U.S. patent number 3,900,592 [Application Number 05/382,308] was granted by the patent office on 1975-08-19 for method for coating a substrate to provide a titanium or zirconium nitride or carbide deposit having a hardness gradient which increases outwardly from the substrate.
This patent grant is currently assigned to Airco, Inc.. Invention is credited to Kurt D. Kennedy, Glen R. Scheuermann.
United States Patent |
3,900,592 |
Kennedy , et al. |
August 19, 1975 |
Method for coating a substrate to provide a titanium or zirconium
nitride or carbide deposit having a hardness gradient which
increases outwardly from the substrate
Abstract
A method for coating a substrate with titanium nitride or
titanium carbide or zirconium nitride or zirconium carbide is
described wherein physical vapor deposition in a vacuum is used,
and wherein the substrate is biased by an electrical potential and
the composition of the deposit is changed by introducing a gas
during the deposition to produce a hardness gradient in the deposit
which increases outwardly from the substrate.
Inventors: |
Kennedy; Kurt D. (Berkeley,
CA), Scheuermann; Glen R. (Novato, CA) |
Assignee: |
Airco, Inc. (Montvale,
NJ)
|
Family
ID: |
23508397 |
Appl.
No.: |
05/382,308 |
Filed: |
July 25, 1973 |
Current U.S.
Class: |
427/569;
427/249.19; 427/577; 428/212; 427/580; 428/217 |
Current CPC
Class: |
C23C
14/0021 (20130101); C23C 14/027 (20130101); Y10T
428/24942 (20150115); Y10T 428/24983 (20150115) |
Current International
Class: |
C23C
14/00 (20060101); C23C 14/02 (20060101); C23c
011/08 () |
Field of
Search: |
;117/93,93.1GD,16R,107,131 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Martin; William D.
Assistant Examiner: Newsome; John H.
Attorney, Agent or Firm: Fitch, Even, Tabin &
Luedeka
Claims
What is claimed is:
1. A method for coating a substrate with a nitride or carbide of
titanium or zirconium, comprising, placing the substrate in an
evacuated environment, evaporating titanium or zirconium from a
crucible in the evacuated environment to produce a vapor and
causing the vapor to deposit on the substrate initially as titanium
or zirconium, applying an electrical potential during deposition
sufficient to produce a voltage difference of at least 200 volts
between the substrate and the crucible, and introducing a reactant
gas with a gradually increasing partial pressure to the vapor to
change the composition of the deposit from its initial composition
to increasing nitride or carbide in the direction outwardly from
the substrate to produce a hardness gradient in the deposit which
increases outwardly from the substrate.
2. A method according to claim 1 wherein the reactant gas is
nitrogen in order to produce a nitride coating.
3. A method according to claim 1 wherein the reactant gas is
methane in order to produce a carbide coating.
4. A method according to claim 1 wherein the reactant gas is
acetylene in order to produce a carbide coating.
5. A method according to claim 1 wherein the substrate is biased
negative with respect to ground.
6. A method according to claim 1 wherein the substrate is heated
during deposition.
Description
This invention relates to coated substrates and, more particularly,
to the coating of a substrate to produce a high hardness
coating.
The production of high hardness coatings on substrates may be
desired in a wide variety of applications. For example, it is well
known that the production of a titanium carbide coating on the
surface of tungsten carbide cutting tools or wear parts produces
significantly longer cutting or wear life than is possible with the
uncoated tools or parts. Another example is the coating of wear
surfaces in the combustion chambers of internal combustion engines,
particularly those of the rotary type, with high hardness coatings
of titanium nitride or titanium carbide.
In order to accomplish this deposition, much work has been done in
the area of physical vapor deposition processes, hollow cathode
sputtering processes, chemical vapor deposition processes, and
reactive physical vapor deposition processes. Prior art
applications of such processes, however, have failed to produce
hardness values as high as may be required in many instances.
Moreover, in many instances of prior art deposition processes, the
rate of deposition has been lower than that desirable for high
production techniques. In other cases of prior art deposition
techniques, mechanical failure of the coating at the interface with
the substrate has occurred.
It is an object of the present invention to provide an improved
method for coating a substrate.
Another object of the invention is to provide a method for coating
a substrate in which very high hardness of the coating is
obtained.
It is another object of the invention to provide a method for
coating a substrate in which relatively higher deposition rates may
be achieved than in many prior art methods.
