U.S. patent number 3,658,577 [Application Number 04/862,813] was granted by the patent office on 1972-04-25 for vapor phase deposition of silicide refractory coatings.
Invention is credited to Gene F. Wakefield.
United States Patent |
3,658,577 |
Wakefield |
April 25, 1972 |
**Please see images for:
( Certificate of Correction ) ** |
VAPOR PHASE DEPOSITION OF SILICIDE REFRACTORY COATINGS
Abstract
Refractory coatings are formed upon the periphery of objects by
passing a vaporous reactant stream in contact with the objects
which are tumbled in a rotary deposition zone. In addition,
reactant vapors are passed through a reactant generating zone
positioned adjacent and preferably enclosed within the rotary
deposition zone which is heated to the reaction temperature to
thereby generate at least a portion of the reactant vapors utilized
in the deposition of the refractory coating. For example, titanium
tetrachloride vapors are passed over chromium and titanium metal
chips positioned within the generation zone to produce chromium
dichloride and titanium trichloride reactant vapors. A suitable
apparatus is also provided for generating at least a portion of the
vaporous reactants and combining them with other vaporous reactants
and directing them onto tumbling objects to be coated within a
rotary deposition chamber.
Inventors: |
Wakefield; Gene F. (Richardson,
TX) |
Family
ID: |
25339430 |
Appl.
No.: |
04/862,813 |
Filed: |
October 1, 1969 |
Current U.S.
Class: |
427/242;
427/255.391; 427/255.393; 427/255.5 |
Current CPC
Class: |
C23C
16/42 (20130101); C23C 16/44 (20130101) |
Current International
Class: |
C23C
16/44 (20060101); C23C 16/42 (20060101); C23c
011/00 (); C23c 013/00 () |
Field of
Search: |
;117/106,107,107.1,107.2 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Leavitt; Alfred L.
Assistant Examiner: Glynn; Kenneth P.
Claims
I claim:
1. A method of forming a protective coating on the surface of a
compatible substrate which comprises:
contacting a particulate mass of elemental chromium and a
particulate mass of elemental titanium with a reactant stream
comprising titanium tetrachloride, thereby forming a reactant
stream comprising titanium trichloride and chromium dichloride;
tumbling said substrate in a rotary deposition zone;
heating said particulate mass of chromium, said particulate mass of
titanium, and said substrate in a common heating zone; and
contacting said substrate with silicon tetrachloride, hydrogen, and
the reactant stream produced by reacting said titanium
tetrachloride with the elemental titanium and chromium, thereby
forming a refractory silicide coating on said substrate.
2. A method as defined by claim 1 wherein said titanium, said
chromium, and said substrate are maintained at a temperature at
about 900.degree. C.
Description
This invention relates to vapor phase deposition of refractory
materials upon a substrate. In another aspect, this invention
relates to an improved method and apparatus for forming a
continuous refractory coating on the periphery of an object.
Refractory metals, such as tantalum, molybdenum, columbium
(niobium) and tungsten, for example, are especially desirable for
applications requiring high strength at elevated temperature,
particularly where ease of fabrication and ductility are needed.
However, before any of these metals can satisfy a wide range of
requirements, they must receive a suitable protective coating, such
as an oxidation resistant and/or an abrasive resistant coating. For
example, titanium and chromium, being metallurgically compatible
with the refractory metals, form a good base coating which, when
alloyed with silicon, or reacted with carbon or nitrogen will
protect them against oxidation, and/or abrasion.
Various chemical vapor phase deposition processes have been
developed for depositing protective coatings on substrates,
including substrates of refractory metals. These protective
coatings include silicon carbide, titanium carbide, silicon
nitride, titanium nitride, metal carbonitrides, and
titanium-chromium-silicon alloys, to name a few. When depositing
some of the newer solid solution or alloy layers, problems have
been encountered in the formation and maintaining of suitable
vaporous reactant streams. For example, attempts to co-reduce
titanium and chromium halides produced separately, and individually
introduced into a deposition chamber, failed to yield satisfactory
co-deposits of titanium and chromium alloys upon the substrate.
