U.S. patent number 3,787,225 [Application Number 05/141,957] was granted by the patent office on 1974-01-22 for aluminum plating process.
This patent grant is currently assigned to The Dow Chemical Company. Invention is credited to Frederick L. Acker, Charles B. Roberts.
United States Patent |
3,787,225 |
Roberts , et al. |
January 22, 1974 |
ALUMINUM PLATING PROCESS
Abstract
Described is a closed loop method of producing a volatile
aluminum hydride trimethylamine complex, depositing aluminum from
the complex onto a substrate, and recycling trimethylamine vapor
released during deposition to produce additional aluminum hydride
trimethylamine complex.
Inventors: |
Roberts; Charles B. (Midland,
MI), Acker; Frederick L. (Saginaw, MI) |
Assignee: |
The Dow Chemical Company
(Midland, MI)
|
Family
ID: |
22497967 |
Appl.
No.: |
05/141,957 |
Filed: |
May 10, 1971 |
Current U.S.
Class: |
427/252 |
Current CPC
Class: |
C23C
16/20 (20130101) |
Current International
Class: |
C23C
16/18 (20060101); C23C 16/20 (20060101); C23c
011/00 () |
Field of
Search: |
;117/107.2,16R,71R,71M,47R,47A ;23/281,289 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Kendall; Ralph S.
Assistant Examiner: Massie; J.
Attorney, Agent or Firm: Griswold & Burdick Selby;
Robert S. Grace; S. S.
Claims
1. A closed loop process for plating aluminum onto a substrate
comprising:
a. contacting a substantially nonvolatile solid aluminum
hydride-ether complex with trimethylamine vapor to form a volatile
aluminum hydride trimethylamine adduct and ether;
b. contacting the substrate, heated to at least the decomposition
temperature of the adduct, with the adduct in a substantially
oxygen and moisture free environment for a sufficient time to
deposit aluminum onto the substrate and produce hydrogen and
trimethylamine vapor; and
c. recirculating the trimethylamine vapor of step (b) to step (a)
to
2. The process of claim 1 wherein the trimethylamine vapor is mixed
with a carrier gas prior to step (a), the gas being substantially
chemically and physically inert to the vapor, substrate and
products formed in the
3. The process of claim 1 wherein the trimethylamine vapor is
heated to
4. The process of claim 1 wherein the contacting of step (a) is
carried out at a pressure of from about 0.2 to about 15 gauge
pounds per square inch.
5. The process of claim 1 wherein the ether is selected from the
group
7. The process of claim 1 including the additional step of removing
hydrogen from the trimethylamine vapor decomposition product of
step (b).
8. The process of claim 1 including the additional step of removing
ether
9. The process of claim 1 wherein the contacting of step (b) is
carried out with a substrate catalyzed with a transition metal
decomposition catalyst effective in achieving a lower decomposition
temperature of the adduct selected from the group consisting of
compounds of titanium, zirconium,
10. The method of claim 3 wherein the contacting of step (a) is
carried out at a pressure of from about 0.2 to about 15 pounds per
square inch, the ether is diethylether and the ether is removed
from the decomposition products of step (b).
Description
BACKGROUND OF THE INVENTION
This invention relates to an electroless process for the plating of
aluminum on various substrates. More particularly it pertains to
the conversion of a substantially nonvolatile aluminum hydride to a
volatile aluminum hydride and the plating of metallic aluminum from
vapors of the volatile aluminum hydride.
It is known that metallic aluminum can be plated from aluminum
hydrides by contacting a substrate with such hydrides at or about
the decomposition temperature of the aluminum hydride. Such a
process usually requires a relatively high temperature to cause
decomposition of the aluminum hydride; however, employment of a
catalyst can effectively reduce the decomposition temperature of
aluminum hydride. A process for catalytic decomposition of aluminum
hydride is described in U.S. Pat. No. 3,462,288. A process for
vapor plating aluminum onto a substrate by cyclically contacting a
heated substrate with a heat decomposable aluminum-containing
compound, such as the aluminum hydride trimethylamine complex,
AlH.sub.3.sup.. (CH.sub.3).sub.3 N, is described in U.S. Pat. No.
