U.S. patent number 3,762,882 [Application Number 05/156,090] was granted by the patent office on 1973-10-02 for wear resistant diamond coating and method of application.
This patent grant is currently assigned to Di-Coat Corporation. Invention is credited to Zigmund R. Grutza.
United States Patent |
3,762,882 |
Grutza |
October 2, 1973 |
WEAR RESISTANT DIAMOND COATING AND METHOD OF APPLICATION
Abstract
A process for producing an extremely hard and wear resistant
coating on a basis metal comprising the electro-deposition of fine
grained diamonds and diamond particles in a metal matrix upon said
basis metal. The coating comprises a uniform electrolytic deposit
of a metal matrix having embedded therein diamonds and diamond
particles ranging between 0.01 micron to 30 microns in size.
Inventors: |
Grutza; Zigmund R. (Detroit,
MI) |
Assignee: |
Di-Coat Corporation (Detroit,
MI)
|
Family
ID: |
22558053 |
Appl.
No.: |
05/156,090 |
Filed: |
June 23, 1971 |
Current U.S.
Class: |
428/615; 428/636;
428/934; 205/109; 428/932 |
Current CPC
Class: |
C25D
15/02 (20130101); Y10S 428/934 (20130101); Y10T
428/12493 (20150115); Y10S 428/932 (20130101); Y10T
428/12639 (20150115) |
Current International
Class: |
C25D
15/00 (20060101); C25D 15/02 (20060101); B23p
005/00 (); C23b 005/02 (); C23b 005/08 () |
Field of
Search: |
;204/16,181,45-55
;29/195C |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Kaplan; G. L.
Claims
I claim:
1. A method for electrodepositing a composite wear-resistant plate
consisting essentially of metal and diamond particles on the
surface of an element comprising making said element a cathode in
an electroplating bath of said metal having suspended therein
diamond particles in the form of fine powder having a particle size
from about 0.01 to about 30 microns average diameter and
electrolyzing said bath with externally applied current of
sufficient density to electrophoretically deposit said diamond
particles and said metal in a composite plate on said surface while
said diamond particles are suspended in said bath and while at the
same time keeping said bath in a quiescent state.
2. The method as set forth in claim 1 wherein the metal is selected
from the group consisting of antimony, bismuth, cadmium, chromium,
cobalt, copper, gold, indium, iron, lead, nickel, palladium,
platinum, silver, tungsten, tin and zinc.
3. The method as set forth in claim 1 wherein said diamonds are
from approximately 0.01 micron to 15 microns average diameter.
4. The method as set forth in claim 1 wherein said diamonds are
from approximately 0.01 micron to 1 micron average diameter.
5. The method as set forth in claim 1 wherein said bath contains
suspended therein about 150 carats per liter of diamond
particles.
6. The method as set forth in claim 1 and further including the
step of pretreating the diamond particles by washing the diamond
particles, soaking said particles in a wetting agent of the anionic
type, and rinsing said particles in water before suspending said
particles in said bath.
7. The method as set forth in claim 1 wherein the metal is
essentially nickel and wherein said bath comprises at least one
nickel salt selected from the group consisting of nickel sulfate
and nickel chloride.
8. The method as set forth in claim 1 wherein said diamond
particles are particles of synthetic diamonds and further including
magnetizing the cathode.
9. A composite wear resistant electroplate on a metal surface
comprising diamond particles in a metal matrix, said particles
having relatively smooth and ragged surfaces and having an average
particle diameter of from about 0.01 to 30 microns and being
electrophoretically deposited in the matrix in a spatially oriented
pattern wherein said smooth surfaces of said particles are directed
outwardly from said metal surface and said ragged surfaces are
directed inwardly toward said metal surface,made by a method
comprising making said metal surface a cathode in an electroplating
bath of said metal having suspended therein said diamond particles
and electrolyzing said bath while said particles are in suspension
and while keeping said bath in a quiescent state with externally
applied current of sufficient density to electrophoretically
deposit said diamond particles and metal on said surface in a
composite electroplate.
10. The electroplate as set forth in claim 9 wherein said diamond
particles are washed before being suspended in said electroplating
bath.
