U.S. patent number 3,753,768 [Application Number 05/085,823] was granted by the patent office on 1973-08-21 for aliminum plating process.
This patent grant is currently assigned to Sumitomo Chemical Company Limited. Invention is credited to Eiichi Ichiki, Kazuo Iida, Yasuhiko Inoue, Yoshihiro Kondo.
United States Patent |
3,753,768 |
Ichiki , et al. |
August 21, 1973 |
ALIMINUM PLATING PROCESS
Abstract
Aluminum plating according to which aluminum film formed has no
cracks and pin-holes on its surface, a uniform thickness, excellent
luster and is strongly bonded to the substrate can be attained by
heat treating a substrate covered with aluminum at 400.degree. C
the melting point of aluminum for 10 seconds 30 minutes in an inert
atmosphere said heat treatment being preceded by or followed by
treating of the covered substrate with a surface treating agent
comprising active hydrogen-containing compound, oxygen or halogen
and thereafter taking out thus treated substrate into the air.
Inventors: |
Ichiki; Eiichi (Niihama,
JA), Iida; Kazuo (Niihama, JA), Inoue;
Yasuhiko (Niihama, JA), Kondo; Yoshihiro
(Niihama, JA) |
Assignee: |
Sumitomo Chemical Company
Limited (Osaka, JA)
|
Family
ID: |
13929553 |
Appl.
No.: |
05/085,823 |
Filed: |
October 30, 1970 |
Foreign Application Priority Data
|
|
|
|
|
Nov 1, 1969 [JA] |
|
|
44/87965 |
|
Current U.S.
Class: |
427/253; 427/229;
427/377; 427/383.5; 148/273; 427/320; 427/383.1; 427/383.7 |
Current CPC
Class: |
C23C
16/56 (20130101); C23C 8/02 (20130101) |
Current International
Class: |
C23C
16/56 (20060101); C23C 8/02 (20060101); C23c
011/02 () |
Field of
Search: |
;117/107.2,35V,62,227
;75/68C,68R,68A,68B ;148/6.27 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Kendall; Ralph S.
Claims
What is claimed is:
1. In a method for aluminum plating of a substrate by contacting a
heated substrate with an alkyl aluminum compound to cause thermal
decomposition of said alkyl aluminum compound, an improvement which
comprises heat treating said substrate covered with aluminum at a
temperature of not lower than 400.degree. C, but below the melting
point of aluminum for 10 seconds -- 30 minutes in an inert
atmosphere, then contacting thus treated substrate with a small
amount of a surface treating agent selected from active
hydrogen-containing compound, oxygen and halogen, and thereafter
taking out the substrate into the air.
2. A substrate plated with aluminum according to the method as
claimed in claim 1.
3. A method according to claim 1, wherein the alkyl aluminum
compound is selected from dialkyl aluminum hydride, trialkyl
aluminum having alkyl groups of two-20 carbon atoms and a mixture
thereof.
4. A method according to claim 1, wherein the substrate heated to
300.degree.-600.degree. C. was contacted with liquid or vapor of
the alkyl aluminum compound to plate the substrate with
aluminum.
5. A method according to claim 1, wherein the heat treatment was
carried out at 450.degree.-600.degree. C. for 20 seconds -- 15
minutes.
6. A method according to claim 1, wherein the active-hydrogen
containing compound is selected from the group consisting of water,
ammonia, primary and secondary amine compounds, sulfides, mono- and
poly-hydric alcohols, carboxylic acids, and inorganic acids.
7. A method according to claim 6, wherein the primary and secondary
amine compounds are selected from the group consisting of dimethyl
amine, and monobutyl amine.
8. A method according to claim 6, wherein the sulfide is selected
from the group consisting of hydrogen sulfide, ethyl thioalcohol,
dodecyl thioalcohol.
9. A method according to claim 6, wherein the mono- and poly-hydric
alcohols are methanol, ethanol, isopropyl-alcohol, butanol,
ethylene glycol, propylene glycol and glycerine.
10. A method according to claim 6, wherein the carboxylic acid is
selected from the group consisting of acetic acid, naphthenic acid,
stearic acid, adipic acid, maleic acid and phthalic acid.
