U.S. patent number 3,769,084 [Application Number 05/887,678] was granted by the patent office on 1973-10-30 for method for forming carbon coating and composite article with a carbonaceous coating thereon.
This patent grant is currently assigned to Hitachi, Ltd.. Invention is credited to Tetsuo Gejyo, Tadashi Saito.
United States Patent |
3,769,084 |
Saito , et al. |
October 30, 1973 |
METHOD FOR FORMING CARBON COATING AND COMPOSITE ARTICLE WITH A
CARBONACEOUS COATING THEREON
Abstract
A carbon coated layer having good property for controlling the
secondary electron emission and electron reflecting effect is
deposited on a metal article surface having an amorphous nickel
layer plated thereon by heating at a temperature of from 500 to
680.degree.C in an atmosphere containing at least one hydrocarbon
gas selected from the group consisting of acetylene, ethylene,
ethane and propane having a partial pressure of 5 to 50 Torr.
Inventors: |
Saito; Tadashi (Tokyo,
JA), Gejyo; Tetsuo (Tokyo, JA) |
Assignee: |
Hitachi, Ltd. (Tokyo,
JA)
|
Family
ID: |
14113435 |
Appl.
No.: |
05/887,678 |
Filed: |
December 23, 1969 |
Foreign Application Priority Data
|
|
|
|
|
Dec 25, 1968 [JA] |
|
|
43/94551 |
|
Current U.S.
Class: |
428/634; 427/78;
427/294; 428/680; 428/936; 205/192; 427/122; 428/457; 428/935 |
Current CPC
Class: |
H01J
9/146 (20130101); C23C 16/26 (20130101); Y10T
428/31678 (20150401); Y10S 428/935 (20130101); Y10T
428/12944 (20150115); Y10T 428/12625 (20150115); Y10S
428/936 (20130101) |
Current International
Class: |
C23C
16/26 (20060101); H01J 9/14 (20060101); B44d
001/14 (); B44d 001/18 (); C01b 031/00 () |
Field of
Search: |
;117/46CB,46CG,216,217,131,226 ;29/195 ;204/38R,49
;423/448,450,458 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Martin; William D.
Assistant Examiner: Sofocleous; M.
Claims
We claim:
1. A method for forming a carbon coated metal substrate which
comprises the steps of (a) forming an amorphous nickel layer on the
surface of a metal substrate to thereby form an amorphous nickel
plated metal substrate and (b) heating said amorphous nickel plated
metal substrate at a temperature of 500.degree. C. to 680.degree.
C. in an atmosphere comprising a hydrocarbon having a partial
pressure of 5 to 50 Torr., thereby coating said amorphous nickel
plated metal substrate with carbon.
2. A method according to claim 1, wherein said amorphous nickel
layer has a thickness of about 2 .mu..
3. A method according to claim 1, wherein said amorphous nickel
layer is electrolytically formed.
4. A method according to claim 1, wherein said amorphous nickel
layer is nonelectrolytically formed.
5. A method according to claim 1, wherein said hydrocarbon is at
least one member selected from the group consisting of acetylene,
ethylene and ethane.
6. A method according to claim 1, wherein said atmosphere
comprising hydrocarbon comprises at least one member selected from
the group consisting of acetylene, ethylene, ethane and propane
having a partial pressure of 5 to 50 Torr. and a carrier gas
selected from the group consisting of an inert gas and
hydrogen.
7. A carbon coated metal article, which comprises a metal
substrate, an amorphous nickel plated layer on said substrate and a
carbon coating on said amorphous nickel plated layer said carbon
coating being formed by heating said amorphous nickel plated metal
substrate in an atmosphere containing a hydrocarbon at a partial
pressure of 5 to 50 Torr. at a temperature of from 500.degree. C.
to 680.degree. C.
8. A metal coated article according to claim 7, wherein the
substrate of said metal article is a member selected from the group
consisting of mild steel, nickel, copper, molybdenum and stainless
steel.
9. A shadow mask for color television which comprises a metal
substrate, an amorphous nickel plating layer thereon, and a carbon
coating on said amorphous nickel plating layer, said carbon coating
being coated on said amorphous nickel plating layer by heating a
metal substrate having an amorphous nickel plating layer in an
atmosphere comprising a hydrocarbon having a partial pressure of 5
to 50 Torr. at 500.degree.-680.degree. C.