11. The electroplate as set forth in claim 9 wherein said diamond
particles are particles of synthetic diamonds and the method of
making includes magnetizing the cathode.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to the field of electroplating and more
particularly to the electrodeposition of fine to micro-fine
diamonds and diamond particles on a basis metal. The imvention also
relates to an electrolytic deposit of a metal matrix having
occluded therein fine to micro-fine diamonds and diamond particles
and to the plating baths from which the coating are deposited.
2. Description of the Prior Art
It is well known in the electroplating field that the dispersion of
certain solid and bath insoluble particles in an electroplating
bath will result in the deposition on the basis metal of a coating
of the metal of the electroplating bath having dispersed therein
the particles of the solid material. The usual procedure has been
to suspend in a nickel electroplating bath finely divided particles
of certain metals and/or the bath insoluble oxides or salts of
these metals. The coating thus produced usually enhances the
appearance of the plated article or serves to protect the basis
metal from corrosion. However, prior to the present invention, it
was not known in the art to electrodeposit a metal matrix having
embedded therein very fine diamonds upon the surface of an element
to produce an extremely hard and wear resistant coating.
Previously, when it was desired to apply a diamond containing
coating to the surface of an article, such as a grinding wheel
dresser or the like, the surface was first coated with an adhesive
and diamond particles were then sprinkled thereon or manually
embedded therein. The diamonds were then rolled or pressed through
the adhesive up against the surface of the article. This method, as
well as the coating produced thereby, have several major
disadvantages. One of these is that minor irregularities may be
produced because of the differences in particle size which are
inherent in any screening or sizing operations of the diamond
particles. Another is the difficulty encountered in accurately
positioning the diamonds so that their apexes project the desired
amount out of the surface of the adhesive. A third is the
difficulty of producing a coating containing more than one layer of
diamonds embedded therein.
SUMMARY OF THE INVENTION
The present invention comprises a method of forming a wear
resistant coating on an article by the electro-deposition of fine
and micro-fine diamond particles upon said article. The article to
be plated is made a cathode and a layer which consists essentially
of metal and of diamond particles is applied to the surface of the
article by simultaneously electroplating said metal and
electrophoretically depositing said diamonds from a bath consisting
essentially of a salt or acid containing the metallic ion or
radical in solution and of said diamonds in suspension.
The plate deposited by this method consists of a metal matrix
containing occluded diamond particles. The diamonds are evenly and
uniformly distributed throughout the metal matrix thus forming a
uniform and continuous plate. The thickness of the deposit can be
varied and is dependent on the factors of current strength and the
time the article is left in the electrolyzed bath. The density or
concentration of the diamonds occluded in the metal matrix can be
varied by varying the amount of diamonds present in the plating
bath. It is possible to obtain a very thin metal coating containing
one layer of diamond particles or a thicker metal coating
containing a plurality of layers.
The plating baths of the present invention consist of aqueous
solution of the common electroplating metals such as cadmium,
antimony, bismuth, chromium, cobalt, copper, gold, indium, iron,
lead, nickel, palladium, platinum, rhodium, silver, tungsten, tin,
zinc and the like. The metals are present in the form of soluble
salts or acids. Various additives such as leveling and brightening
agents may be added to these baths. The diamonds are suspended in
the baths in the form of fine particles having an average diameter
of from between sub-micron size to 30 microns, although sub-micron
size particles, particles having an average diameter of less than 1
micron, are preferred as they produce fine and smooth plate.
Diamond particles above 15 microns in diameter produce some
roughness, especially on shelf areas where the particles can
settle. With most of the baths the maximum improvement in wear
resistance of the articles is attained when about 50 to 150 carats
(10 to 30 grams) per liter of the fine diamond particles are
dispersed in the baths.
The coating formed by this method is extremely tough and wear
resistant due to the occluded diamonds. Any articles that come in
contact with other surfaces, such as the wear, cutting or grinding
surfaces of tools, tool parts, taps, knives, saws, die punches,
gauges, shears, engine components and the like can be coated with
this coating to prolong their useful operating lives by reducing
wear and to reduce friction. Thus, for example, it has been found
that a cigarette filter cutting blade coated with the diamond plate
has a useful operating life up to four times greater than an
untreated blade. It has also been found that the frictional forces
between two surfaces coated with the coating of the present
invention are substantially reduced.
