A NEW RUST PROOF BLACK FINISH FOR
IRON AND STEEL
By Charles H. Proctor
The
slogan of a nationally known paint manufacturer protect the surface and
you protect all, is truly applicable to the metal fabricating industry
whose product must of necessity be exposed to atmospheric influences, which
produce-corrosion and the resulting rustthe great destroyer of ferrous
metal.
We have been advised by metallurgists
and investigators of atmospheric corrosion of iron and steel, that if it were
possible to produce an absolutely pure iron, its surface would not rust. They
cite as an example an iron pillar located near one of the great gates of the
City of Delhi, India, that has stood for 1600 years, exposed to the ravages
of atmospheric influence and destruction and still stands as a remarkable example
of the rust resisting qualities of pure iron. We can wander over the civilized
world and find examples of architectural iron fabricated hundreds of years ago
by master blacksmiths at the village forges that have resisted the action of
atmospheric influence for generations. What is the reason? Is it possible that
in those long years ago, the workers in iron, for steel was unknown, did produce
a better iron or incorporate some factors that did produce a better iron? It
is not for me to discuss this phase of the subject. Metallurgists and research
chemists still have a world field in which to exploit their ideas. My work is
to produce commercial results, as the plater states when theory is discussed;
he remarks theory is splendid, but I must produce the goods. We all know the
ravages of rust when we consider for a moment that five million tons of coal,
our greatest natural asset, were used in 1916 and at this date possibly more,
in making one million tons of steel to replace that which was lost by rust.
The importance of the saving of these products and the labor entering into them
can be readily appreciated. One railroad alone reported several years ago a
daily loss covering its entire system of eighteen tons per day of metal due
to corrosion.
There must come a day when more attention
must be paid to the protection of iron and steel from atmospheric corrosion
and the resultant rust, the great destroyer, if future ages are to enjoy and
benefit from the wonderful metals, iron and steel, we so lightly cast aside.
Nature has been bountiful to America in natural resources but as a nation we
are wasteful and profligate of these natural resources. Never again in the history
of man will natures laboratory place below the surface of the earth and
in the hills and mountains, the natural resources we have been blessed with
throughout the world. Evolution of men and material only occur upon the surface
of the earth, not down in its depths beyond the reach of the life-giving sun.
It is not for me to elaborate upon
scientific truths; they are always with us but some day humanity of the future
must do so to conserve the natural resources that is left from the iron age
of today.
In the electroplating industry nearly
every first-class plater that has made a thorough study of his art understands
the methods in vogue for the deposition of metals upon iron and steel to protect
the surface against corrosion and rust, and incidentally heat, and chemical
applications which in a great measure protects steel and iron from rust when
correctly applied to their surfaces.
Zinc and cadmium are pre-eminent
as metal factors. Aluminum is used to some extent by the calorizing method;
a sister method to sherardizing.
In the production of rust proof black
finishes upon iron and steel by heat methods, the Bower Barff, Bradley, Bon
Tempi and Gesner methods are used to a more or less extent. They are all based
upon the patents of Bower and Barff, granted in 1857, and consist essentially
of heating iron and steel in a closed retort to cherry red at about 1200 deg.
F., then superheated steam is injected into the retort, which finally results
in the formation of an adhering and penetrating coating of black magnetic oxide
of iron, when the surface is finally protected with an oil such as linseed oil
and dried thoroughly a rust resisting black finish results.
The Bradley, Bon Tempi and Gesner
patents are essentially a modification of the Bower-Barff process, a hydrocarbon
such as benzine or gasoline being injected with the steam. The patentees claimed
much superior results to that obtained by the Bower and Barff method. This decision
is still an open question, and debatable.
In the great hotels of American,
the Bower-Barff finish plus later modifications, is used extensively upon builders
hardware and results in a very lasting finish, unaffected by oxidation and atmospheric
rust. There are only three or four nationally known builders hardware
manufacturers who produce this finish in American.
The Parker process is quite extensively
used as a black rust proof finish, and without the final protective oil coating;
as a basis for better rust resisting enameled surfaces applied to steel, etc.
The Parker process is based upon the original patents of, Coslett and Richards
of England. One of the original patents of Coslett expired last year, so is
now public property.
Zinc is still the great factor in
the protection of steel from corrosion, rust and whether applied by the molten
or electrodepositing method, it will possibly never be replaced, due to the
low cost of the metal.
Cadmium, due to its much higher cost,
will be used for specific purposes. Its resistance to chlorine laden atmospheres
of the sea coast makes it applicable to iron and steel surfaces when the cost
of the metal is not prohibitive.