10. An electric discharge tube plate material which comprises a
metal substrate, an amorphous nickel plating layer thereon, and a
carbon coating on said amorphous nickel plating layer, said carbon
coating being coated on said amorphous nickel plating layer by
heating a metal substrate having an amorphous nickel plating layer
in an atmosphere comprising a hydrocarbon having a partial pressure
of 5 to 50 Torr. at 500.degree.-680.degree. C.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a method for forming carbon coating and a
composite article with a carbonaceous coating thereon, and more
particularly to a method for forming carbon coating on a metal
plate and a composite metal member with a carbonaceous coating
thereon. Such composite metal member is usable for a shadow mask of
a color picture tube and an anode member of an electric discharge
tube, or in various fields. For example, in the color picture tube,
a color effect has been considerably impaired by the primary
electron reflection and the secondary electron discharge from the
shadow mask. Accordingly, it has been necessary to reduce such
primary electron reflection and secondary electron discharge from
the shadow mask, and it has been presumed effective to coat a
shadow mask with a substance of low atomic weight, particularly
carbon. Thus, the art of coating the shadow mask with such
substance has been important to establish.
2. Description of the Prior Art
Heretofore, a method for depositing graphite onto a metal by
thermally decomposing acetylene at a temperature of 1,000.degree.
.+-. 25.degree.C [A.E.B. Presland and P.L. Walker: 7 Jr. Carbon 1
(1969)] or a method for coating a nickel plate with carbon by
thermally decomposing methane, ethane, ethylene, etc. on the nickel
plate at 870.degree.-1030.degree.C [Y. Tamai et al.: 6 Jr. Carbon
593 (1968)] has been known as the conventional method for coating a
metal plate with carbon, but any of these two methods is directed
to formation of carbon coating by thermal decomposition of
hydrocarbon at a temperature higher than 800.degree.C.
However, a mild steel plate having a thickness of 0.15-0.3 mm is
usually used for a shadow mask for television receiver, and
accordingly, if it is heated to a temperature higher than
800.degree.C, the shadow mask is considerably deformed and no more
used practically. Thus, heating to a temperature higher than
800.degree.C must be absolutely avoided.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a method for
forming a carbon coating on a metal substrate by thermally
decomposing a hydrocarbon at a temperature lower than 800.degree.C
and obtain a composite article with a carbonaceous coating.
The object of the present invention can be attained by forming an
amorphous nickel plating on a substrate metal by electrolysis or
non-electrolysis, heating the nickel-plated substrate metal in an
atmosphere of at least one of such saturated and unsaturated
hydrocarbons as acetylene, ethylene, ethane and propane or a
gaseous mixture consisting of said hydrocarbon and at least one of
hydrogen and inert gases (5-50 Torr) at 500.degree.-680.degree.C
and thereby thermally decomposing said hydrocarbon.
The amorphous nickel plating layer deposited by electrolysis or
non-electrolysis acts as a catalyst for thermal decomposition of
hydrocarbon, and thus the thermal decomposition reaction proceeds
at about 600.degree.C, which is by more than 200.degree.C lower
than the conventional, lowest temperature possible for the thermal
decomposition.
Not only the catalytic action of the amorphous nickel plating layer
deposited by electrolysis or non-electrolysis is more effective
than a nickel plate, but also the uniformity and adhesiveness of
carbon coating deposited on said amorphous nickel plating layer are
better than those of the carbon coating deposited on the nickel
plate, mild steel plate, copper plate, molybdenum plate, stainless
steel plate or other metal plate.
Furthermore, said amorphous nickel plating layer considerably
accelerates a carbon build-up speed.
The present invention now will be explained in detail, referring to
the drawings.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 shows a block diagram of a thermal decomposition apparatus
used for conducting the present method.
FIG. 2 shows influences of the presence of amorphous nickel plating
deposited on the surface of thin metal plate, upon the carbon
build-up speed.
FIG. 3 is a cross-sectional view of a composite metal plate with a
carbonaceous coating.
Explanation is made of the apparatus for effecting carbon coating
shown in FIG. 1. A hydrogen cylinder 1, an argon cylinder 2, and a
hydrocarbon cylinder 3 are provided with cocks 4, 5 and 6 for
controlling gas flow rates and flowmeters 7, 8 and 9 respectively,
and a constant flow rate of said hydrocarbon gas or a gaseous
mixture of said hydrocarbon and argon and/or hydrogen is always fed
to a reaction tube 12 as a reactant gas during the thermal
decomposition reaction.
Procedures of operation for effecting carbon coating are given
below.
a. A specimen 10 is placed on a specimen base 11.
b. Cocks 4, 5, 6 and 16 are closed and cocks 14 and 15 are opened.