This is true because of resultant non-uniform mixing of the two
halide gas streams and inadequate control of the composition of the
reactant gas stream. Furthermore, in the separate production of the
halides of the metals by the reaction of hydrogen chloride gas, for
example, with the individual metals, the unreacted hydrogen
chloride gas tends to inhibit the deposition of the titanium metal.
Thus, the formation and control of the vaporous reactant streams
has been conventionally very difficult to accomplish.
Additionally, problems have been encountered in obtaining uniform
deposits of a protective coating about the entire periphery of an
object, particularly irregularly shaped objects such as nuts and
bolts, which are used for high temperature fasteners, such as for
example, fasteners for a rocket nose cone. It is essential that the
entire periphery of these objects obtain a uniform coating to
prevent damaging corrosion from eroding and weakening any portion
thereof. Therefore, it is necessary that the entire periphery of
these objects be subjected to the vaporous reactant atmosphere.
One object of this invention is to provide an improved process and
apparatus for forming a protective coating on the periphery of an
object.
Another object of this invention is to provide an improved process
and apparatus for forming and effectively mixing a vaporous
reactant stream and directing it upon a tumbling object to be
coated in a rotating vapor deposition zone.
A further object of this invention is to provide a method and
apparatus for applying a uniform refractory or protective coating
on the periphery of an object by vapor phase deposition, and for
generating at least a portion of the vaporous reactant stream.
According to one embodiment of this invention, a process is
provided for applying a protective coating to the periphery of an
object comprising placing the object within a rotary deposition
zone which causes the object to tumble therein, and directing a
vaporous reactant stream in contact with the tumbling object
wherein at least a portion of said stream is generated by passing a
reactant halogen-containing stream over metal particles in a
generation zone to form a corresponding metal halide. Preferably,
the generation zone is located within a heat zone containing the
rotating vapor deposition zone.
According to another embodiment of this invention, an apparatus is
provided for carrying out the above-described process which
generally includes a rotary vapor phase deposition chamber for
receiving and imparting a tumbling motion to at least one object to
be coated with vapor phase reactant product, an oven means for
enclosing the deposition chamber, nozzle means for introducing
vapor phase reactants into the rotary vapor phase deposition
chamber, and at least one reactant generation chamber positioned
within said oven means and communicating with said nozzle means
.
This invention can be more easily understood from a study of the
drawings in which:
FIG. 1 is an elevational view of a vapor phase deposition apparatus
of this invention with the rotary deposition chamber positioned
outside of the oven;
FIG. 2 is the apparatus of FIG. 1, partially in section, showing
the rotary vapor phase deposition chamber extended within the oven;
and
FIG. 3 is a partial sectional view of FIG. 2 showing a nozzle means
and reactant generation chamber thereof.
Now referring to FIG. 1, the apparatus of this invention is
illustrated which generally comprises rotary vapor phase deposition
reactor means 10 and an oven means 11.
Rotary vapor phase deposition reactor means 10 comprises rotary
deposition chamber 12 rotatably mounted on tubular spindle 13,
which is carried by frame 14. Frame 14 is slidably mounted on guide
rods 15 and is actuated by worm gear 16 which passes through a
cooperating threaded portion of member 17, which extends from frame
14. Crank 18 is operatively attached to the end of worm gear 16
through gear box 19. Thus, a rotational motion of crank 18 will
cause frame 14 to move along guide rods 15 by the action of worm
gear 16 on the threaded portion of member 17.
Now referring to both FIGS. 1 and 2, rotary deposition chamber 12
is mounted to flange 13a of tubular spindle 13 by suitable
fastening means such as nut and bolt assemblies 20. Tubular spindle
13 is rotatably mounted between supports 21 and 22 and has nozzle
means 23 operatively positioned therethrough in a non-rotating,
fixed relationship. Sprocket 24 is affixed to the periphery of
spindle 13 and is attached by a drive chain 25 to driving sprocket
26 of motor 27.
Rotary deposition chamber 12 generally comprises a widened body
portion 12a for receiving at least one object, such as nuts and
bolts as illustrated in FIG. 2, and an elongated neck section 12b
slightly wider in diameter than the width of nozzle means 23, and
flange 12c, having apertures which match with apertures through
flange 13a of spindle 13 for receiving nut and bolt assemblies 20.