11. A method according to claim 6, wherein the inorganic acid is
selected from the group consisting of hydrogen chloride, hydrogen
fluoride, hydrogen bromide and nitric acid.
12. A method according to claim 1, wherein the halogen is selected
from chlroine, fluorine and bromine.
13. A method according to claim 1, wherein the substrate plated
with aluminum is contacted with a solution containing active
hydrogen-containing compound in an amount of 10 - 10,000 ppm.
14. A method according to claim 1, wherein the substrate plated
with aluminum is contacted with an atmosphere of active
hydrogen-containing compound of 0.01 - 20 mmHg.
15. A method according to claim 1, wherein the substrate plated
with aluminum is contacted with a solution containing 10 - 10,000
ppm of oxygen.
16. A method according to claim 1, wherein the substrate plated
with aluminum is contacted with a gas atmosphere containing oxygen
of 0.01 - 100 mmHg.
17. A method according to claim 1, wherein the substrate plated
with aluminum is contacted with a solution containing 10 - 2,000
ppm of a halogen.
18. A method according to claim 1, wherein the substrate plated
with aluminum is contacted with a gas atmosphere containing a
halogen of 0.01 - 20 mmHg.
19. A method according to claim 6, wherein the substrate plated
with aluminum is contacted with the surface active agent at
0.degree. - 300.degree. C.
20. In a method for aluminum plating a substrate by contacting a
heat substrate with an alkyl aluminum compound to cause thermal
decomposition of said alkyl aluminum compound, an improvement which
comprises contacting said substrate covered with aluminum with a
small amount of a surface treating agent selected from active
hydrogen-containing compound, oxygen and halogens, then heat
treating the substrate at a temperature of not lower than
400.degree. C, but below the melting point of aluminum for 10
seconds -- 30 minutes and thereafter taking out thus treated
substrate into the air.
21. A method according to claim 20, wherein the alkyl aluminum
compound is selected from dialkyl aluminum hydride, trialkyl
aluminum having alkyl groups of two-20 carbon atoms and a mixture
thereof.
22. A method according to claim 20, wherein the substrate heated to
300.degree.-600.degree. C. was contacted with liquid or vapor of
the alkyl aluminum compound to plate the substrate with
aluminum.
23. A method according to claim 20, wherein the heat treatment was
carried out at 450.degree.-600.degree. C. for 20 seconds -- 15
minutes.
24. A method according to claim 20, wherein the active-hydrogen
containing compound is selected from the group consisting of water,
ammonia, primary and secondary amine compounds, sulfides, mono- and
poly-hydric alcohols, carboxylic acids, and inorganic acids.
25. A method according to claim 24, wherein the primary and
secondary amine compounds are selected from the group consisting of
dimethyl amine, and monobutyl amine.
26. A method according to claim 24, wherein the sulfide is selected
from the group consisting of hydrogen sulfide, ethyl thioalcohol,
dodecyl thioalcohol.
27. A method according to claim 24, wherein the mono- and
poly-hydric alcohols are methanol, ethanol, isopropyl-alcohol,
butanol, ethylene glycol, propylene glycol and glycerine.
28. A method according to claim 24, whrein the carobxylic acid is
selected from the group consisting of acetic acid, naphthenic acid,
stearic acid, adipic acid, maleic acid and phthalic acid.
29. A method according to claim 1, wherein the inorganic acid is
selected from the group consisting of hydrogen chloride, hydrogen
fluoride, hydrogen bromide and nitric acid.
30. A method according to claim 20, wherein the halogen is selected
from chlorine, fluorine and bromine.
31. A method according to claim 30, wherein the substrate plated
with aluminum is contacted with a solution containing active
hydrogen-containing compound in an amount of 10 - 10,000 ppm.
32. A method accoding to claim 20, wherein the substrate plated
with aluminum is contacted with an atmosphere of active
hydrogen-containing compound of 0.01 - 20 mmHg.
33. A method according to claim 20, wherein the substrate plated
with aluminum is contacted with a solution containing 10 - 10,000
ppm of oxygen.
34. A method according to claim 20, wherein the substrate plated
with aluminum is contacted with a gas atmosphere containing oxygen
of 0.01 - 100 mmHg.
35. A method according to claim 20, wherein the substrate plated
with aluminum is contacted with a solution containing 10 - 2,000
ppm of halogen.