3,206,326. However, this patent teaches the employment of vapors of
a heat decomposable aluminum compound as the starting aluminum
source material. The suggested aluminum hydride trimethylamine
complex is generally extremely sensitive to moisture and also has
an offensive odor. Additionally the aluminum hydride aminate
generally contains less than about 30 percent by weight aluminum.
The combination of these properties not only make it difficult, but
generally uneconomical to transport the aluminum hydride aminate
from the supplier to the coating operation. Moreover, the
trimethylamine formed, as aluminum is deposited on the substrate,
is frequently lost to the atmosphere or otherwise not
recovered.
It is an object of this invention to provide an electroless
aluminum deposition process which employs a relatively nonvolatile
aluminum hydride as a starting material.
It is another object of this invention to provide an aluminum vapor
deposition process which employs an aluminum hydride compound
having a low vapor pressure as the starting material and a
recirculatory system for usable by-products.
Other objects and advantages of this invention will become apparent
during the course of the following discussion.
SUMMARY OF THE INVENTION
It has been found that a substrate can be satisfactorily plated
with aluminum and the aforementioned objects achieved in the
hereinafter described process. A substantially nonvolatile solid
aluminum hydride-ether complex is contacted with trimethylamine
vapor. The aluminum hydride-ether complex is characterized as being
reactive with trimethylamine vapor to form a volatile aluminum
hydride trimethylamine adduct and the ether. Illustrative of such
adduct is aluminum hydride trimethylamine, AlH.sub.3.sup..
N(CH.sub.3).sub.3, aluminum hydride bistrimethylamine,
AlH.sub.3.sup.. [N(CH.sub.3).sub.3 ].sub.2, and the like.
Due to the sensitivity of most volatile aluminum hydride compounds
to the presence of moist air, it is usually desirable that the
application of the aluminum hydride plate be conducted in a
substantially anhydrous, inert atmosphere. The substrate is,
therefore, preferably inserted into the closed loop plating system
through a substantially gas impervious interchange means such as
generally described in U.S. Pat. Nos. 3,474,823 and 3,519,398.
However, the plating system can be dried after the substrate is
positioned in said system. The substrate can be heated to at least
the decomposition temperature of the volatile aluminum hydride
trimethylamine adduct either before or subsequent to insertion into
the closed loop system by any means known to those skilled in the
art. The heated substrate is then contacted with the adduct for a
sufficient time to decompose the adduct and deposit aluminum onto
the substrate and simultaneously release hydrogen and
trimethylamine vapor. The aluminum coated substrate is then removed
through the gas impervious interchange means in substantially the
same manner in which it was inserted.
The trimethylamine vapor produced during decomposition of the
aluminum hydride trimethylamine adduct is generally contaminated
with the by-product hydrogen and the ether (unless the ether is
previously removed). The ether and optionally the hydrogen can be
separately or simultaneously removed from the trimethylamine vapor
effecting purification of said vapor. If the explosion hazard of
hydrogen is unimportant, the hydrogen can remain mixed with the
vapor and used as a carrier gas. The purification can be carried
out by selective refrigeration and condensation of the gases or by
other methods known to those skilled in the art. The trimethylamine
vapor is recirculated to the original contacting step where the
aluminum hydride trimethylamine adduct was formed. Recirculation of
the vapor is preferably carried out by use of a standard
commercially available pump. However, recirculation can be
accomplished by condensing the vapor in a cylinder and vaporizing
the trimethylamine prior to introducing it into the original
contacting step.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The described aluminum hydride-ether complex has the general
formula (AlH.sub.3).sub.n.sup.. R, wherein n has a numerical value
of from 1 to 5 inclusive, and R is an ether group. The ethers
usually employed are the lower aliphatic ethers such as ethyl,
propyl or butyl ethers, but those containing an aromatic group such
as methylphenyl ether, ethylphenyl ethers, propylphenyl ether or
the alicyclic ethers are also useful. Diethylether, tetrahydrofuran
and dioxane, which respectively form aluminum hydride etherate,
(AlH.sub.3).sub.3.sup.. C.sub.4 H.sub.10 O, aluminum hydride
tetrahydrofuranate, AlH.sub.3.sup.. C.sub.4 H.sub.8 O and aluminum
hydride dioxinate, AlH.sub.3.sup.. C.sub.4 H.sub.8 O.sub.2, are
preferred herein. The above aluminum hydride-ether complexes are in
a suitable physical form to react with trimethylamine to provide a
volatile aluminum hydride trimethylamine complex, such as a porous
body, particulate or a block having a large surface area.