Rotary deposition chamber 12 can be made of any suitable ceramic
material such as quartz.
The outlet of nozzle means 23 is positioned to direct reactants on
the objects 50 positioned within the widened portion 12a of rotary
deposition chamber 12. Reactant inlet conduits 28, 29 and 30 are
operatively connected to nozzle means 23, as will be described in
relation to FIG. 3, below. Outlet conduit means 31 operatively
communicates with annular zone 32 between reactant nozzle means 23
and rotary deposition chamber 12.
Oven 11 carries a suitable heating chamber 33 (shown in broken
line), which communicates with a pair of cooperating hinged oven
doors 34. Each oven door carries a semi-circular recessed portion
35 on its outer edge for receiving elongated neck portion 12b of
rotary deposition chamber 12 when in closed position.
Now referring to FIGS. 1-3, and particularly FIG. 3, nozzle means
23 is illustrated in detail. As shown in FIG. 3, nozzle means 23
generally comprises a tubular member 36 which is operatively
connected to feed inlet conduit 30 within support member 22 and has
a downturned outlet end 37. In addition, nozzle 23 carries
generation chamber 38 therewithin. Conduits 39 and 40 communicate
with reactant inlet conduits 29 and 28, respectively. The outlet of
conduit 39 extends through tubular body 36 and is substantially
concentric with downturned outlet 37. The outlet of tube 40 is
positioned adjacent outlet 37. It is noted that any number of
conduits 40 can be utilized within the scope of this invention
according to the particular reactants utilized. For example, one or
more conduits 40 can be positioned on nozzle means 23. If desired,
the outlet end of conduit 40 can be positioned in a downturned
manner adjacent outlet 37.
Reactant generation chamber 38 can comprise one or more chambers
contained within porous plugs 41 and 42. As illustrated, generation
chamber 38 carries a partition member 43, which separates the
chamber into two individual generation chambers 38a and 38b
containing either similar or dissimilar metallic particles 44 and
45, respectively. Holes 46 through porous plugs 41 and 42 can be
varied in size and number to control the relative proportions of
reactant gas flow through the two chambers 38a and 38b.
The process and apparatus of this invention finds particular
utility in applying protective coatings to the periphery of objects
with vaporous metal compounds which have relatively low vapor
pressures at room temperature. In addition, this invention is
especially useful for generating highly reactive metal sub-halide
reactants from the more stable metal halides which have high vapor
pressures at room temperature. The metal sub-halides are not only
more reactive but result in a reduced amount of by-product acid
vapor which generally inhibits the deposition rate on the
substrate.
Thus, this invention can be utilized to apply various protective
coatings to the surface of objects. However, it will be described
in detail hereinbelow with reference to the deposition of a complex
silicide refractory compound coating consisting of titanium,
chromium, and silicon. The introduction of chromium to a plating
environment is generally very difficult, since the vapor pressure
of chromium is relatively low even at elevated temperatures. This
invention will assure that chromium is introduced to the plating
environment used in coating the periphery of an object. In
addition, this invention can be used to form a more reactive halide
specie of a vaporous metal halide reactant.
Thus, in a preferred embodiment, particulate chromium is positioned
in one of the generating chambers, for example, 38b within tubular
body 36, and particulate titanium is placed within the other
generating chamber 38a. Rotary deposition chamber 12 is removed
from spindle 13 and objects 50 are positioned therewithin. Next,
rotary deposition chamber 12 is affixed to flange 13a of spindle 13
by nut and bolt assemblies 20. Hand crank 18 is actuated to move
frame 14 along guide rods 15 toward oven 11. As rotary deposition
chamber 12 extends within oven 11, oven doors 34 are closed in a
manner as illustrated in FIG. 2 such that elongated neck portion
12b of rotary deposition chamber 12 extends between cooperating
semicircular recesses 35.