36. A method according to claim 30, wherein the substrate plated
with aluminum is contacted with a gas atmosphere containing a
halogen of 0.01 - 20 mmHg.
37. A method according to claim 20, wherein the substrate plated
with aluminum is contacted with the surface active agent at
0.degree. - 300.degree. C.
38. A substrate plated with aluminum according to the method as
claimed in claim 20.
Description
This invention relates to an aluminum plating process and more
particularly it concerns a process for effecting excellent aluminum
plating on a substrate by contacting a heated substrate with an
alkyl aluminum compound to cause thermal decomposition of said
alkyl aluminum.
By the term "a substrate covered with aluminum" is meant a
substrate which has been covered with aluminum produced by thermal
decomposition of an alkyl aluminum compound which is caused by
contact of the heated substrate with the alkyl aluminum compound,
but which has not yet been taken out into the air.
It has been proposed by K. Ziegler et al. to plate a substrate with
aluminum by contacting a heated substrate with a liquid alkyl
aluminum compound or with vapor of an alkyl aluminum compound to
cause thermal decomposition of said alkyl aluminum. In this
respect, see, for example, Japanese Pat. No. 234069.
However, such method for plating a substrate with aluminum provides
such serious drawbacks as mentioned below.
That is, the aluminum film plated on the substrate has cracks and
pin-holes which cause deterioration of the corrosion resistance,
the oxidation resistance at a high temperature and the electric
characteristics. Furthermore, the thickness of aluminum film is not
uniform, luster of the surface is extremely poor and the aluminum
film tends to peel off when bended.
As the results of the inventors' intensive research to overcome
said drawbacks, it has been found that said drawbacks can
completely be eliminated.
One object of this invention is that a substrate covered with
aluminum is heat treated at a temperature of not lower than
400.degree.C, but below the melting point of aluminum in an inert
atmosphere and thereafter the thus treated substrate is taken out
into the air
Another object is that a substrate covered with aluminum is
contacted with a very small amount of a surface treating agent
selected from active hydrogen-containing compounds, oxygen and
halogens, then is heat treated at a temperature of not lower than
400.degree. C, but below the melting point of aluminum in an inert
atmosphere and thereafter is taken out into the air or that a
substrate covered with aluminum is heat treated at a temperature of
not lower than 400.degree. C, but below the melting point of
aluminum, then is contacted with a very small amount of a surface
treating agent selected from active hydrogen-containing compound,
oxygen and halogen and thereafter is taken out into the air.
According to the method of this invention, the aluminum film which
has no cracks and pin-holes on its surface, has uniform thickness,
exhibits excellent surface luster and is bonded strongly to the
substrate and is not peeled off therefrom can be obtained.
Other objects will be apparent from the description
hereinafter.
Alkyl aluminum compounds used in this invention include any alkyl
aluminu compounds capable of depositing aluminum by thermal
decomposition. Among them, the following are preferable because
they are easily thermally decomposed and are economical. That is,
dialkyl aluminum hydride or trialkyl aluminum having alkyl groups
of two - 20 carbon atoms such as triethyl aluminum, diethyl
aluminum hydride, trinormal propyl aluminum, triisopropyl aluminum,
trinormalbutyl aluminum, dinormalbutyl aluminum hydride,
triisobutyl aluminum, diisobutyl aluminum hydride, trinormalbenzyl
aluminum, trinormalhexyl aluminum, trinormaloctyl aluminum,
tri-2-ethylhexyl aluminum, di-2-ethylhexyl aluminum hydride, and
tridecyl aluminum, or mixtures thereof.
Furthermore, the alkyl aluminum compound may be used together with
a compound capable of producing a complex compound with the alkyl
aluminum compound such as an alkali metal compound, an ether, a
tertiary amine, a quaternary ammonium salt, etc., which are
mentioned in U.S. Pat. Nos. 3,154,407 and 3,273,996 to attain
plating of aluminum in high purity. In addition, the alkyl aluminum
compound may be used in admixture with an inert organic solvent
such as hexane, heptane, octane, cyclopentane, cyclohexane,
benzene, toluene, xylene, petroleum, paraffins, alkyl benzene,
diphenyl, etc.
