U.S. patent number 3,850,701 [Application Number 05/409,682] was granted by the patent office on 1974-11-26 for anode coated with magnetite and the manufacture thereof.
This patent grant is currently assigned to The Japan Carlit Co., Ltd.. Invention is credited to Reiichi Itai, Hideo Kanai.
United States Patent |
3,850,701 |
Itai , et al. |
November 26, 1974 |
ANODE COATED WITH MAGNETITE AND THE MANUFACTURE THEREOF
Abstract
An anode coated with magnetite is manufactured by
electrodepositing iron on a metallic substrate consisting of
titanium, zirconium, tantalum, or niobium and the like in an
electrolyte containing ferrous sulfate, dipping said iron deposited
substrate into a solution of ammonium ferric oxalate under a
reduced pressure, and then heating said treated substrate in an
atmosphere of a gaseous mixture of hydrogen and steam. The anode
manufactured in this way is quite suitable for the production of
chlorine, chlorates, and bromates, and, furthermore, it is also
usable for electrolytic oxidation processes in general and as an
anode for electro-winning of copper, for electrolysis of sodium
sulphate, for cathodic protection, and for electrodialysis.
Inventors: |
Itai; Reiichi (Maebashi,
JA), Kanai; Hideo (Maebashi, JA) |
Assignee: |
The Japan Carlit Co., Ltd.
(Tokyo, JA)
|
Family
ID: |
12533938 |
Appl.
No.: |
05/409,682 |
Filed: |
October 25, 1973 |
Foreign Application Priority Data
|
|
|
|
|
Apr 6, 1973 [JA] |
|
|
48-38749 |
|
Current U.S.
Class: |
428/472.2;
148/287; 205/229; 205/196; 204/290.12 |
Current CPC
Class: |
C25C
7/02 (20130101); C25B 11/077 (20210101); C23F
13/02 (20130101) |
Current International
Class: |
C25B
11/00 (20060101); C25C 7/00 (20060101); C23F
13/02 (20060101); C23F 13/00 (20060101); C25B
11/04 (20060101); C25C 7/02 (20060101); C23c
011/10 (); B01k 003/04 () |
Field of
Search: |
;204/29F,37,48
;148/6.35,6.3 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Welsh; John D.
Attorney, Agent or Firm: Flynn & Frishauf
Claims
What is claimed is:
1. A process for manufacturing an anode coated with magnetite
comprising electrodepositing iron onto an electric conductive
corrosion-resistant metallic substrate, such as titanium,
zirconium, tantalum, niobium, and the like in an electrolyte
containing ferrous sulfate, dipping said iron deposited substrate
into a solution containing about 10 - 30 g/l ammonium ferric
oxalate for about 20 min under a reduced pressure of 10 - 30 mm Hg
abs., and then heating said treated substrate at 550.degree. -
700.degree.C for about 2 - 5 hrs. in an atmosphere of a
hydrogen/steam gaseous mixture consisting of hydrogen of a content
in a range of 10 - 25 percent by volume and steam of a content in a
range of 75 - 90 percent by volume.
2. A process for manufacturing an anode coated with magnetite
according to claim 1 wherein said composition of the electrolyte
containing ferrous sulfate consisting of 100 - 150 g/l of ferrous
sulfate (heptahydrate), 100 g/l of ammonium sulfate, and about 3 -
10 g/l of an additive selected from a group consisting of ammonium
salts of an organic acid, phenol, formalin and hexamethylene
tetramine, and mixtures thereof.
3. A process for manufacturing an anode coated with magnetite
according to claim 1 wherein said electrodeposition is carried out
under a bath temperature in a range of 10.degree. - 40.degree.C, a
cathodic current density of 1.0 - 2.5 A/dm.sup.2 , and the
electrodeposition time being about 7 - 20 min.
4. An anode coated with magnetite, manufactured by a process which
comprises electrodepositing iron onto an electric conductive
corrosion-resistant metallic substrate, such as titanium,
zirconium, tantalum, niobium, and the like in an electrolyte
containing ferrous sulfate, dipping said iron deposited substrate
into a solution containing about 10 - 30 g/l ammonium ferric
oxalate for about 20 min. under a reduced pressure of 10 - 30 mm Hg
abs., and then heating the treated substrate at 550.degree. -
700.degree.C for about 2 - 5 hrs. in an atmosphere of a
hydrogen/steam gaseous mixture consisting of hydrogen of a content
in a range of 10 - 25 percent by volume and steam of a content in a
range of 75 - 90 percent by volume.