The present invention also includes the electroplate comprising a
metal matrix containing occluded diamond particles which is
produced by the aforementioned method. Likewise included in the
present invention are the various plating baths containing
suspended therein the fine and micro-fine diamond particles. This
invention also relates to various articles, such as cutting blades,
drills, die punches, bearings, and the like having deposited on
their surface a plate comprising a metal matrix containing occluded
diamond particles.
The present invention has many advantages over other previous types
of coatings. One of these lies in the extreme hardness possessed by
the coating, said hardness due to the presence of diamond
particles. Another advantage is that the diamond particles are
uniformly distributed throughout the metal matrix. Still another
advantage resides in the fact that the diamonds being deposited in
the coating electrophorically rather than manually as in the prior
art, they are generally of the same size, are accurately
positioned, and are identically oriented in the matrix.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In practice the article to be coated is made the cathode and
immersed in a plating bath containing soluble metal salts or acids
of the matrix metal. The cathode consists essentially of the matrix
metal. The diamonds, which have been pretreated, are suspended in
the bath in the form of fine bath insoluble particles and are kept
in suspension by a period of initial agitation which is terminated
when the solution is electrolyzed. The average particle diameter of
the diamonds can be between 0.01 micron and 30 microns and
preferably should not be greater than 15 microns. This particle
size has been found to be preferred and advantageous, with the most
preferred particle being of sub-micron size averaging from about
.01 to about 1 micron.
The concentrations of the diamond particles depend upon the type of
bath in which they are dispersed and the density of the diamonds
desired in the matrix. Thus in a Watts type nickel bath a
concentration of 100 carats (20 grams) per liter is found to give
optimum results, producing a nickel matrix containing 40 percent
diamond particles. In a chrome bath, on the other hand, it has been
found that for optimum results a diamond concentration of about 150
carats per liter is necessary.
It has been found that the untreated diamonds may tend in some
instances to agglomerate in the solution and to form roughness and
lumpiness in the plate. To overcome this problem the diamonds are
subjected to a special treatment before being introduced into the
plating bath. The treatment consists of cleaning the diamonds by
immersing them in hydrochloric acid. The diamonds are then cleaned
a second time by immersion in a solution of sodium hydroxide. After
the diamonds have been cleaned they are soaked in a solution of
coumarin sulfate and sulfuric acid. The amount of time that the
diamonds are soaked in the coumarin sulfate can be as long as 24
hours. The diamonds are then rinsed several times in water and
thereafter are soaked in a wetting agent of the anionic type. After
exposure to the wetting agent the diamonds are again rinsed with
water. Finally the diamonds are air-dried and added to a
concentrated solution of metallic salt or acid of the bath to be
added immediately to the bath or stored for a period of time.
Alternatively the treated diamonds can be added directly to the
bath rather than to a concentrated solution of metal salt or acid
of the metal. The treated diamonds are suspended in the bath at
random and do not tend to agglomerate but plate out as discrete and
individual particles.
The preferred metal matrix is one consisting essentially of nickel.
But other metals, depending upon the purpose to which the coated
surface is to be put, can be used. Among these metals are those
that are used in the more common types of plating baths: antimony,
bismuth, cadmium, chromium, cobalt, copper, gold, indium, iron,
lead, palladium, platinum, silver, tungsten, tin and zinc.