Substrates to be plated include, for example, metals such as iron,
steel, aluminum, copper, brass pottery, glass, organic and
inorganic resins, etc.
The substrate is preferably cleaned prior to plating.
The substrate is heated to a temperature higher than thermal
decomposition temperature of alkyl aluminum compound, preferably of
300.degree. - 600.degree. C and is contacted with plating solution
or plating vapor. The substrate may be heated by known heating
methods and e.g., resistance heating, induction heating, etc., may
be employed depending upon kind or shape of the substrate. The
induction heating is preferable for continuous heating of
especially thin metal sheet.
As the method for obtaining a substrate covered with aluminum
according to this invention, either one of the method according to
which a heated substrate is contacted with a liquid alkyl aluminum
compound and the method according to which a heated substrate is
contacted with vapor of an alkyl aluminum compound may be used.
Election of either one of these methods depends upon kind and shape
of the substrate to be plated. The substrate may be covered with
aluminum by thermal decomposition of an alkyl aluminum compound on
a substrate by one time heating or by intermittent two or more
heatings. The latter is especially preferable. Further, there is
the case that the latter method does not necessitate heat-treating
of a substrate covered with aluminum.
The thermal decomposition may be carried out in the presence of a
compound capable of accelerating the thermal decomposition such as
titanium chloride, titanium bromide, vanadium chloride, iron
chloride, copper chloride, etc. which are mentioned in U.S. Pat.
No. 3,306,732. Addition of said compound is useful especially for
plating a substrate of low heat stability.
The thermal decomposition is required to be carried out in an inert
atmosphere, but no critical limitation is present in pressure for
operation.
The substrate covered with aluminum as mentioned above is then fed
to a heat treatment step or is firstly contacted with a very small
amount of a surface treating agent selected from the group
consisting of active hydrogen-containing compounds, oxygen and
halogen, and thereafter fed to the heat treatment step. The heat
treatment in this invention is carried out by heating and keeping
the substrate at a temperature of not lower than 400.degree. C, but
below the melting point of aluminum, preferably of 450.degree. -
600.degree. C.
When the heat treating temperature is lower than 400.degree. C,
good surface properties cannot be obtained and furthermore a long
period of time is required for heat treatment. For example, with a
substrate of iron, a reaction occurs between iron and aluminum and
the aluminum film is apt to peel off.
In this invention, the aluminum heat treatment is effected in the
presence of an inert gas or a molten salt. Usually, nitrogen, argon
and helium are effectively used, but it should be noted that this
invention is not limited to the use thereof.
The heat treating time somewhat varies depending upon kind and
shape of the substrate, thickness of aluminum film and heating
temperature, but generally is 10 seconds - 30 minutes. However,
with a substrate of iron, too long treating time causes a reaction
between aluminum and iron to deteriorate the plate surface and
hence industrially, the substrate is preferably kept for 20 seconds
- 15 minutes.
After completion of the heat treatment, the substrate is taken out
into the air or firstly is contacted with a small amount of a
surface treating agent selected from the group consisting of active
hydrogen-containing compound, oxygen and halogen and thereafter
taken out into the air.
The contact of the substrate with a surface treating selected from
the active hydrogen-containing compound, oxygen and halogen may be
carried out before said heat treatment. As mentioned above, the
contact of the substrate with a very small amount of a surface
treating agent selected from active hydrogen-containing compound,
oxygen and halogen before or after the heat treatment results in
more excellent aluminum plating than that attained only by heat
treatment.
Illustrative of the active hydrogen-containing compounds to be
contacted with the substrate covered with aluminum are compounds
containing at least one substitutable hydrogen such as water,
ammonia primary or secondary amine compounds, e.g., dimethyl amine,
monobutyl amine, etc.; sulfides, e.g., hydrogen sulfide, ethyl
thioalcohol, dodecyl thioalcohol, etc.; mono- or poly-hydric
alcohols, e.g., methanol, ethanol, isopropylalcohol, butanol,
ethylene glycol, propylene glycol, glycerine, etc.; carboxylic
acids, e.g., acetic acid, naphthenic acid, stearic acid, adipic
acid, maleic acid, phthalic acid, etc.; and inorganic acids, e.g.,
hydrogen chloride, hydrogen fluoride, hydrogen bromide, nitric
acid, etc.