Description
BACKGROUND OF THE INVENTION
A magnetite anode has hitherto been manufactured by casting as a
hollow cylinder or a hollow plate, but disadvantages of the product
were inferior workability, limited shapes available and inferior
electric conductivity. An improved anode coated with magnetite was
proposed in order to eliminate these disadvantages by allowing iron
containing iron oxide to deposit electritically on a substrate
consisting of iron or titanium, or by coating a solution containing
iron compound which generates iron oxide on heating, followed by
subjecting the treated substrate to heat treatment in a gaseous
atmosphere consisting of a mixture of hydrogen and steam. Although
the disadvantages limited in shapes and inferior electric
conductivity of the product were eliminated by this improvement,
other disadvantages due to coarse-grained and less durable
magnetite coating which leads to an extremely short life of the
product remained. Such a product, therefore, can not be accepted as
a satisfactory product for industrial use.
SUMMARY OF THE INVENTION
An essential object of this invention is to provide a process for
manufacturing an anode coated with magnetite with industrially
advantageous performance.
Another object of this invention is to provide a process for
forming a fine-grained and durable magnetite coating on a metallic
substrate.
Still another object of this invention is to provide a process for
manufacturing an anode coated with magnetite having an industrially
advantageous life.
The aforementioned, objects, other objects and the merits of this
invention will be made clear by the description hereunder.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
This invention relates to a process for manufacturing an anode
coated with magnetite which comprises electrodepositing iron on a
metallic substrate of an electrically conductive,
corrosion-resistant metal such as titanium, zirconium, tantalum, or
niobium by using an electrolyte containing ferrous sulfate, then
dipping said iron deposited substrate in a solution containing
about 10 - 30 g/l of ammonium ferric oxalate under a reduced
pressure of 10 - 30 mm Hg abs., further heating said treated
substrate at a temperature of between 550.degree. and 700.degree.C
in an atmosphere of a gaseous mixture of hydrogen and steam wherein
the hydrogen content is 10 - 25 percent by volume and the steam
content is 75 - 90 percent by volume. Any commercially available
materials in the forms of a plate, wire, screen or rod of titanium,
zirconium, tantalum, or niobium may be used as an electrically
conductive, corrosion-resistant metallic substrate.
As an electrolyte for electrodepositing iron, a sulfate bath is
preferable. When a chloride bath is used, although it is commonly
used now in industry, close control of the temperature, pH, and the
composition of the bath is necessary in order to obtain a
fine-grained and firmly deposited metal bonded to the metallic
substrate. When a sulfate bath in accordance with this invention is
used, on the other hand, satisfactory results of the
electrodeposition can always be obtained under a wider range of the
conditions of electrodeposition. In addition to this, the sulfate
bath is less readily oxidized by the air than the chloride bath,
and therefore said electro-deposition can be carried out in the
absence of the ferric salt. The presence of a ferric salt
accelerates, the generation of hydrogen on the electrodepositing
surface, causing undesirable formation of pinholes, lowering the
cathodic current efficiency and resulting in less adherent
deposits, as is described in Japanese Pat. No. 219,829. The sulfate
bath in accordance with this invention contains no ferric salt and
gives an essentially high cathodic current efficiency, thus
assuring a satisfactory deposit with few pinholes and a good
adherence.
The composition of the electrolyte for electrodepositing iron
consists of, for instance, 100 - 150 g/l of ferrous sulfate
(heptahydrate), 100 g/l of ammonium sulphate and about 3 - 10 g/l
of additives such as an ammonium salt of an organic acid, phenol,
formalin, or hexamethylene tetramine, etc. Electrodeposition is
carried out at a temperature of 10.degree. - 40.degree.C and at a
cathodic current density of 1.0 - 2.5 A/dm.sup.2 for about 7 - 20
min. Under these conditions the atmospheric oxidation of the
ferrous salt in said electrolyte is retarded, and almost no
hydrogen is generated at the electrodepositing surface, thus, a
uniform and fine-grained deposit is obtained.
As a subsequent treatment following said electro-deposition, the
iron deposited substrate is dipped into a solution of ammonium
ferric oxalate ( (NH.sub.4).sub.3 Fe(C.sub.2 O.sub.4).sub.3 ).
