. These were immersed eight
times, eight over night periods, and the cadmium is still on them. If you were
going to get any injurious action, the cadmium certainly would have been taken
off in that length of time. Experience has shown that they can use these shroud
pins, put them in meat over night for—I don’t know, they don’t
know themselves, but they have told me as much as one hundred times before
the cadmium is appreciably attacked. Possibly at the end of that time it has
been
worn off by pushing in and pulling out.
MR. STERLING: How would that apply to
salt and pickled or brined meats?
MR. DUBPERNELL:
I imagine it would be all right in that case, too. But you have to be careful;
you can’t go too far. Fresh products are all right. It is
something salty and neutral or alkaline in reaction. But the minute you get anything
that may turn acid, for example, if you don’t wash these things off and
leave particles of meat on them, as the meat decomposes it will corrode the
cadmium. If you keep using it in fresh products it is perfectly all right.
A. E. S. PAGE
Assembled Expert Scraps With and Without Significance
It looks like
our capitol has at last gone dry.
Did you notice R. J. Hazucha and
J. Oberender doing a lot of taxi riding Sunday evening? Rudy says there was
no beer and John agrees.
The Platers looked so tarnaly
sober many were taken for Senators in the corridors
of the hotel.
H. Flanagan sure
forgot his knickers, and we missed his good wife. Also Mrs.
Tom Haddow, even if Tom don’t play with knickers.
A. P. Munning, Capt. Taylor,
Van Winkle Todd, Archie MacDermid and Sam Huenerfauth were there. Did you see
them spreading the stuff that makes good around the lobby.
Our
good friend, Dr. De Baun, was there as usual and we’re glad he was.
Balti.-Wash.
Branch members did themselves proud and we all thank them.
Dr. Blum
sure did not get much sleep during the annual meeting and his good wife gave
freely of her good offices.
Our past editor sure ought to be able to watch
around now after that wonderful
testimonial of friendship.
Horace, Phil
and Oliver, three must get theres. ”Yes.”
Did you notice
those Slattery’s, John, Tom and the missus, all busy?
Oh
boy! Did you notice the way the gang ate those box lunches at the Navy Yard?
Some
thought that visit to the Tomb of the Unknown Soldier and depositing our respects
in form of wreath by Boy Scout R. Mesle. Offices also.
Did you see Ed Musick and Geo. Laurence at the desk? Horses.
Yea.
Where was E.
Lamoureux H. H. Williams and Ed Willmore?
|