The heating element of oven 11 is actuated to heat rotary
deposition chamber 12, generation chamber 38, and objects 50 to a
suitable reaction temperature, e.g., 900.degree. C. Next, motor 27
is actuated to cause drive chain 25 to rotate spindle 13 at a
suitable speed, for example, from about 0.5 to about 15 rpm. This
rotating action causes the rotation of rotary deposition chamber 12
and thereby causes the tumbling of parts 50 therewithin. Next,
suitable reactants are supplied by conduits 28-30. Titanium
tetrachloride is passed into generation chamber 38 from feed
conduit 30. Silicon tetrachloride is passed into conduit 39 of
nozzle means 23 from feed conduit 29, and reducing hydrogen is
passed through conduit 40 of nozzle means 23 from feed conduit 28.
Exhaust gases are removed from annular space 32 within rotary
deposition chamber 12 by exhaust conduit 31. The action of the
titanium tetrachloride on the chromium particles contained within
chamber 38b is generally as follows:
2 TiCl.sub.4 + Cr .fwdarw.2 TiCl.sub.3 + CrCl.sub.2.
In addition, the reaction of the titanium tetrachloride on the
titanium metal particles contained within generation chamber 38a is
as follows:
3 TiCl.sub.4 + Ti .fwdarw.4 TiCl.sub.3.
Thus, a reactant feed stream consisting essentially of titanium
trichloride and chromium dichloride is passed to outlet 37 of
nozzle means 23 from porous plug 42. In addition, the vaporous
reactants from porous plug 42 are intermixed with silicon
tetrachloride passed from the outlet of conduit 39. The resulting
reactant feed mixture is passed downwardly into the interior of
rotary deposition chamber 12 in contact with the tumbling parts
50.
Hydrogen supplied to the interior of rotary deposition chamber 12
reduces the metallic halides emitted from outlet 37 of nozzle 23
when contact is made with an object 50 to form a complex silicide
refractory compound consisting essentially of titanium, chromium,
and silicon, thereby leaving a by-product of hydrogen chloride
which is removed from deposition chamber 12 via conduit 31 as
described above.
After the deposition process, reactant flow is cut off, oven doors
34 are opened, and hand crank 18 is actuated to thereby pull frame
14 from the interior of oven 11. The coated objects are then
removed from rotary deposition chamber 12 after it is removed from
spindle 13.
It must be understood that various vapor phase chemical deposition
processes can be carried out according to this invention. For
example, metallic particles utilized in generation chamber 38 can
be metals selected from Groups IVB, VB, VIB, VIIB and VIII of the
Periodic Table, carbon, silicon, and boron, or mixtures thereof.
The reactant gas passed through generation chamber 38 can be any
suitable reactant known in the art which will combine with the
metal, volatilize the same, and later react with a suitable
reducing agent such as hydrogen within the rotary deposition
chamber. For example, metal halides, molecular halogen, and acid
vapors such as hydrogen chloride.
Thus, this invention can be utilized to deposit uniform refractory
coating such as metal carbides, metal nitrides, metal carbonitrides
and silicide coatings on the periphery of objects tumbling within
the rotary vapor phase deposition zone. For example, if it is
desired to deposit a metal carbonitride, such as titanium
carbonitride, on the surface of an object within the rotary
deposition zone, titanium particles can be positioned within
generation chamber 38, and titanium tetrachloride passed
therethrough to form a feedstream of titanium trichloride. The oven
in this instance can be heated to a temperature in the range from
abour 400.degree. to about 1,200.degree. C. Next, molecular
nitrogen and/or an easily decomposable nitrogen-containing
compound, an easily decomposable carbon-containing compound
(alternatively, an easily decomposable nitrogen and
carbon-containing compound) is passed through conduit 39. Molecular
hydrogen is passed through conduit 40.
Suitable carbon-containing reactant compounds include cyclic and
acyclic hydrocarbons having up to about 18 carbon atoms which
readily decompose at the deposition temperature. Examples of
suitable hydrocarbons include the parafins, such as methane,
ethane, propane, butane, pentane, decane, pentadecane, octadecane,
and aromatics such as benzene and halogen substitute derivatives
thereof.
Suitable reactant compounds containing both carbon and nitrogen
include aminoalkenes, pyridines, hydrazines, and alkylamines. Some
specific examples include diaminethylene, triaminoethylene,
pyridine, trimethylamine, triethylamine, hydrazine,
methylhydrazine, and the like.
Thus, the above described reactants can be utilized to form a
titanium carbonitride coating on the surface of objects 50 tumbling
within rotating deposition chamber 12.