Electro zinc plating is constantly
increasing in volume. The automotive industries use zinc electro-plated products
extensively and the zinc mercury cyanide solutions are gradually eliminating
the acid zinc type of solutions, due to its greater throwing power and greater
hardness of the zinc mercury deposit which increases its resistance to friction
and wear, and atmospheric corrosion.
I learned the other day in the Middle
West that one of the greatest manufacturing industries in the world, whose product
is found over the entire civilized world, will discard all acid zinc solutions
in favor of the cyanide type this year, due to reasons heretofore stated. The
firm in question has been experimenting with zinc deposits for several years
in its research engineering departments, in New York and Chicago. I have developed
a rust proof black finish for steel that is very simple of application. The
method can be installed in any plating department that must produce rust-resisting
finishes upon steel or iron. The basic idea is not new because three years ago
I presented a paper at an educational session of New York Branch entitled, The
Production of Imitation Silver Deposits by the Aid of Zinc Cyanide Deposits
and Antimony Oxide. This original paper, then, was the basis for what
I am pleased to term a new rust proof black finish. The details of the production
of the finish are as follows:
Process for Producing a Rustproof
Black Finish Upon Zinc Plated Steel Surfaces
Part No. 1
The steel articles to be zinc plated must be clean from grease, oils, etc.,
and free from rust and scale. The usual procedure in cleansing steel goods for
plating can and should be adhered to.
Part No. 2
The articles should then be immediately plated in the Duozinc Cyanide solution.
Water . . . . . . . . . . . .1 gallon
Cyanegg . . . . . . . . .4 ounces
Zinc Cyanide . . . . . 4 ounces
Caustic Soda . . . . .4 ounces
Cyanobrite . . . . . .1/8 ounce
E. M. F. 5 to 6 volts. Amperage 25 S. F.
Minimum Temperature 110/120° F.
Anodes Duozinc Electrolytic Spelter 2% Mercury.
Time of Plating, 10 minutes minimum.
Part No. 3
Immediately after Duozinc plating, wash thoroughly in cold water, then immerse
in the following solution for a moment:
Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 gallon
Caustic Soda . . . . . . . . . . . . . . . . . . . . . . 4 ounces
White Powdered Antimony Oxide . . . .1/2 ounce
Temperature 120/140° F.
A dead black adherent coating will
result, remove from the solution quickly, then wash in cold and boiling water
and dry with heat.
The black coating should be protected
with a thin coat of lacquer (air drying).
Black Nubelac N. L. L.2050
B. and Nubelac Thinner N. 331 in proportion of 3 parts to 1 part lacquer is
an excellent protective coating. The Nubelac products are manufactured by the
Nubian Paint & Varnish Co., Chicago, Ill.
We have found that Benzole colored
with Nigrosine Black (Benzole Soluble) and a small amount of a cheap furniture
varnish to obtain an adherent mixture will answer the purpose. This mixture
should not cost more than 40 cents per gallon.
Any cheap air drying black mixture
can be used or any form of black lacquer commercially advertised.
If a dipping process is used to give the articles the final black protective
coating, then it is possible that an air blast can be used to an advantage in
blowing off excess and drips.
The use of antimony solutions in
the coloring of metals is nothing new. I have advocated them in one form or
the other for years. Hiorns, in his splendid work entitled, Metal Coloring
and Bronzing, published in London in 1892, gives considerable detail covering
bronzing and coloring of various metals with antimony chloride and hydrochloric
acid and antimony sulphide, and sodium hydrate. See pages 213 and 234. In the
same work a formula is mentioned on page 212, due to Botteger an authority on
electro-plating and metal coloring covering sodium hydroxide, mercury and antimony
chloride. Duillo, on page 234 of Hiorns work, mentions an
antimony solution for producing a black color upon zinc which requires an oil
or varnish to protect the black, or it will rub off. There exists a U. S. patent,
No. 1,436,729, dated November 28, 1922, for black coatings upon zinc prepared
from water 150 gallons; sodium hydroxide 76% 2 pounds, butter of antimony 1
pint. The solution must be heated to 212 deg. F. Prior art was established by
Hiorns in 1892 for coloring zinc black with antimony salts and sodium hydroxide
solution. Therefore, in my opinion the patent referred to is invalidated and
the writer does not consider in presenting this paper that he infringes upon
any existing patent.
