US 3926773 A
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1 Dec. 16, 1975 United States Patent [191 Koziol et al.
8 MN m WT "A n WL D1 1.? A R m0 mm N E T A P N m E R O F Martinsons 86 68 BL 222 7777 9999 NH 2 56 8803 0987 2232 6367 2 3333  Inventors: Konrad Koziol; Hans-Carl Rathjen,
both of Rothenbach, Pegnitz;
1,812,522 6/1970 Germany......,.,................ 204/290 F Karl-Heinz Sieberer, Zirndorf near Nuremberg, all of Germany Primary E.\aminerF. C. Edmundson  Asslgnee' Flrma Conradty Germany Attorney, Agent, or FirmMcG1ew and Tuttle  Filed:
Sept. 27, 1973  ABSTRACT A valve metal anode, for electrolytical processes, hav- Appl. No.: 401,542
Related US. Application Data  Continuation of Ser. No. 163,256, July 16, 1971,
ing an electron-active covering layer, comprises electron-activating substances, counteracting passivation abandoned.
of the anode, anchored in a stntered porous carrier layer of valve metal. The carrier layer which is sin-  Foreign Application Priority Data July 16, 1970 tered onto the cleaned valve metal base may consist of Germanym,....................r... 2035212 a powder of the same metal or of the crystallographically similar metal. The infusion of the active substances into the carrier layer can be accomplished by impregnating and drying or baking the active sub- Rs wm RI 4B m5 2 C 3 RH A091 B .5 2 W L H 0 m U1 1] 2.1 55
C25B 11/10 204/290 F, 290 R stances, by precipitating them from the vapor phase,
 Field of 1 References Cited UNITED STATES PATENTS 2,631,115 3/1953 Fox et a1. 204/290 F 10 4 Drawmg F'gures 7/1969 Csizi 204/219 U.S. Patent Dec. 16, 1975 3,926,773
I'I'I'I' 'I'I'I'Im I "null b FIG! FIGZ INVENTORS lfO/V/PAD KOZ/OL HANS- 67794 174 THJf/V BY/ffl/PL HEM Z 57E BEPER ATTORNEY METAL ANODE FOR ELECTROCHEMICAL PROCESSES AND METHOD OF MAKING SAME This is a continuation, of application Ser. No. 163,256 filed July 16, 1971, now abandoned.
FIELD OF THE INVENTION This invention relates to anodes for electrochemical processes and, more particularly, to an improved valve metal anode having an electron-active covering layer.
BACKGROUND OF THE INVENTION The high state of development of new large electrolytic cells, reflected above all in low cell voltages, high current and energy yields, ease of operation and operating safety of electrolysis plants, is due to a number of measures and improvements relating, not in the least, to the electrode.
Technical anode materials must meet a number of specifications including, among others, the corrosion resistance of the anode material and the progress of the anode process with a sufficiently high speed and the least possible excess voltage. Anode materials used heretofore on a large industrial scale meet these constantly increasing demands only partially. For example, there is a certain amount of unavoidable burning off when graphite anodes are used. In modern large cells this requires expensive equipment for the maintenance of a constant spacing between the anode and the cathode, in addition to which a relatively high expense is necessary for brine cleaning.
In addition to graphite anodes, anodes of platinum, metals of the platinum group, and their alloys also have been used. Such anodes always have the disadvantage of very high investment costs and of a relatively heavy wear of noble metal. Anodes of platinized titanium have recently become known, mainly for price reasons, but they have always failed in the sector of Hg electrolysis for reasons of their great amalgam sensitivity.
The expression valve metals has lately become very popular for the group of metals including titanium, tantalum, niobium, zirconium, tungsten and molybdenum. It is known that these valve metals passivate very quickly when used in aqueous solutions, due to the development of a dense cover layer of an oxidic nature, thereby becoming extremely corrosion-resistant in many electrolyes. However, the passive layers of these metals have no electron conductivity in the electric potential ranges here in question, so that very high field densities occur in the layers. Above a certain potential, called breakthrough potential", this leads to the destruction of the passivating layers. Despite the fact that these metals have great corrosion resistance, no anode process can be carried out with these metals in the passive state. It is usually not noted that, even in the noble metals, the Flade potential, which is the potential at which the metal passes over from the active to the passive state, is considerably more negative than the normal potential. Accordingly, at higher potentials the noble metals also are cove red by passive layers in electrolytes. In platinum, a monomolecular oxygenchemisorption layer on the metal surface will already lead to passivity. It is immaterial, for this passive layer mechanism, whether the cover layer of an oxidic nature is generated on the noble metal in the electrolyte or whether oxidic noble metal cover layers are applied prior to immersion in the electrolyte, as proposed for the dimensional stable anodes in German Pat. No. l8 14 567. These passive layers on noble metal bases. in contrast to the passive layers of the valve metals, distinguish themselves by their good electron conductivity. thus permitting carrying out of the anode process.
It is obvious, however, that the anchoring of foreign substances to the carrier metal, such as cubic-face-centered platinum to titanium which, at the temperatures used, is most densely compacted hexagonally as a rule, is problematical. Also, the mechanical durability of oxide layers adhering to metal is unsatisfactory because, due to the difference in contractional behavior under rapid temperature changes, stresses will develop in the boundary area between the oxide and the metal, and these stresses cause the oxide to flake off, as is clearly demonstrated by specimens which have been oxidized for some time in air at elevated temperatures. As is known, this method of rapid temperature change is also employed frequently, in industry, for the removal of scale layers. This should also explain adequately the susceptibility of the anodes, according to German Pat. No. l8 14 567, which are provided with ceramic semiconductor coatings, and in which the active cover layer, provided with a chlorine releasing catalyst rests on the bare or on the oxide layer covering the valve metal base.