Those active hydrogen-containing compounds are used as a solution
which contains 10 - 10,000 ppm, preferably 100 - 1,000 ppm (weight
basis) of said compound dissolved in aromatic hydrocarbons such as
benzene, toluene, xylene, naphthalene, alkyl benzene, etc.,
aliphatic hydrocarbons such as pentane, hexane, octane, decene,
etc., and mixtures thereof or as an atmosphere of the active
hydrogen-containing compound of 0.1 - 20 mmHg, preferably 0.1 - 10
mmHg.
In case of treatment with oxygen, the substrate is contacted with
said aromatic or aliphatic hydrocarbon containing 10 - 10,000 ppm,
preferably 100 - 1,000 ppm (weight basis) of oxygen or is used as
an oxygen atmosphere of 0.01 - 100 mmHg, preferably 0.1 - 80
mmHg.
Furthermore, when halogens such as fluorine, chlorine, bromine,
etc. are used, they are used as a halogen atmosphere of 0.01 - 20
mmHg, preferably 0.1 - 10 mmHg or as a solution containing 10 -
2,000 ppm of a halogen dissolved in a suitable solvent such as a
paraffin. When the halogen is contacted in a vapor phase, the vapor
alone is not contacted, but the vapor is diluted with an inert gas
and the treatment is carried out under normal pressure or higher
pressure.
Said treatment is carried out at 0.degree. - 300.degree. C,
preferably 15.degree. - 200.degree. C.
As mentioned above, the method of this invention provides the
following advantages as compared with the conventional method in
which the substrate covered with aluminum is taken out without
further treatments.
That is, the aluminum film on the substrate has no cracks and
pin-holes on its surface, has a uniform thickness, exhibits
excellent surface luster and is bonded strongly to the
substrate.
The substrate plated with aluminum in accordance with this
invention has high corrosion resistance and oxidation resistance at
a high temperature and excellent electric characteristics.
Furthermore, the substrate plated can be subjected to metal surface
treatment, such as known sealing treatment, stabilizaton treatment
and alumite finishing. Due to these excellent characteristics the
industrial value of this invention is extremely great.
The following Examples are given by way of specifically
illustrating this invention and are not intended to be construed as
limiting in any case.
EXAMPLE 1
A steel sheet of 50 mm .times. 50 mm .times. 0.6 mm was washed with
water and subsequently with alcohols and then dried. Thus treated
steel sheet was used as a specimen.
The whole process steps from the heat treatment of the specimen
until taking out it into the air were carried out in argon
atmosphere.
Said specimen was heated to 400.degree. C in argon atmosphere and
thereafter was dipped in 500 cc of an alkyl aluminum solution which
comprises 81 percent by weight of diisobutyl aluminum hydride, 11
percent by weight of diethyl aluminum hydride, 5 percent by weight
of triisobutyl aluminum, and 3 percent by weight of triethyl
aluminum at 20.degree. C.
After lapse of one minute, the specimen was withdrawn from the
solution and deposited alkyl aluminum was maintained in argon
atmosphere at 100.degree. C and washed away.
Furthermore, the same procedure as mentioned above was repeated
once more to effect aluminum plating. Subsequently, the specimen
thus plated with aluminum was heated to 450.degree. C in argon
atmosphere. After the specimen was kept at that temperature for 5
minutes, it was cooled to room temperature in argon gas and then
taken out into the air.
Thus obtained substrate plated with aluminum has a film of 1.1 .mu.
in thickness and has excellent luster of silver white.
Furthermore, an acid resistance test was made by dipping in 500 cc
of 25 weight percent aqueous nitric acid solution at 20.degree. C
said plated substrate which was covered by solid paraffin in a
width of 10 mm around said substrate.
Even after lapse of 30 minutes, no bubbles were generated and no
change was observed in the plate surface.
For comparison, the same another specimen which was plated with
aluminum in the same manner as mentioned above was taken out into
the air without heat treatment.
Thus obtained substrate plated with aluminum has a film of 1.1 .mu.
in thickness and its surface showed silver white. The same acid
resistance test was made with this substrate. After lapse of 11
minutes, bubbles were generated and after lapse of 20 minutes the
aluminum film on the substrate was nearly peeled off.