The solution I have advocated to
produce the black finish upon the zinc plated surface, acts instantly and is
adherent. Tests made with steel automobile rims finished by the process and
without the final coat of protective black lacquer or other medium in the testing
department of one of the largest automobile rim manufacturing plants in the
United States, have found that the rust-resisting qualities of a regular zinc
plated steel rim, plated in the Duozine cyanide solution has been increased
from the normal 48 to 60 hours salt spray test, using the regular 20 per cent
salt spray test, to 120 hours or more, or an increase in resistance to corrosion
and rust of more than 100 per cent. With the application of the final coating
of black lacquer or similar protective coating for the black finish, the corrosion
resistance would be further increased.
It is the authors opinion that
the process being simple in application can be used extensively in the metal
fabricating industry, when of necessity a rust proof black finish is desirable
and should prove to be a valuable addition to present known methods in the electro-plating
industry.
RESEARCH ON SPOTTING OUT
AT THE BUREAU OF STANDARDS
As you all know, during the past
two years the American Electroplaters Society has been engaged in collecting
from manufacturers funds to be used for co-operative researches on electroplating
at the Bureau of Standards. The goal is a fund of $10,000 per year for three
years, based on contributions of $50 or more per year from each subscribing
firm. To date about $4,000 per year has been raised, and the campaign is being
continued by their Research Committee. All of the branches have learned from
Mr. R. J. OConnor, Chairman of the Research Committee, just what each
member can do to help the committee.
Mr. W. P. Barrows, who has been working
in the electroplating section of the Bureau, has been appointed as a Research
Associate on this fund, and is just starting an investigation of the causes
and prevention of spotting out. While this difficulty is especially
experienced with the so called oxidized finishes on such articles
as builders hardware and lighting fixtures, which consist of iron or steel,
plated with copper or brass, treated with a sulphide solution, and finally lacquered;
it is also occasionally observed on silver or gold plated articles, and even
on solid brass that has not been plated. The information gained will undoubtedly
be useful to every plater.
In company with Dr. Blum, Mr. Barrows
recently visited a number of plants, mostly in Connecticut, and received much
valuable information, and samples of both satisfactory and defective products.
All the manufacturers visited expressed their willingness to co-operate in this
investigation.
The exact course of the researches will depend upon the information derived
from the preliminary study now in progress. The indications are that numerous
factors may be involved, such as porosity of the cast or rolled metal, or variations
in the methods of cleaning, plating, rinsing, oxidizing and lacquering
the articles, or in the nature of the materials used in wrapping, or in the
conditions of storage, exposure or use. A considerable period will undoubtedly
be required to determine the relative effects of each of these possible factors.
Whenever the results warrant, progress reports will be published in the Review.
In order that this investigation
may be made as comprehensive as possible, the Bureau will be glad to receive
from platers or manufacturers, typical samples of spotted products, with full
information regarding their origin and history.
As above indicated, this is just
the beginning of the research work on these funds collected or subscribed by
the Electroplaters Society. All of you no doubt think of other objects
that should be studied.
When more funds are available, additional
researches on electroplating will be started at the Bureau. The progress made
will depend largely on the interest and support of the electroplaters and their
employers.
SILVER PLATING OF TABLEWARE
By Mr. Elmer Roy Unruh, Dayton
Branch
The electro-plating with silver was
the first of all the electro-metallurgical processes to be carried out on a
large scale, silver plating having been carried on practically for more than
75 years.
All silver plating is conducted in
cyanide solutions, not because it is impossible to deposit silver from other
types of solutions, but because the metals to be plated would precipitate silver
from the solution of its ordinary salts, and silver deposited from solutions
of such salts as the nitrate or acetate is usually in very coarse crystals.
Silver deposited from regular cyanide
baths is rather coarsely crystalline and frosted in appearance. To remedy this,
carbon disulphide dissolved in sodium cyanide solution or in an old silver solution
is added to the bath in small quantities to produce a bright deposit.
The fact that most of the metals
are above silver in the electrochemical series and therefore tend to precipitate
it from its solutions makes difficult the plating of such metals with adherent
coatings of silver. The treatment required for any metal depends upon the potential
of that metal in the silver solution, which in turn depends upon the composition
and silver ion concentration of the solution. It has been found that the potential
of silver, and therefore the silver ion concentration, is decreased in a silver
solution by the addition of free cyanide. This is the explanation for the use
of a silver strike high in free cyanide content for the initial plating upon
many metals. From a cyanide silver solution containing no free cyanide, iron
or steel can readily deposit silver by immersion, but from solutions with much
free cyanide no such deposition occurs. This is confirmed by the fact that in
silver solutions containing no free cyanide the potential of iron was found
to be negative to silver (able to throw silver out of solution), while in those
containing free cyanide the potential of iron is positive to silver (not able
to displace it.)