Both natural and synthetic or man-made diamonds can be used in the
present invention. It has been found, however, that the man-made
diamonds plate out faster than do the natural diamonds. Thus, under
identical conditions a solution having suspended therein man-made
diamonds will produce a plate having a slightly greater diamond
density than a plate produced from a solution having suspended
therein natural diamond particles. This phenomena is greatly
increased when the cathode is polarized. In order to increase the
density of the diamond particles in the matrix, in other words to
increase the rate of co-deposition of diamonds, a magnet is
attached to the cathode. The synthetic diamonds will then plate out
at a rate approximately 25 to 50 percent higher than if the cathode
was not polarized. The plate thus deposited will contain 25 to 50
percent more diamonds per unit area than one formed with an
unpolarized electrode. However, if natural diamonds are used in a
plating bath having a magnet attached to the cathode, the rate of
co-deposition of the diamonds is not appreciably increased. This is
thought to be a function of the mechanism by which the particles
plate out. Although this mechanism is not clearly understood, it is
possible that the adsorption of hydrogen ions and nickel ions by
the particles would give the particles a positive charge and in
this way they would tend to plate out. In addition, while naturally
occurring diamonds are not semi-conductors, the man-made diamonds,
due to the presence of small metal particles therein, are
semi-conductors. Adding a magnet to the cathode also tends to
produce a situation wherein two forces are acting on the synthetic
diamonds; magnetic and electrical, while with natural diamonds only
the electrical force is acting upon the diamonds. Nevertheless,
regardless of the mechanism of the co-deposition of these particles
and independent of whether they are naturally occurring or
made-made, the deposition of the particles starts immediately and
they plate out as uniform dispersions in the metal plate. Thus at
any point in the plating procss the surface of the metal plate has
distributed over its surface very many fine diamond particles in
various stages of being embedded in the surface.
Below are listed examples of the baths of this invention in which
the diamond particles are used.
EXAMPLE I
Grams/liter NiSO.sub.4 300 - 450 NCl.sub.2 30 - 75 H.sub.3 BO.sub.3
30 - 45 Diamond particles, .01 to 1 micron average diameter 1 - 20
pH = 2.5 - 4.0
EXAMPLE II
Grams/liter SbS.sub.3 40 - 60 Na.sub.2 CO.sub.3 90 - 110 Diamond
particles, .01 to 15 microns average diameter 1 - 20
pH = 2.0 - 5.0 EXAMPLE III Grams/liter BiO 30 - 50 HClO.sub.4 100 -
110 Diamond particles, .01 to 30 microns average diameter 1 - 20 pH
= 2.0 - 5.0
EXAMPLE IV
Grams/liter CrO.sub.3 250 - 450 H.sub.2 SO.sub.4 1.25 - 2.5 Lead
Anode Cathode current density, amp/sq. ft., 60 - 100 pH = acidic
diamond particles, .01 to 30 microns average diameter 10 - 30
EXAMPLE V
Grams/liter CoSO.sub.4.sup.. 7H.sub.2 O 500 NaCl 17 H.sub.3
BO.sub.3 45 Cathode current density, amp/sq.ft., 30 - 165 diamond
particles, .01 to 30 microns average diameter 1 - 20
EXAMPLE VI
Grams/liter Cu SO.sub.4.sup.. 5H.sub.2 O 150 - 300 H.sub.2 SO.sub.4
50 - 75 pH = acidic Cathode current density, amp/sq.ft., 15 - 40
diamond particles, .01 to 30 microns average diameter 1 - 20
EXAMPLE
VII Grams/liter KAu (CN).sub.2 2.1 KCN 15 Na.sub.2 HPO.sub.4.sup..
12H.sub.2 O 4 Cathode current density, amp/sq.ft., 1 - 5 diamond
particles, .01 to 30 microns average diameter 1 - 20
EXAMPLE
VIII Grams/liter In.sub.2 O.sub.3 200 H.sub.2 SO.sub.4 250 H.sub.2
SO.sub.4 120 - 200 Platinum anodes Cathode current density, amp/sq.
ft., 18 Diamond particles, .01 to 30 microns average diameter 1 -
20
EXAMPLE IX
Grams/liter FeSO.sub.4.sup.. 7H.sub.2 O 160 FeCl.sub.2.sup..