Naturally, the rate of chemical reaction to produce the aluminum
hydride aminate is directly proportional to the aluminum
hydride-ether complex surface area exposed to the trimethylamine
vapor.
Substantially any normal solid material is suitable as a substrate
in the aforedescribed process. For example, metals such as iron,
magnesium, brass and copper; polymers such as polyolefins,
polyamides and polymeric fluorocarbons, glass, paper, cloth, carbon
and graphite, wood, ceramics and the like are all platable with
aluminum by the process of this invention. The nature of the
surface being plated determines to a large extent the brightness of
the aluminum plate. In general, the use of a smooth, nonporous
surface, as found on most metals and some polymer films, produces a
brighter plate than a relatively porous surface, as those
encountered with paper or cloth. On the surfaces of some polymers,
such as polyethylene, polytetrafluoroethylene,
acrylonitrile-butadienestyrene polymers and polypropylene, it has
been found that even better adhesion of the aluminum plate is
achieved if the surface has been made more polar, that is by
sulfonation, corona discharge and the like, prior to plating with
the aluminum. To increase the vapor flow rate and improve the
contact between the vapor and aluminum hydride-ether complex, it is
oftentimes desirable to mix a substantially chemically and
physically inert carrier gas with the vapor prior to contact of the
vapor with said complex. Examples of suitable carrier gases are
hydrogen, nitrogen, helium, neon, argon, krypton, xenon and the
like. The rate of reaction between the trimethylamine vapor and the
aluminum hydride-ether complex to form the volatile aluminum
hydride trimethylamine adducts can be increased by heating the
trimethylamine vapor prior and/or simultaneously with contact of
said complex with said vapor. Desirably the vapor is heated to a
temperature of from about 25.degree.C. to about 65.degree.C.
The rate of aluminum deposition on the heated substrate can be
controlled by adjusting the rate at which the aluminum hydride
trimethylamine is formed. The aluminum deposition rate can
additionally be controlled by variance of the pressure within the
aluminum deposition chamber. Since the volatilization rate of
aluminum hydride trimethylamine is inversely proportional to the
pressure, a low pressure, especially lower than atmospheric, will
increase the vaporization rate of the adduct and consequently
increase the aluminum deposition rate onto the substrate.
Preferably the pressure is from about 0.2 to about 15 pounds per
square inch (guage).
As before described, the substrate should be heated to at least the
decomposition temperature of the aluminum hydride trimethylamine
vapor. This temperature is generally from about 120.degree.C. to
about 400.degree.C. It has, however, been discovered that when in
contact with certain transition metal catalysts, volatilizable
aluminum hydrides can be used to produce plating of metallic
aluminum at temperatures substantially below the usual
decomposition temperature of such hydrides, i.e., about
25.degree.C. to about 100.degree.C. and preferably about
50.degree.C. to about 100.degree.C. The use of such catalysts
permits the deposition of a uniform adherent plate or coating of
metallic aluminum, usually in the form of a bright plate, on
substantially any substrate at relatively low temperatures.
