[0001] Electroformed copper foils are the backbone of modern electronic devices. As integrated
circuits have found their way into ever increasing numbers of products, the quantity
of foil required has increased correspondingly yet the rate at which these foils
could be produced has been limited because even the best dimensionally stable anodes
available were not capable of withstanding the conditions required for optimum foil
production. The anodes of the present invention are particularly suitable for producing
high purity, pore-free copper foils at high speed and low cost under severe conditions
because these anodes withstand high acid concentrations, current densities and temperatures
which would rapidly destroy the anodes known to the prior art. In particular, the
anodes of the present invention are formed by a three step process which is extremely
sensitive in its details but, when carried out properly, produces extremely robust
and durable anodes.
[0002] In the first step of the process, platinum is electrodeposited on a valve metal substrate
which has been thoroughly descaled, degreased and cleaned. It is critical that the
platinum be applied to a thickness of from at least about 150 microinches up to about
400 microinches, preferably the thickness will be at least about 225 microinches,
more preferably at least about 250 microinches.
[0003] The second step of the process involves a thermal treatment referred to as "densification"
which is essential for obtaining the anodes of the present invention. In the "densification"
step, the platinum coated anode is heated in air and maintained at a temperature between
600 and 775°C for about ¼ to 2 hours or until the stress is relieved in the electrodeposited
coating and pores resulting from the electrodeposition process have closed.
[0004] The final step in the process is applying a catalytic oxide outer coating consisting
essentially of at least about 97% IrO₂ and up to about 3% Rh₂O₃ by applying thermally
decomposable iridium and rhodium compounds to the "densified" platinum coated substrate,
then decomposing the compounds by heating in air to form the oxides. It has been found
that it is essential to effect the decomposition at temperatures of no more than about
600°C as the products formed are much less durable when higher temperatures (for example,
around 690°C) are used. The amount of the thermally decomposable compounds applied
should be sufficient to provide a loading of at least about 15 m²/g of iridium (calculated
based on the weight of the metal), preferably 20 m²/g, more preferably m²/g.
[0005] The substrates to which the coating is applied may be any of the well known film
forming metals which, if uncoated, will rapidly passivate by formation of an adherent
protective oxide film in the electrolyte for which the anode is intended. Typical
substrates are formed from titanium, tantalum, vanadium, tungsten, aluminum, zirconium,
niobium and molybdenum in the form of tubes, rods, sheets, meshes, expanded metals
or other specialized shapes for specific applications. For formation of electrolytic
copper foil, it is particularly preferred to use anodes in the shape of cylinders
or as a portion of a cylinder which conform to the shape of the mandrel or drum so
that the electrolytically formed foil will be of uniform thickness and may easily
be removed from the cathode drum. In many cases, the core of the anode will be copper
or another highly conductive metal such as aluminum or highly conductive ferrous alloys
clad with a film forming metal outer layer such as titanium.
[0006] Prior to application of the electrolytic layer, the substrate is cleaned and descaled
such as by blasting with aluminum oxide particles in an air jet, then chemically cleaned
and degreased. Normally, the anode is coated immediately subsequent to degreasing
but the anodes may be stored for for a few days between degreasing and coating without
ill effect.
[0007] The electrolytic coating of platinum may be applied by immersing the substrate in
an aqueous, platinum, electroplating bath opposite a conventional dimensionally stable
counterelectrode and passing a current of from about 7 to about 70 amps per square
foot through the substrate until at least 150, preferably 225, more preferably 250
microinches of platinum have been applied. Any conventional platinum electroplating
bath may be used. Typically, such baths are in aqueous dispersons, solutions or admixtures
containing compounds of platinum such as ammine, nitrito or hydroxy complexes, as
well as various known additives for brightening, improving the ductility of the deposited
film and isolating impurities as well as improving the conductivity of the bath. Typical
platinum compounds include H₂PtCl₆, K₂Pt(OH₂), H₂Pt(NO₂)₂S0₄ and diammine dinitroplatinum
(II). Useful formulations for platinum electroplating baths are disclosed in F. Lowenheim,
Modern Electroplating, 3rd Ed. 1974, pp. 355-357 and
F. Lowenheim,
Electroplating, McGraw Hill 1978, pp. 298-299. Prepared concentrates for preparing and replenishing
platinum electroplating baths are commercially available. To achieve a high quality
platinum layer, the temperature of the bath should preferably be maintained at from
about 150 to about 200°F (65° to 93°C).
[0008] After the platinum coat has reached the desired thickness, the anode may be removed
from the bath and subjected to a thermal treatment termed "densification" to stress
relieve the coating and close pores therein. If the "densification" step is omitted,
or not performed properly, the anodes formed are less durable as they passivate prematurely.
Thermal densification can be accomplished by heating the platinum coated anode in
air, nitrogen, helium, vacuum or any convenient atmosphere to a temperature of between
about 550°C and 850°C for from about 15 minutes to several hours depending on the
nature of the as deposited platinum film. It may be determined that the thermal densification
step is complete by visually observing the coating and noting when pore closure occurs
and the coating becomes much more highly reflective.