2H.sub.2 0 30 - 40 NH.sub.4 Cl 20 - 25 Cathode current density,
amp/sq. ft., 50 pH = 3 Diamond particles, .01 to 30 microns average
diameter 1 - 20
EXAMPLE
X Grams/liter Pb (OH).sub.2 PbCO.sub.3 150 HF (50 per cent) 240
H.sub.3 BO.sub.3 105 Diamond particles, .01 to 30 microns average
diameter 1 - 20
EXAMPLE XI
Grams/liter Palladium diamino nitrite 10 NH.sub.4 NO.sub.3 100 Na
NO.sub.3 10 NH.sub.4 OH 50 (cc) Diamond particles, .01 to 30
microns average diameter 1 - 20
EXAMPLE XII
Grams/liter Platinum diamino nitrite 10 NH.sub.4 NO.sub.3 100
NaNO.sub.2 10 NH.sub.4 OH 50 (cc) pH = 2 - 2.5 Diamond particles,
.01 to 30 microns average diameter 1 - 20
EXAMPLE XIII
Grams/liter SnCl.sub.2 30 - 50 NiCl.sub.2 240 - 320 NH.sub.4
HF.sub.2 60 NH.sub.4 OH - to pH of 2.0 - 2.5 Diamond particles, .01
to 30 microns average diameter 1 - 20
EXAMPLE XIV
Grams/liter AgCN 35 KCN 37 K.sub.2 CO.sub.3 38 Cathode current
density, amp/sq. ft., 1 - 2 Diamond particles, .01 to 30 microns
average diameter 1 - 20
EXAMPLE XV
Grams/liter NaCN 90 CdO 30 Cathode current density, amp/sq. ft., 10
- 15 Diamond particles, .01 to 30 microns average diameter 1 -
20
EXAMPLE XVI
Grams/liter Sodium tungstate 38 Sodium hydroxide 60 Dextrose 60
Diamond particles, .01 to 30 microns average diameter 1 - 20
EXAMPLE XVII
Grams/liter
__________________________________________________________________________
Zn (CN).sub.2 60 NaCN 23 NaOH 53 Cathode current density, amp/sq.
ft., 8 - 20 Diamond particles, .01 to 30 microns average diameter 1
- 20
In addition to the contents of the various plating baths as set
forth in the above examples, the plating baths may also contain
materials such as "addition agents" employed in small amounts to
affect the crystalline nature of the deposit, brighteners, leveling
agents, buffers to keep the solution at the desired pH, and salts
which can increase the conductivity of the baths if the salt or
acid containing the metallic ion or radical is not sufficiently
conductive. The concentrations and proportions of the above, as
well as the ingredients given in the foregoing examples, may be
varied to produce different results. Thus for example, a common
nickel plating solution may have the metal ion in the shape of
NiSO.sub.4, NH.sub.4 Cl, or (NHhd 4).sub.2 SO.sub.4 to increase the
conductivity of the bath; NiCl.sub.2 to assist anode corrosion;
H.sub.3 BO.sub.3 which acts as a buffer to maintain the pH of the
solution; a wide range of high-molecular-weight organic "addition
agents" such as organic sulfon compounds, examples of which are O
or P-Toluene sulfonamide, o-Benzoyl sulfamide, O-benzoyl sulfimide,
naphthalene, mono-, di-, or tri-sulfonic acid, sulfonated aryl
aldehydes, etc. to give smoother and finer grained deposits; and
brighteners such as cadmium sulfate. In the case of a tin bath the
tin salt may be furnished by Na.sub.2 SnO.sub.3, the conducting
salt by NaOH which also assists anode corrosion, the addition agent
to effect the deposit being glucose or other organic materials. The
bismuth bath may contain glue and cresol as addition agents; the
cadmium bath may contain glue, casein, molasses and gorilac as
addition agents; the silver bath may contain small amounts of
CS.sub.2 as a brightener; and the tin bath may contain sodium
acetate as a buffer.
The co-deposition rate of the diamonds is dependent on the size of
the particles, their concentration in the solution, and the current
density. Thus, for example, one carat of diamonds of 5 microns
average diameter in 5 milliliters of solution will plate out in
such a manner that a 90 percent diamond concentration will result
in a plate one mil thick. Diamond particles up to 15 microns in
size can be plated out at a current density as low as 2 amps/sq.
ft. However, diamond particles larger than 30 microns are deposited
with greater difficulty, even at high current densities.