Although no such treatment to an electrodeposited surface with iron
has hitherto been known, it is considered as a kind of sealing
treatment which reinforces electrodeposits. It has been confirmed
that by said treatment the durability of the final product as an
anode is remarkably increased as compared to one to which said
treatment is not applied. Said treatment is performed by dipping
the iron deposited substrate in a sealing solution containing about
10 - 30 g/l of ammonium ferric oxalate, at about 10.degree. -
25.degree.C, then by allowing said iron deposited substrate to
stand for about 20 min under a reduced pressure of 10 - 30 mm Hg
abs. A concentration of ammonium ferric oxalate below 10 g/l is too
dilute to be effective, and above 30 g/l, an undesirable deposition
of crystals will occur. Further, if the pressure is higher than 30
mm Hg abs., the replacement of the air within pinholes with said
solution is only imperfectly accomplished and only unsatisfactory
results are obtained. The minimum pressure is limited by the
saturated vapor pressure of the sealing solution. Ammonium ferric
oxalate permeated iron deposit is decomposed by a heat treatment as
hereunder described, and generates gaseous ammonia and carbon
dioxide, leaving only iron oxides. There are no particular
difficulties in the subsequent operations.
A desired composition of magnetite and the best electric
conductivity and the corrosion-resistant property of the product
can be obtained by carrying out said heat treatment while
maintaining conditions strictly within the range prescribed in the
foregoing.
Said heat treatment is preferably carried out at a temperature
ranging from 550.degree. and 700.degree.C. The reaction is very
slow at a temperature below 550.degree.C, requiring longer time for
the operation. At a temperature higher than 700.degree.C, more
ferrous oxide forms and the desirable magnetite composition may not
be obtained. The preferable range of composition of the gaseous
mixture in which said heat treatment is to be carried out is from
10 to 25 percent by volume of hydrogen and from 75 to 90 percent by
volume of steam. In an atmosphere of a gaseous mixture containing
less than 10 percent by volume of hydrogen and more than 90 percent
by volume of steam, more ferric oxide will form, on the other hand,
when the hydrogen content is higher than 25 percent by volume and
the steam content lower than 75 percent by volume in said gaseous
mixture, more ferrous oxide will form. In either of these cases,
the desirable magnetite composition may not be or is difficult to
be obtained. Moreover, when the hydrogen content is higher than 25
percent by volume, difficulties due to the hydrogen embrittlement
of the metallic substrate may arise.
The gaseous hydrogen-steam mixture of this invention is prepared by
saturating hydrogen with steam by passing hydrogen in water
maintained at an appropriate temperature decided by taking the
vapor pressure. Said gaseous mixture is introduced into a tube
furnace to perform said heat treatment. The time required for said
heat treatment is about 2 - 5 hr. Finally, a magnetite-coated layer
of 3 - 20 .mu. in thickness is obtained.
By carrying out the treatment in accordance with the process of
this invention a fine-grained magnetite-coated layer having
desirable durability may be formed on the surface of a metallic
substrate having high electric conductivity and sufficient
corrosion-resistance. In particular, said sealing treatment of the
iron deposit in an ammonium ferric oxalate solution produces a
final product as anode having a life of one year, more than twice
as that whereby no such treatment has been applied, thus offering a
practical advantage.
The anode coated with magnetite manufactured in accordance with
this invention is quite suitable for the manufacture of chlorine,
chlorates, and bromates. Moreover, said anode can be used for any
electrolytic oxidation processes in general, and as an anode for
electro-winning of copper, as an insoluble anode for electrolyzing
sodium sulphate, for cathodic protection, and for
electro-dialysis.
The embodiment of this invention will be explained further in
detail by the Examples and the Comparative Examples described
hereunder.
EXAMPLE 1
A previously polished titanium plate 200 mm .times. 50 mm and 1 mm
thick was defatted in a boiling 10 percent NaOH solution, and was
dipped into a 5 percent hydrofluoric acid solution at room
temperature for 1 min, and then washed with water.
Electro-deposition was carried out for 19 min in an electrolyte at
25.degree.C consisting of 130 g/l of ferrous sulfate
(heptahydrate), 100 g/l of ammonium sulfate and 6 g/l of formalin
by using said titanium plate as a cathode (a cathodic current
density = 2.5 A/dm.sup.2) and a low carbon steel as an anode. After
the electrodeposion was completed, said iron deposited titanium
plate was washed well with water, and then dipped into a solution
of 20 g/l of ammonium ferric oxalate at 13.degree.C, and was
allowed to stand for 20 min under a reduced pressure of 15 mm Hg
abs. produced by a vacuum pump and dried under the reduced pressure
and was then subjected to heat treatment at 650.degree.C for 2.5
hrs. in an atmosphere of a hydrogen/steam gaseous mixture
consisting of 20 percent by volume of hydrogen and 80 percent by
volume of steam prepared by passing hydrogen into hot water at
94.degree.C. On the surface of the product the formation of a
magnetite-coated layer was clearly recognized. The thickness of
said layer was confirmed to be 20 .mu. by weighing said product.