[0009] After thermal densification is complete, the anode may be cooled then coated with
an iridium oxide outer layer by thermal decomposition of iridium containing compounds
in an oxygen containing atmosphere. Iridium compounds that may be used include hexachlororidic
acid (NH₄)₂IrCl₆ and IrCl₄, as well as iridium resinates and other halogen containing
compounds. Typically, these compounds are dispersed in any convenient carrier such
as isobutanol, and other aliphatic alcohols, then applied to the substrate by any
convenient method such as dipping, brushing on or spraying. In most cases an amount
of iridium bearing carrier is applied which is sufficient to deposit a loading of
from about 0.5 to about 3.0 grams per square meter, preferably 1 to 2 grams per square
meter, of iridium (calculated as metal) on the substrate, which is then fired in air
at from about 400°C to no more than about 550°C, preferably 450°C to about 500°C,
to drive off the carrier and convert the iridium compounds to the oxides. This procedure
is repeated until the total amount of iridium applied is at least about 15, preferably
at least about 20, more preferably at least about 25 grams per square meter (calculated
as metal). The temperature of the thermal decomposition step is extremely critical.
As will be demonstrated in the following Examples, when a decomposition temperature
in excess of about 600°C is used for decomposition of the iridium compounds, the resulting
anode is much less durable, but when the iridium compound is decomposed at temperatures
of 600°C or below, preferably from about 400°C to about 550°C, more preferably from
450°C to 500°C, the resulting anode is surprisingly durable and long lived even when
evolving oxygen in baths at temperatures in excess of about 65°C which will normally
ruin the prior art anodes in short order.
[0010] In many cases, it will be advantageous to include up to about 3% Rh₂O₃ in the iridium
oxide film to promote adhesion. This may be accomplished by incorporation of any convenient,
conventional rhodium compound into the iridium bearing coating composition. Rhodium
resinates are particularly convenient.
[0011] Copper foils may be electroformed using the anodes of the present invention by immersing
the anode in a bath at a pH of from -2 to 3 containing suitable copper species such
as copper sulfate, copper chloride and other soluble platinum compounds opposite a
cathode such as stainless steel or other corrosion resistant alloys and passing a
current of from about 400 to about 2,000 amps per square foot of anode (4,300 to 21,000
A/m²) through the bath and evolving oxygen at the anode. It is considered particularly
surprising that the anodes of the present invention exhibit high durability even when
used at bath temperatures in excess of 65°C up to about 90°C. It is also considered
surprising that anodes of the present invention remain suitable for use at a sulfuric
acid concentration from about 100 to about 250 grams/liter even when operating at
current densities from about 500 up to about 3,000 amps per square foot (5,400 to
32,000 A/m²). Under these conditions, prior art anodes rapidly become useless and
even anodes similar to the present invention, but not prepared strictly in accordance
therewith, fail rapidly. It is extremely desirable for copper foil producers to be
able to use these severe conditions as under these conditions more efficient, rapid
and economical production of foil can be achieved. Thus, the anodes of the present
invention satisfy a long felt but unsatisfied need for anodes which were capable of
being used under conditions which are suitable for high speed, energy efficient production
of high purity, pore free films of electrolytic copper foil. They are also extremely
suitable for those applications in which a porous foil is desired as well as for other
applications involving oxygen evolution such as electrogalvanizing, electrowinning
and electrosynthesis.
Example 1
[0012] This Example illustrates the production of an anode in accordance with the present
invention. A substrate of titanium of dimensions 4" by 8" by 0.062" was descaled,
cleaned and degreased, then electrolytically coated with platinum to a thickness of
250 microinches. The platinum coating was then densified by heating in air at 690°C
for 3/4 hour. After cooling, a coating consisting of about 98% IrO₂ and 2% Rh₂O₃ was
applied by painting the substrate with a solution of hexachlororidic acid and a rhodium
resinate dispersed in butanol, then firing in air at 450°C and repeating this procedure
15 times until the coating weight reached 15 grams of iridium (as metal) per square
meter. When used in electroforming of copper foils at a pH of about 0, a current density
of about 1860 ASF (20,000 A/m²), and a temperature of about 60°C, the anode was still
operating at this writing after 4,000 hours at an essentially constant overvoltage
of 2.83 volts.
Example 2
[0013] The procedure of Example 1 was repeated except that the iridium oxide (third step)
was formed at 690°C. When used under conditions similar to those in Example 1 (pH
0, current density 1860, and temperature of 60°C) the anode failed after 620 hours.
1. An anode for oxygen evolution consisting essentially of a substrate of a film forming
metal having a multilayer coating thereon, at least one interior layer consisting
essentially of substantially pore free platinum having been applied electrolytically
to a thickness of at least about 200 microinches, then densified by heat treating
in an oxygen containing atmosphere at from 600 to 775°C;
at least one of the exterior layers consisting essentially of at least about 97% iridium
oxide and up to about 3% rhodium oxide, said exterior layer having been applied by
thermal decomposition of thermally decomposable platinum group metal compounds in
an oxygen containing atmosphere at a temperature of not more than about 600°C.
2. The anode of Claim 1 wherein the exterior layer is formed by thermal decomposition
at a temperature of from about 400 to about 550°C.
3. The anode of Claim 1 wherein the interior layer has a thickness of at least about
225 microinches.
4. The anode of Claim 1 wherein the interior layer has a thickness of at least about
250 microinches.
5. The anode of Claim 4 wherein the exterior layer is formed by thermal decomposition
at a temperature of from about 450 to about 500°C.
6. A process for electroforming of copper foil in an aqueous bath containing over
100 grams per liter of sulfuric acid, using a current density of at least about 500
amps per square foot at a temperature of over 65°C using the anode of any of Claims
1 through 5.