Then, exhaustion of gas is effected by a vacuum pump 18.
c. When the inside of the reaction tube becomes vacuum
(10.sup.-.sup.2 Torr or less), the cock 15 is closed, and then the
cock 4 is opened to introduce hydrogen into the reaction tube. When
the inside of the reaction tube reaches the atmospheric pressure,
the cock 16 is opened to attain a constant flow rate of the
hydrogen stream.
d. The specimen 10 is elevated to a predetermined temperature by
means of an electric furnace 13.
e. The cocks 4 and 16 are closed, and the cock 15 is opened.
Exhaustion of gas is carried out by the vacuum pump 18.
f. When the inside of the reaction tube becomes vacuum
(10.sup.-.sup.2 Torr or less), the cock 15 is closed, and a gas of
a definite composition is introduced into the reaction tube by
adjusting the cocks 4 and 6, while watching the flowmeters 7 and 9.
When the inside of reaction tubes reaches the atmospheric pressure,
the cock 16 is opened to attain a definite flow rate of the gas
stream.
g. After a predetermined period of time, the cocks 4, 6 and 16 are
closed, and the cock 15 is opened. Exhaustion of gas is carried out
by the pump 18.
By carrying out the procedures (a) to (g), coating of the specimen
with carbon can be completed.
When said carbon coating is carried out in a reactant gas under a
pressure less than the atmosphere, the reactant gas of a definite
pressure is introduced into the reaction tube in said operation
(f), and then the reduced pressure can be attained by closing cocks
4 and 6.
Further, when argon is used as a carrier gas, the cock 5 for
feeding argon gas is adjusted while watching the flowmeter 8 in
said operation (f) in place of the cock 4 for supplying the
hydrogen and the flowmeter 7.
In the present invention, hydrocarbon undergoes the thermal
decomposition reaction represented by the following general
formula:
C.sub.n H.sub.m .fwdarw. n( + (m/2)H.sub.2 (m and n are
integers.)
Said hydrocarbon includes acetylene, ethylene, ethane and propane
alone or their gaseous mixtures.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
To clarify the effect of the present invention, thin plates (2.0
.times. 1.5 .times. 0.02 cm) of such metals as mild steel, copper,
molybdenum and stainless steel were plated with amorphous nickel by
electrolysis or non-electrolysis and used as specimens.
The conditions for amorphous nickel plating by non-electrolysis are
given below:
Mild steel plates were subjected to surface treatments of
trichloroethylene defatting, quirinse pickling, water washing and
drying. When said surface-treated mild steel plate was dipped into
a non-electrolytic plating solution (bath composition: 30 g/l of
NiCl.sub.2.sup.. 6H.sub.2 O, 10 g/l of NaH.sub.2 PO.sub.2.sup..
H.sub.2 O and 10 g/l of NaC.sub.2 H.sub.3 O.sub.2) for 10 minutes,
an amorphous nickel plating having a thickness of about 2 .mu. was
obtained. The pH of the plating bath was 4-8, and the bath
temperature was 80.degree.C.
The conditions for amorphous nickel plating by electrolysis were
given below:
Surface defatting and washing were carried out in the same manner
as in the nickel plating by non-electrolysis.
Plating bath composition:
240 g/l of Nickel sulfate
45 g/l of Nickel chloride
30 g/l of Boric acid
pH =4-4.5, 40.degree.C
Anode: Nickel plate containing 10 percent of phosphorus
Electrolysis condition: 1 A/dm.sup.2, 1.2 V
The thus prepared specimens were subjected to different thermal
decomposition conditions and the thus obtained results are shown in
Table 1, Examples 1 to 18. Examples 1 to 5 of Table 1 are to
investigate the optimum thermal decomposition temperature of
acetylene reactant gas.
In order to efficiently prevent the secondary electron discharge
and electron reflection as in the color picture tube, it is an
essential requirement that a uniform and thick carbon coating
having a high apparent density be deposited on a substrate with a
good adhesiveness.
Accordingly, if any of average thickness, apparent density,
adhesiveness and uniformity be extremely worse, an improvement in
color effect by the carbon coating is considerably reduced. The
values of the adhesiveness and the uniformity in Table 1 are based
on the values of Example 3. In Example 1, a gaseous mixture of
acetylene and hydrogen (containing 50 percent by volume of
hydrogen) was subjected to reaction at a thermal decomposition
temperature of 480.degree.C under a pressure of 10 Torr for 35
minutes. Under such conditions, the average thickness was 0.7 .mu.,
the apparent density 0.4, the adhesiveness 0.5 and the uniformity
0.3, and these properties were considerably worse. This is because
the thermal decomposition temperature is too low and as a result
the thermal decomposition is not carried out sufficiently.