Transition metal decomposition catalysts useful herein are
compounds of titanium, zirconium, hafnium, vanadium, niobium and
tantalum. In instances where the catalyst is applied to the
substrate in a solvent, it is preferable that the metal be in the
form of a compound which is soluble to the extent of at least 1
.times. 10.sup.-.sup.6 weight percent of the solvent employed. For
example, such compounds as ZrCl.sub.4, NbCl.sub.5, VOCl.sub.2,
VOCl.sub.3, TiCl.sub.3, TiCl.sub.4.sup.. 2[(C.sub.2 H.sub.5).sub.2
O], TiCl.sub.4, TiBr.sub.4, TiI.sub.4, VCl.sub.4, Ti(OC.sub.2
H.sub.5).sub.2 Cl.sub.2, TiCl.sub.2.sup.. (i-OC.sub.3
H.sub.7).sub.2, TiCl.sub.2.sup.. 2[(C.sub.2 H.sub.5).sub.2 O], and
Ti(BH.sub.4).sub.3.sup.. 2[(C.sub.2 H.sub.5).sub.2 O] have proven
effective. Some of the transition metal catalysts defined herein
have a more pronounced effect than others in lowering the
decomposition temperature of the aluminum hydride. The chlorides,
bromides, iodides and oxychlorides of titanium, niobium, vanadium
and zirconium generally seem to be more effective than compounds of
the other transition metals. TiCl.sub.4 has been found to be
particularly effective in achieving lower decomposition
temperatures of aluminum hydride compounds.
By controlling the substrate temperature when it is contacted with
the aluminum hydride trimethylamine vapor and by addition of the
transition metal decomposition catalyst to only selected areas of
substrate, it is possible to form an aluminum plate only on such
selected areas. In this manner, ornamental designs, outlines,
printed circuits and the like may be produced. Likewise, all or a
portion of a selected substrate may be coated or plated with
aluminum to enhance the ability of such surface to adhere to other
metals. Of particular utility is the aluminum coating of glass,
ceramic, metal or polymer surfaces to enhance their bonding to
adhesive polymers and copolymers, such as the copolymers of
ethylene and acrylic acid. Once the desired form and quantity of
decomposition catalyst is applied to the substrate, the catalyzed
surface is heated and contacted with the aluminum hydride
trimethylamine vapor.
Particular embodiments of the present method can be carried out as
hereinafter described.
A closed plating system is maintained in a dry box atmosphere
having a maximum moisture content of less than about 1 part per
million. A glass beaker, heated to 150.degree.C., is inserted
within a plating chamber in the system through a gas impervious
interchange. Trimethylamine vapor is then passed through an
enclosed conduit to a container. Said container is enclosed at two
opposite ends by screens having a mesh of adequate size to prohibit
passage of 200 mesh particulate. Aluminum hydride etherate,
(AlH.sub.3).sub.3.sup.. C.sub.4 H.sub.10 O, particulate (200 mesh)
is periodically supplied to the container, through a gas impervious
interchange, while the trimethylamine flows through the particulate
to form aluminum hydride trimethylamine. An aluminum coating is
deposited on the glass beaker as aluminum hydride trimethylamine
flows, at atmospheric pressure, through the plating chamber and
therein contacts the heated glass. A uniform aluminum plate is
formed after about one hour of aluminum hydride trimethylamine
contact. Diethylether is removed from the trimethylamine released
during the plating step by liquefying the ether at about
-10.degree.C. Hydrogen is then removed by liquefying the
trimethylamine at about -78.degree.C. The so purified
trimethylamine is volatilized and recirculated by pumping, through
the aluminum hydride etherate. The trimethylamine is replenished as
necessary.
Employing substantially the same procedure as described above a
glass article is catalyzed by exposure to TiCl.sub.4 vapors before
being placed in the plating chamber. Deposition of an adherent
aluminum plate on the glass occurs at about 25.degree.C.
* * * * *