As mentioned previously, the preferred metal matrix is one
consisting essentially of nickel. The diamond particles can be
suspended in a variety of nickel baths. However, all of these baths
are of the same general type, i.e., nearly neutral or slightly acid
solutions in which the nickel is present principally as a single
salt, usually the sulfate. One bath which has been found especially
effective contains 40 - 50 ounces per gallon of NiSO.sub.4, 5 - 6
ounces per gallon of NiCl.sub.2, 5 - 6 ounces per gallon of H.sub.3
BO.sub.3, 100 carats per liter of diamond particles of an average
diameter of 0.01 to 15 microns, and a pH of 3 - 6. This bath is
operated at a current density of 50 amps/sq. ft. and leveling
agents such as sulfonated aryl aldehydes are maintained at 0.7%.
Another nickel bath which produces excellent results consists of 45
- 60 ounces per gallon of NiSO.sub.4, 8 - 10 ounces per gallon of
NiCl.sub.2, 5 - 6 ounces per gallon of H.sub.3 BO.sub.3, 1 ounce
per gallon of NH.sub.4 Cl, 100 carats of diamond particles of 0.01
to 30 microns average diameter, and a brightening agent of the
sulfonimide type. The bath is operated at a current density of 40
amps/sq. ft., at a temperature of 150.degree.- 160.degree. F., and
at a pH of 2.5 - 3.0. Still another nickel bath which has been
found to be useful contains 26 ounces per gallon of NiSO.sub.4, 3.3
ounces per gallon of NH.sub.4 Cl, 4 ounces per gallon of H.sub.3
BO.sub.3, 100 carats per liter of micro-fine diamond particles, and
a pH of 5.6 - 5.9. This bath is operated at a current density of 25
- 50 amps/sq. ft. at a temperature of 110.degree.- 140.degree. F. A
nickel bath which has been found to produce extremely fine grained
nickel is one which contains 26 ounces per gallon of NiSO.sub.4, 23
ounces per gallon of NiCl, 2 ounces per gallon of NH.sub.4 Cl, 5 -
6 ounces per gallon of H.sub.3 BO.sub.3, and a pH of 1.5. This bath
is operated at a current density of 25 - 100 amps/sq. ft. and
contains 115 - 120 carats per liter of fine to micro-fine diamond
particles.
It will be noticed that all four of these nickel baths have a high
metal (nickel) ion content. Furthermore, "fine" diamond particles
are, for the purposes of this invention, defined as those particles
having an average diameter of from 1 micron to 30 microns, while
"micro-fine" diamonds are those having an average diameter of from
0.01 micron to 1 micron. With the aforementioned nickel baths
operated under the described conditions a plate is formed which
comprises approximately 60 percent nickel and 40 percent diamonds.
This ratio can be varied as desired by changing the concentration
of the diamond particles. The thickness of the plate can also be
varied by varying the time and current density.
The plate produced from the above described nickel baths has
excellent adhesion to the substrate surfaces. Microscopic
examination of the surface of the plate shows an "orange peel"
effect. That is to say, the surface of the plate resembles an
orange peel in that rather than being uniformly even it possesses
concavities and convexities. The diamond particles are distributed
evenly throughout the concave and convex surface areas. It is the
presence of the concave and convex surface areas that is thought to
be responsible for decreasing the frictional forces between a
surface in contact with the electroplated article. It is believed
that air or oil and other lubricating agents are trapped in the
concavities and thus have a lubricating or buoying effect when the
two surfaces are in contact with each other. It is also likely that
the nickel oxidizes to form a thin film of nickel oxide, especially
on the convex areas, which also acts as a lubricant, thereby
further reducing the frictional force.
The diamond particles are found to be aligned in a uniform
configuration throughout the entire matrix. The diamond particles
are all aligned with their sharp, uneven or ragged edges directed
toward the substrate surface while their rounded or even ends are
aligned facing outwardly from the substrate metal and the matrix.
Thus it is the smooth or rounded ends of the diamond particles
rather than the sharp or ragged edges which come into contact with
a corresponding surface. This too reduces the frictional forces as
well as insuring that the contacting surface will not be scored or
scratched by the diamonds' rough edges.
If desired, the diamond containing plate, which can be as thin as
.000039 inch or as thick as 0.25 inch but which is usually kept at
a thickness of 0.0001 inch, can be given a final chromium plate of
about 0.2 mil thickness to protect the softer nickel or other
matrix metal.
* * * * *