The appearance of said product was uniformly black and fine-grained
and no crack was observed therein.
EXAMPLE 2
A tantalum plate of 200 .times. 50 mm and 2 mm in thickness was
defatted in a boiling 10 percent NaOH solution and was dipped in an
aqueous solution of 5 percent hydrofluoric acid for 1 min. It was
then washed with water, and was electrodeposited for 10 min in an
electrolyte at 20.degree.C consisting of 100 g/l of ferrous sulfate
(heptahydrate), 100 g/l of ammonium sulfate, 3 g/l of phenol, and 5
g/l of ammonium phthalate by using said tantalum plate as a cathode
(cathodic current density = 1.0 A/dm.sup.2), with the use of a low
carbon steel as an anode. After the electrodeposition was
completed, said iron deposited tantalum plate was washed well with
water, and was then dipped into a solution containing 30 g/l of
ammonium ferric oxalate at 23.degree.C, and was then allowed to
stand for 25 min under a reduced pressure of 28 mm Hg abs. After
said treatment was finished, it was dried in vacuum and was
heat-treated at 580.degree.C for 4 hrs. in an atmosphere of a
hydrogen/steam gaseous mixture consisting of 15 percent by volume
of hydrogen and 85 percent by volume of steam prepared by passing
hydrogen into hot water maintained at 95.degree. - 96.degree.C. By
this treatment a uniform and fine-grained magnetite-coated layer of
4.6 .mu. in thickness was obtained.
EXAMPLE 3
A 200 .times. 50 mm titanium net having a wire diameter of 1 mm and
mesh of 1 mm was defatted in a boiling 10 percent solution of NaOH,
and was dipped into an aqueous solution of 5 percent hydrofluoric
acid at room temperature for 1 min, and then washed.
Electrodeposition was carried out for 15 min in an electrolyte
maintained at 35.degree.C consisting of 150 g/l of ferrous sulfate
(heptahydrate), 100 g/l of ammonium sulfate and 10 g/l of ammonium
citrate by using said titanium net as a cathode (cathodic current
density = 2 A/dm.sup.2) and a low carbon steel as an anode. After
said electrodeposition was completed, it was washed well with
water, and was dipped into a solution containing 25 g/l of ammonium
ferric oxalate at 10.degree.C, and was allowed to stand for 20 min
under a reduced pressure of 12 mm Hg abs. The treated substrate was
then dried in vacuum and was heated at 670.degree. C for 2 hrs. in
an atmosphere of a hydrogen/steam gaseous mixture consisting of 20
percent by volume of hydrogen and 80 percent by volume of steam
prepared by passing hydrogen into hot water at 94.degree.C. By this
treatment a magnetite-coated layer of about 13 .mu. in thickness
was obtained.
EXAMPLE 4
An electrolyte consisting of 250 g/l sodium chloride, 70 g/l of
sodium chlorate, and 2 g/l of sodium bichromate was electrolyzed at
60.degree.C for 11 months with an anodic current density of 10
A/dm.sup.2 by using an anode coated with magnetite prepared as
described in Example 1 as an anode with the use of a mild steel
plate as a cathode. The current efficiency was 85 percent and the
average cell voltage was 3.38 V. The required energy per ton sodium
chlorate was 6,000 kwh. During this period almost no change was
observed on the surface of the anode.
Comparative Example
Table 1
__________________________________________________________________________
Time of the The State of the Surface Anode Electrolysis* of the
Anode
__________________________________________________________________________
An anode prepared by Almost no change was the process of this 11
months observed. invention (Example 1). An anode prepared by A
stripping off of the the process of this magnetite-coated layer was
invention except that 4.5 months distinctly observed, and dipping
in an aqueous the substrate was laid solution of ammonium bare.
ferric oxalate was omitted. An anode prepared by the The stripping
off of the process of this inven- 2 months magnetite-coated layer
tion except that the was slightly observed, heat treatment was
carried but the surface was out at 800.degree.C. colored brown. An
anode prepared by the Same as above. process of this invention 3
months except that heat treatment was carried out at 450.degree.C.
__________________________________________________________________________
* Same conditions of electrolysis as in Example 4.
EXAMPLE 5
Sea water having a sodium chloride concentration of 27 g/l, pH = 8,
and 25.degree.C in temperature, was electrolyzed by an anodic
current density of 3 A/dm.sup.2, using an anode coated with
magnetite prepared by the process described in Example 3 with the
use of a mild steel as a cathode. A solution containing 0.5 g/l of
sodium hypochlorite was continuously obtained. Even after 6 months
no abnormalities were observed on said coated anode.
* * * * *