A further object of the invention is to provide a method for
coating a substrate in which a very strong mechanical bond between
a high hardness coating and a relatively softer substrate is
achieved.
Other objects of the invention will become apparent to those
skilled in the art from the following description, taken in
connection with the accompanying illustration which is a
photomicrograph enlarged 325 times of the cross section of a
substrate coated with titanium nitride in accordance with the
invention,
Very generally, the method of the invention comprises placing the
substrate in an evacuated environment and evaporating titanium or
zirconium metal in the evacuated environment to produce a vapor and
causing the vapor to deposit on the substrate. The composition of
the vapor is changed by reacting it with a gas during deposition to
produce a hardness gradient in the deposit which increases
outwardly from the substrate. To improve deposition rate and
hardness, an electrical potential is applied to the substrate
during the deposition process sufficient to produce a voltage
difference of at least 200 volts between the substrate and the
crucible.
Referring now in greater detail to the method of the invention, the
method is applicable to coating a variety of substrates, including
metals such as aluminum, magnesium, iron, and alloys thereof, and
to coating metal composites such as tungsten carbide. The
particular materials used depends upon the use of the product being
manufactured. For example, a coating of titanium nitride on a
titanium carbide substrate will produce a very hard product
suitable for use in cutting tools and wear parts.
As was the case in connection with the substrates, the nature of
the deposit put down will also depend upon the end use for the
product being manufactured. Coatings deposited in accordance with
the invention may comprise titanium nitride, titanium carbide,
zirconium nitride or zirconium carbide for wear parts, cutting
tools, or corrosion resistance, etc. Generally speaking, the
invention is applicable to any situation wherein it is desirable to
produce a hard coating on a relatively softer substrate.
The equipment utilized to carry out the method of the invention may
be of any suitable type in which a vapor of the material to be
deposited is produced in a vacuum. Heating of the coating material
in order to vaporize same may be accomplished by such means as
resistance heating, induction heating, or preferably electron beam
heating. Equipment for accomplishing high vacuum vapor deposition
is known in the art and is commercially available on the market
from the Airco Temescal Division of Airco, Inc., Berkeley, Calif.
The particular structure of the equipment is not critical to the
invention and therefore will not be further described herein.
The substrate to be coated is placed in the deposition chamber
either through a suitable vacuum lock, or directly at atmospheric
pressure with subsequent evacuation of the chamber. The manner in
which the substrate is supported is dependent upon the substrate
shape and the evaporation conditions in the chamber. Preferably,
the initial pressure in the chamber is of the order of 1 millitorr
or less.
In order to enhance the deposition rate, the quality of the
deposit, and the hardness of the deposit, an electrical potential
is applied to the substrate during deposition. The electrical
potential is sufficient to produce a glow discharge. Typically, an
electrical bias of negative 200 volts or greater will produce the
desired glow discharge. The electrical biasing will also tend to
heat the substrate, which is desirable in most cases to enhance the
quality of the deposit.
The titanium or zirconium of which a nitride or carbide is to be
deposited is evaporated within the evacuated environment. As used
herein, the term "titanium" is meant to include pure titanium and
titanium base alloys as well. The term "zirconium" is meant to
include pure zirconium and zirconium base alloys as well. As is
known in the art, the metal thus evaporated will pass in the vapor
form within the evacuated environment and when vapor particles
thereof strike the substrate, they will condense on the substrate
and thereby form a deposit on the surface thereof. The particular
conditions under which this occurs are well known to those skilled
in the art and therefore will not be further detailed herein.
If the hard coating deposited on the substrate has a substantially
higher strength than the substrate material, the respective
dimensional responses of the substrate and the coating to thermal
or mechanical forces may be substantially different. As a result,
very high shear forces may concentrate at the interface between the
coating and the substrate. If this interface is weak for any
reason, such as poor adhesion or the presence of discontinuities or
foreign substances, failure can result.
To avoid such failure, the method of the invention creates a
hardness gradient in the coating. Ideally, this is accomplished by
making the mechanical and thermal properties of the coating and the
substrate at the interface identical. Transition from the
mechanical and thermal properties at the interface to the higher
strength properties on the outer surface of the deposit are made to
occur gradually from the interface to the outer surface. The
elimination of thermal and mechanical property discontinuities
distributes shear stresses over a volume, rather than concentrating
them at a surface plane at the interface, thus rendering the
resultant product more resistant to thermal or mechanical
cycling.