At the thermal decomposition temperatures of Examples 2 to 4, the
average thickness was 5-11 .mu., the apparent density 0.5-1.8, the
adhesiveness 0.8-1.0, and the uniformity 0.53-1, and thus a carbon
coating having a good influence upon the improvement in color
effect was obtained in Examples 2 to 4.
When the thermal decomposition temperature reached 700.degree.C,
the average thickness was considerably reduced to 3 .mu., the
apparent density 0.9, the adhesiveness 0.48 and the uniformity 0.4,
because the catalytic action of the nickel plating seemed to be
lowered at that temperature.
It is seen from the foregoing result that the thermal decomposition
temperature is suitably 500.degree.C to 680.degree.C, and most
preferably about 600.degree.C.
The experiment on the pressure of the reactant gas reveals, as
clearly shown in Examples 6-9, that the adhesiveness was 0.4 and
the uniformity was 0.51 under 200 Torr of Example 9 , and that the
reactant gas pressure was suitably 5-50 Torr. Further, it was found
that the adhesion state at the edge part of a shadow mask was
considerably more improved, if the pressure was lower.
An influence of the amorphous nickel plating layer upon the carbon
build-up speed is hereunder examined. In FIG. 2, the carbon deposit
amount is indicated on the ordinate and the time on the abscissa,
whereby the carbon build-up speeds on the different substrate metal
plates are shown individually. The curve 19 is for a metal plate
for an amorphous nickel plating layer of the present invention, the
curve 20 for a nickel plate and the curve 21 for a mild steel plate
having no nickel plating layer.
As is clear from FIG. 2, the carbon build-up speed, that is, a
speed of forming a carbon coating on a substrate is considerably
higher when a substrate having a nickel plating layer thereon is
used, than when simply a nickel plate or mild steel substrate is
used. A case only of acetylene is shown in Example 15, where the
average thickness is 4 .mu. and the apparent density 1.5
g/cm.sup.3, and the adhesiveness and the uniformity are somewhat
inferrior to those of Example 3.
In FIG. 3, a cross-sectional view of a carbon-coated metal plate
prepared by carbon coating of the present invention is given,
wherein numeral 22 is a carbon coating film, 23 an amorphous nickel
plating layer and 24 a substrate metal plate.
Further, comparison of Example 3 with Examples 16 and 17 in Table 1
reveals that the carbon coating deposited on a substrate plated
with amorphous nickel by non-electrolysis is superior in the
average thickness, apparent density, adhesiveness and uniformity,
to the mild steel plate and the nickel plate.
It is seen from the foregoing that in coating a thin metal plate
with carbon by thermal decomposition of hydrocarbon, it is an
important essential requirement for the present invention to effect
amorphous nickel plating on the thin metal plate in advance by
electrolysis or non-electrolysis.
Examples 1-9 and 13-18 show the cases where acetylene is a main
reactant gas, but it is possible to effect carbon coating by
thermal decomposition of other reactant gases than acetylene, for
example, ethane, ethylene and propane, at a thermal decomposition
temperature of 600.degree.C, though the properties of deposited
carbon coating are somewhat poorer than those obtained from
acetylene, as shown in Examples 10 to 12.
Examples 13 and 14 show cases where other copper and molybdenum
plates than the mild steel plates are used, and a practical carbon
coating can be effected, though the properties of deposited carbon
coating are somewhat poorer than those of Example 3.
The foregoing results can be summarized as follows:
1. The thermal decomposition speed of hydrocarbon is higher when an
amorphous nickel plating is applied to a shadow mask substrate in
advance by electrolysis or non-electrolysis than when the mild
steel plate or the nickel plate is used as a substrate
directly.
2. The secondary electron discharge- and electron
reflection-controlling effect of carbon coating film deposited on
the amorphous nickel-plated substrate by electrolysis or
non-electrolysis is considerably higher than those of carbon
coating film deposited directly on the mild steel plate or the
nickel plate.
3. Thermal decomposition reaction is suitably carried out in a
temperature range of 500.degree. to 680.degree.C, and the most
preferable temperature is about 600.degree.C.
4. The pressure of reactant gas is suitably in a range of 5-50
Torr, and the most preferable pressure is 10 Torr.
5. Saturated and unsaturated hydrocarbons or a gaseous mixture
consisting of said hydrocarbon and hydrogen and/or argon are
suitable as a reactant gas.
6. Acetylene, ethylene, ethane and propane are suitable as
saturated and unsaturated hydrocarbons, and acetylene is most
suitable. ##SPC1##
* * * * *