This invention can be more easily understood from a study of the
following examples which are given for illustrative purposes
only.
EXAMPLE 1
In this example an apparatus was utilized which was substantially
the same as that illustrated in the drawings. Widened portion 12a
of rotary deposition chamber 12 comprised a cylindrically shaped
body 5 inches in diameter and 6 inches long. Prior to the run, 10
1/4 inches diameter by 11/2 inches long hexhead bolts made of a
refractory columbium alloy were placed within chamber 12, pure
titanium metal chips were positioned within generating chamber 38b
and pure chromium chips were placed within generating chamber
38a.
Next, frame 14 was moved forward and oven doors 34 closed so that
widened portion 12a of rotary deposition chamber 12 was positioned
within oven 11 as illustrated in FIG. 2. The interior of oven 11
was maintained at 900.degree. C. Motor 27 was actuated to cause
spindle 13 and rotary deposition chamber 12 to rotate at a speed of
11 rpm.
Reactants were next passed in through reactant inlet conduits 28,
29 and 30. A stream consisting of 0.238 liter per minute of
titanium tetrachloride and 17.3 liters per minute of argon was
passed through inlet conduit 30 to tubular body 36 and through
generation chamber 38. A stream of 0.12 liter per minute of silicon
tetrachloride in 1.38 liters per minute of argon was passed through
inlet conduit 29 and conduit 39 of nozzle means 23. Ten liters per
minute of hydrogen was passed in through inlet conduit 28 and
conduit 40 of nozzle means 23. This reactant flow continued for a
period of 270 minutes. At the end of the deposition time, there was
shown to be substantial weight loss of the chromium and titanium
chips from generating chamber 38. Each bolt was found to have an
average of 330.7 milligrams of silicide coating (a coating
consisting essentially of titanium, chromium, and silicon) thereon.
This coating was substantially uniform over the entire portion of
the bolt including the threaded portion and resulted in a
substantially oxidation resistant surface thereof. The coating
thickness was between 2 and 3 mils, and oxidation tests at
2,400.degree. F in an oxidation environment showed an increased
life of 80 times of that of similar uncoated bolts.
EXAMPLE 2
The apparatus as described above was utilized except in this
instance, 10 1/4 inches diameter by 11/2 inches long hexhead bolts,
10 hex nuts for the bolts, and 10 1/4 inches diameter by 1 inch
long threaded studs all made of a refractory columbium alloy were
utilized as the substrates within rotary deposition chamber 12.
After the 30 substrates were loaded into the rotary deposition
chamber 12, the run was conducted in substantially the same manner
as described in relation to FIG. 1. However, furnace 11 was
maintained at 990.degree. C and the flow of reactants was as
follows: 0.140 liter per minute of titanium chloride and 10.2
liters per minute of argon were passed through generating chamber
38 containing the titanium and chromium chips; 0.084 liter per
minute of silicon tetrachloride and 2.66 liters per minute of argon
were passed through conduit 39 of nozzle means 23; and 7 liters per
minute of hydrogen together with 3 liters per minute of argon was
passed through conduit 40 to the interior of rotary deposition
chamber 12. The flow of reactants continued for a period of 480
minutes.
After the run was completed, it was found that there was a
substantial loss of weight of the chromium and titanium chips from
generating chambers 38a and 38b. In addition, it was found that the
average weight gain of the hexhead bolts was 528.2 milligrams per
bolt, the average weight gain of each hex nut was 118.6 milligrams,
and the average weight gain of each of the threaded studs was 147.6
milligrams. It was found that the silicide coating was uniform
about the periphery of the objects, even on the threaded
surfaces.
EXAMPLE 3
Example 2 was repeated, except 0.084 liter per minute of
diaminethylene in 2.616 liters per minute of argon was passed
through conduit 39 of nozzle 23 instead of silicon
tetrachloride.
This procedure formed a uniform deposit of titanium carbonitride on
the periphery of the individual substrates.
While this invention has been described in relation to its
preferred embodiments, it is to be understood that various
modifications of this invention will now become apparent to one
skilled in the art upon reading the specification, and it is
intended to cover such modifications as fall within the scope of
the appended claims.
* * * * *