It is the usual practice, especially
in the east, either to silver plate direct on the metal, or immerse in a mercury
dip and then silver plate. Steel articles are given a double silver strike,
first in a solution containing 1/4 oz./gal. of silver, 1/4 oz./gal. copper and
12 oz./gal. sodium cyanide, then in a second solution containing 1/2 oz./gal.
silver and 16 oz./gal. sodium cyanide. Brass and nickel silver articles are
immersed in a mercury dip, an adherent deposit of mercury being precipitated
upon the surface, and struck in a silver strike solution containing 1/2 oz./gal.
of silver and 16 oz./gal. sodium cyanide.
It is the usual practice in the west
to give brass, nickel silver and steel articles a light nickel plate, then silver
strike and silver plate. This is the method we have found most satisfactory
for silver plating tableware.
In the plating of tableware we have
three distinct types of work or three distinct types of metals to prepare for
the plating operation, each one of which requires a slightly different method
of preparation.
One class consists of flatware, such
as forks, spoons and similar articles made of either nickel silver or brass.
The same treatment suffices for both metals, however. The articles come to the
plating room direct from the buffing room and are covered with tripoli composition
and buffing dirt. The articles are placed in baskets and are immersed in boiling
whale oil soap solution and remain here until the tripoli and buffing dirt are
removed, which usually takes from 15 to 30 minutes. The baskets are then agitated
in a warm solution of a good grade of soap chips to remove all the whale oil
soap solution and to brighten the articles. The baskets are then rinsed in boiling
water to remove the soap solution, and the articles are ready for the plating
operation. This may seem a rather lengthy operation for the removal of tripoli
and buffing dirt, but it is the only satisfactory method we have found that
will consistently remove the buffing dirt and tripoli and not impair the polish
and lustre of the work.
After removal from the baskets, the
articles are placed in plating racks and are submitted to the following plating
cycle: (1) Boiling electric potash, and (2) dipped direct into 20% solution
H2SO4, (3) rinsed in running water, (4) returned to boiling electric potash,
(5) rinsed in water, and (6) dipped in 20% solution H2SO4. We found it advisable
to use a separate acid dip for this step and not use acid dip in step (2), as
a greasy scum forms on the surface of the acid due to immersion of articles
covered with hot potash, (7) rinsed in water, (8) nickel plated for 5 minutes
at 2-3 volts, (9) rinsed in water, (10) silver strike, and (11) silver plate.
The second class of work consists
of knives made of the ordinary steel for cutlery purposes. After the knives
are polished they are washed free from grease and emery in hot coal oil and
dried in sawdust. The pattern is then embossed on the handles and the knives
are sent direct to the plating room. The knives are covered with a slight sawdust
film and some grease from the embossing operation. They are placed in baskets
and agitated in a boiling potash solution for 10 minutes and then rinsed in
water and placed in a small racking up tank filled with borax solution. The
knives are removed from the racking up tank and as they are removed each blade
is wiped with a wet rag to remove any scum left by sawdust and placed in a plating
rack. When the rack is filled it is suspended in a storage tank of borax water
until enough racks are ready for a complete run. This method of preparation
may seem rather laborious and costly, but we have found that it pays on this
class of work for each operation plates 200 dozen or more knives day after day
without having a single reject. The racks of knives are now submitted to the
following plating cycle: (1) Boiling electric potash, (2) rinse, (3) 20% H2SO4,
(4) rinse, (5) boiling electric potash, (6) rinse, (7) 20% H2SO4, (8) rinse,
(9) nickel plate 10 minutes at 2-3 volts, (10) rinse, (11) silver strike, (12)
silver plate.
The third class of work consists
of knives having a stainless steel blade and a low carbon steel handle. These
knives are made by welding the handle stock to the blade stock and subsequently
forging, rolling and grinding. When completed this weld is an irregular line
located in the bolster of the knife. It is required that the handles of the
knives be plated and the blade remain unplated. If the usual plating procedure
is followed the plate can be stripped off the stainless steel portion, as stainless
steel does not respond to the same treatment that ordinary steel does, back
to the low carbon steel handle and will expose this irregular weld, presenting
an undesirable appearance, so it is desired that an adherent silver plate be
placed on the small section of stainless steel in the bolster of the knife.