From the foregoing results, it will be seen that with the
substrates plated with aluminum in the same thickness, the
properties of the surface subjected to the heat treatment was
extremely superior to those of the surface subjected to no heat
treatment.
EXAMPLE 2
The same specimen as in Example 1 and which was cleaned in the same
manner as in Example 1 was employed in this Example. The treatment
was carried out in argon atmosphere as in Example 1. The specimen
was pre-heated to 500.degree. C and was dipped in an alkyl aluminum
solution having the same compositions as in Example 1, heated to
200.degree. C.
After lapse of one minute, the specimen was withdrawn and washed
with 500 cc of hexane.
Then, the specimen was heated to 500.degree. C in argon atmosphere
and kept at that temperature for 5 minutes. Thereafter, it was
cooled and taken out into the air. The steel sheet thus plated with
aluminum had excellent luster of silver white and had excellent
surface properties. The average thickness of the aluminum film was
2.1 .mu. determined by weight increased.
The specimen was also subjected to the acid resistance test in the
same manner as in Example 1. Even after lapse of 30 minutes, no
bubbles were generated.
For comparison, the specimen prior to said heat treatment was
cooled in argon and then taken out into the air.
The steel sheet thus plated with aluminum had a grey color and
little luster. The same acid resistance test as mentioned above was
given to the specimen. After lapse of 5 minutes, generation of
bubbles was observed.
For further comparison, instead of said heat treatment, the
specimen was similarly heated to 300.degree. C in argon atmosphere
and kept at that temperature for 5 minutes. Then, it was cooled in
argon and taken out into the air. Thus obtained steel sheet plated
with aluminum showed grey color and had little luster. The specimen
was subjected to the same acid resistance test as mentioned above.
After lapse of 7 minutes, generation of bubbles was observed.
From the above results, it will be seen that with the steel sheets
plated with aluminum in the same thickness, the luster and
properties of the surface treated according to this invention were
superior to those of the surface which was not treated in
accordance with this invention.
EXAMPLE 3
A substrate covered with aluminum treated in the same manner as in
Example 1 until the heat treatment step was contacted with 500 cc
of hexane containing 0.01 percent by weight of water at 20.degree.
C for one minute and then taken out into the air.
Thus obtained steel sheet plated with aluminum showed excellent
luster of silver white and had extremely excellent surface
properties.
Said steel sheet was subjected to the same acid resistance test as
in Example 1. Even after lapse of 50 minutes, generation of bubbles
was not observed.
In said method, instead of water treatment, the steel sheets were
treated with 500 cc of hexane containing 0.01 percent by weight of
ethanol, 500 cc of hexane containing 0.01 percent by weight of
oxygen and argon atmosphere containing chlorine gas of 1 mmHg,
respectively and they were taken out into the air. Thus obtained
steel sheets plated with aluminum showed excellent luster of silver
white and had extremely excellent surface properties.
Each steel sheet was subjected to the same acid resistance test as
in Example 1. The same results as in case of the water treatment
were obtained.
EXAMPLE 4
A substrate covered with aluminum in the same manner as in Example
1 was contacted with 500 cc of hexane containing 0.01 percent by
weight of water at 20.degree. C for one minute. Thereafter, it was
heated to 500.degree. C in argon atmosphere for 5 minutes and kept
at that temperature. Then, the substrate was cooled to room
temperature in argon gas and taken out into the air. Thus obtained
steel sheet plated with aluminum showed excellent luster of silver
white and had extremely excellent surface properties.
This steel sheet was subjected to the same acid resistance test as
in Example 1 to find no generation of bubbles even after lapse of
40 minutes.
In said method, instead of the water treatment, steel sheets were
treated with 500 cc of hexane containing 0.01 percent by weight of
ethanol, 500 cc of hexane containing 0.01 percent by weight of
oxygen and argon atmosphere containing chlorine gas of 1 mmHg,
respectively. Thereafter, they were heat treated as mentioned
above, cooled and then taken out into the air. They had excellent
surface properties as in the case of the water treatment.
Each steel sheet thus treated was subjected to the acid resistance
test as in Example 1 to obtain the same results as in case of the
water treatment.
* * * * *