To this end, the composition of the vapor produced in the evacuated
environment is changed gradually during the deposition process to
produce a hardness gradient in the deposit which increases
outwardly from the substrate. This is accomplished by the
introduction of a reactant gas to the vapor gradually increasing
the gas pressure, such as from about one micron to about 50
microns. Typically, all that is necessary is to turn on a bleed
source and allow a gradual build-up of the partial pressure of the
bleed gas in the vapor. The reactant gas may such as to produce a
nitride or carbide, and may be acetylene, nitrogen, methane, etc.,
for example. A reduction of damaging stress concentrations at the
interface between the coating and the substrate results.
Referring now to the illustration, the photomicrograph enlarged 325
times illustrates the cross section of a substrate coated in
accordance with the invention and illustrating the results of
Vickers Pneumatic hardness tests in kilograms per square millimeter
taken across the cross section. The substrate is indicated at the
very bottom of the illustration and five regions of the coating are
indicated at A, B, C, D and E in the photograph. These regions
represent different partial pressures of nitrogen present during
the evaporation process.
Region A, in which no nitrogen bleed was used, is pure titanium.
Region B was deposited at 3 to 4 microns partial pressure nitrogen,
region C at 4 to 6.5 microns partial pressure of nitrogen, region D
at 10 microns partial pressure of nitrogen, and region E at 12
microns partial pressure of nitrogen. Deposition rates for all
regions was 0.0008 inch per minute except for region E, in which
the rate was 0.0003 inch.
Evaporation occurred from a pure titanium ingot with a 25 kilowatt
electron beam at a starting pressure of 0.01 micron in the vacuum
chamber. The temperature of the substrate was 1600.degree.F.
Pressure of the nitrogen was increased to the 12 micron maximum in
a time period of 40 minutes and then was held constant in the
region E. As may be seen, pure titanium deposited at the substrate
surface in the region A offered relatively low hardness values, and
the Vickers hardness values increased substantially in the regions
B through D. Finally, the outer surface offered the maximum Vickers
hardness of 2,450 kilograms per square millimeter under a 100 gram
load.
The illustration indicates that the surface hardness is
substantially increased by depositing titanium nitride in
accordance with the invention.
The following table set forth below illustrates titanium nitride
hardness as a function of electrical substrate bias and nitrogen
pressure. As ma be seen, there is a general tendency in the range
set out for hardness to increase as a function of gas pressure and
as a function of a negative bias voltage.
TITANIUM-NITRIDE HARDNESS AS A FUNCTION OF BIAS AND NITROGEN
PRESSURE Vickers Hardness Substrate N.sub.2 Pressure Number -
kg/mm.sup.2 Bias-Volts Microns
______________________________________ 300 0 3 1120 -200 3 1220
-400 3 1290 -800 3 1380 -1600 3 1250 -2500 3 1380 -5000 3 235 0 0.3
770 -200 0.3 840 -400 0.3 800 -800 0.3 840 -1600 0.3 810 -2500 0.3
915 -5000 0.3 ______________________________________
The substrate temperature was 1,600.degree.F and the deposition
rate was 1 .+-. 0.3 mils per minute in all cases.
Other titanium base materials which have been successfully
deposited include Ti-3Al-2.5V on aluminum substrates with a
nitrogen bleed to form titanium nitride. The same material has been
coated with the use of a methane and an acetylene bleed to form
titanium carbide in each case.
Zirconium has been deposited in accordance with the invention and
similar results have been achieved. Hardness values of zirconium
nitride deposited by evaporating zirconium with a N.sub.2 bleed
were as follows:
Vickers Hardness N.sub.2 Pressure Number-kg/mm.sup.2 Microns
______________________________________ 494 .015 750 .03 494 .05
1625 .3 1950 1 1000 1.3 2325 1.6 2375 1.9
______________________________________
As may be seen, in the range shown, a general tendency toward
increased hardness with increasing partial pressure of N.sub.2
exists. Zirconium carbide may be produced in a similar manner.
It may therefore be seen that the invention provides an improved
method for coating a substrate in which very high hardness of the
coating is obtained. Relatively high deposition rates may also be
achieved in comparison with many prior art methods. A very strong
mechanical bond is obtained between the high hardness coating and
the relatively softer substrate.
Various modifications of the invention in addition to those shown
and described herein will become apparent to those skilled in the
art from the foregoing description and accompanying illustration.
Such modifications are intended to fall within the scope of the
appended claims.
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