These knives as they come to the
plating room are in the same condition as the ordinary steel knives. They are
placed in baskets and agitated in the boiling potash solution for 10 minutes,
then rinsed and placed in a racking up tank of borax water. They are racked
up from this tank and as soon as they are racked are submitted to the following
plating cycle: (1) Boiling electric potash, (2) rinse, (3) electric concentrated
HCl dip, the knives being cathode, anodes being carbon, (4) rinse, (5) boiling
electric potash, (6) rinse, (7) electric concentrated HCI dip, (8) rinse, (9)
concentrated HCl dip, (10) rinse, (11) nickel plate 10 minutes at 2-3 volts,
(19) rinse, (13) silver strike, (14) silver plate.
The composition of all solutions
used in silver plating tableware is kept under control by regular chemical analyses.
The solution which charges composition
most rapidly and which is the source of much defective work in silver plating
is the silver strike. We have found it advisable to maintain very rigid standard
conditions for striking as regards cement density and composition of solution.
The composition of the strike used in our method is 3/4 Troy oz./gal. silver,
and 10 oz./gal. free cyanide. Strikes are analyzed for silver and free cyanide
content at least weekly and usually twice a week and additions made to maintain
above composition as closely as possible.
Very little trouble is experienced
with the nickel solutions as we deposit a very light nickel plate. The solutions
were originally made up of 20 oz./gal. single nickel salts, 3 oz./gal. sodium
chloride, 3 oz./gal. boric acid. The pH of the nickel solutions is determined
weekly and maintained at 5.9 by additions of boric acid. The nickel and chloride
content is determined monthly and maintained by additions of single nickel salts
and nickel chloride.
Little difficulty is experienced
in the operation of the silver solutions if the composition is kept in the neighborhood
of 4.00-5.00 oz./gal. silver and 7-9 oz./gal. free sodium cyanide and if care
is taken in the use of the carbon disulphide brightening solution. There is
much discussion concerning the carbonate content of silver plating solutions.
Formerly it was customary to freeze out the carbonates during the winter months,
and later the use of carbonates in amounts up to 12 oz./gal. was advocated to
increase the conductivity of the bath. I am of the opinion that the presence
of carbonates up to 12 oz./gal. is beneficial and that the advantages gained
by freezing out the silver solutions is not due to the removal of carbonates
but to the removal of other inert salts. To gain further information along these
lines I operated representative silver solutions for over four years and was
surprised to find one morning this summer that crystals had separated out from
the solution and attached themselves to the anodes and anode rods. Upon analysis
I found the crystals to be sodium fenocyanide. I have not definitely determined
whether they were introduced into the solution as an impurity in the sodium
cyanide or whether they were formed in the solution, but I am sure that the
benefits derived from freezing out silver solutions are due to the removal of
sodium fenocyanide and similar inert salts, rather than due to the removal of
sodium carbonates.
The alkalinity of the cleaning solutions
or potashes is determined weekly and computed in terms of per cent NaOH. The
alkalinity is maintained at from 4-8% sodium by dioxide by additions of one
part caustic soda to two parts soda ash.
In conclusion of this article on
silver plating of tableware I might say that the operations and methods I have
described are those used in producing the better grades of silverware. However
we also produce cheap grades and for this purpose we have found that an automatic
plating machine is very satisfactory in increasing production and reducing the
amount of experienced help required.
We are using a Full Automatic Plating
Conveyor, which has the following cycle:
Electric cleaner . . . . . . . .
3 minutes
Cold rinse . . . . . . . . . . . .35 seconds
Cold rinse . . . . . . . . . . . .10 seconds
Sulphuric acid dip . . . . .35 seconds
Cold rinse . . . . . . . . . . . .10 seconds
Nickel plate . . . . . . . . . . . .5 minutes
Cold rinse . . . . . . . . . .2 1/2 minutes
Silver strike . . . . . . . . . . .35 seconds
Silver plate . . . . . . . . . . . . 3 minutes
Standing rinse . . . . . . . .10 seconds
Cold rinse . . . . . . . . . . . .35 seconds
Dryer . . . . . . . . . . . . . . 6 3/4 minutes
We have also found that this cycle
is satisfactory for work receiving a heavier deposit than that which can be
obtained in three minutes, so we have placed a variable speed moving cathode
silver plating tank in conjunction with the automatic plater so that it can
be used for work receiving a heavier deposit by having an operator remove the
plating rocks from the work hanger of the automatic plater as they come out
of the strike, place them on the variable speed plater to get the deposit and
return the rocks to the work hanger (of course not the same hanger they were
removed from) of the automatic as it enters the silver solution.
ELMER ROY UNRUH
Muncie, Ind.
One kind of Plating is East and another
is West,
While the self-same sneezes blow.
Its the place of the Sales and not the gales
Which bids it where to go.
Like the Hydrogen of the Cathode,
are the ways of the fates. Many salesmen never realize this until they are stopped
at the gates.