SUMMARY OF THE INVENTION The present invention is directed to a metal anode for electrolytical processes and, by way of example, its application to chlorine-alkali electrolysis will be described in some detail, although it should be understood that the anode may be used also in connection with many other electrolysis processes.
The invention is based on the problem of developing an anode in which the active substances, counteracting the passivation of the valve metal are (l) anchored better to the base, (2) connected electron-conductively with a by far larger metal conductor surface, (3) protrude deeply into the valve metal base and thus are enabled to withstand the intensive chemical, mechani' cal and errosive stresses in the electrolysis bath, and (4) are not required, due to this construction, to meet the strict demands of epitaxis and good electron conductivity, thereby largely obviating the limitations of selection.
In accordance with the invention, the problem is solved in a particularly advantageous manner by an electrode in which the active substances, counteracting passivation, are anchored in a porous carrier layer sintered onto the valve metal base. The carrier layer sintered onto the cleaned valve metal base may consist of a powder of the same metal, or of a crystallographically similar metal. The pretreatment of the metal base may be effected by any desired method, such as pickling, steam degreasing, rinsing, grinding, or the like. The size, shape and surface of the metal powder particles vary in accordance with the material and the pro' duction method. The application of the powder particles to the metal base may be accomplished by spraying, rolling, electro-depositing, brushing, and other suitable methods, prior to the sintering operation. To facilitate the application, prior to the sintering operation, binders or adhesives or both may be admixed with the powder. It is expedient to use, as powder, various valve metal powders such as titanium powder or tantalum powder, or a mixture of valve metal powders, or a valve metal alloy present in powder form.
An object of the invention is to provide an improved metal anode for electrochemical processes.
Another object of the'invention is to provide such an anode in which active substances. counteracting passivation. are anchored in a porous carrier layer sintered onto a valve metal base.
A further object of the invention is to provide a method of producing such an anode.
For an understanding of the principles of the invention, reference is made to the following description of typical embodiments thereof, as illustrated in the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS In the drawings:
FIGS. 1 and 2 are cross sectional views schematically illustrating the construction of anodes embodying the invention;
FIG. 3 is an enlarged sector of a covering layer illustrated in FIGS. 1 and 2; and
FIG. 4 is an enlarged sector of a porous carrier layer with embedded activating particles.
DESCRIPTION OF THE PREFERRED EMBODIMENTS Referring to the drawings, the solid basic valve metal body of the anode is indicated at a, and the sintered, porous valve metal layer, which supports the activating substances. is indicated at b, as shown in FIGS. 1 and 2. FIG. 3 represents an enlarged sector of the layer designated b in FIGS. 1 and 2, wherein the activating substances, counteracting passivation, are indicated at c. In FIG. 4, which is an enlarged sector of the porous valve metal powder carrier layer illustrated at b in FIGS. 1 and 2, the embedded activating particles are indicated at 0.
Titanium has the special characteristic of being obtainable in purer form as a powder than in the molten state. Nevertheless, depending upon the method of production and storage, the surface of commercial powders usually is covered with a film of adsorbed gases When stored in air, oxide films will usually form, While storing in a nitrogen atmosphere will cause a partial nitration. Thus, a reducing pretreatment may become necessary before the sintering operation. However, in certain cases, the powders also may be used for sintering without a pretreatment. Tests carried out prove that the most uniform, most stable and yet porous sintered layer is obtained with powders having a rather uniform particle size of approximately 30 mu. The particles were of almost spherical shape, so that the size stated relates to the diameter of the particles.
In some cases, in which a slighter greater porosity is desired, it is recommended to use fillers, the majority of which will readily evaporate during the sintering operation, or which are removed by thermal disintegration. The following ammonium salts, such as ammonium perchlorate, ammonium chromate, ammonium sulfate, and resin diluted with alcohol, are listed, merely by way of example, without necessarily limiting the range of usable agents.
In order to avoid oxidation of the valve metal powder during the sintering process, the latter is carried out either in a vacuum between 1 and S X Torr, or in a definite gas atmosphere, such as argon. The heating rate is determined either by the quality of the vacuum or by thermally disintegrating substances limiting the heating rate in order to avoid damage to the sintered layer. The sintering temperature varies between 800C and 28()()-"C, dependingupon the metal powder and the basemetal. with the heating periods ranging between several hours and hour, again depending upon the temperature.
The infusion of the active substances, counteracting passivation. can be effected by impregnating and drying, and baking them in, or by both, by precipitating them from the vapor phase, galvanically, or by precipitating them from the gaseous phase. Adding a wetting agent frequently results in a further improvement. The active substances may also be ingredients of the sinter mixture before sintering.
All substances of sufficient corrosion resistance during electrolysis, and possessing good electron conductivity in the potential ranges used, so that an anode process can be carried out, are suitable as activating substances. These are all metals and oxides of the platinum metal group, intermediate and mixed oxides of noble and ignoble metals or both, or oxides of ignoble metals alone, which meet the requirements set forth above. Surprisingly, it has been found that, with this construction, even conductive materials of an ignoble character lead to excellent results. Thus, the widely held option that the active layer always must contain noble metal or noble metal compounds, in order to remain effective, is now refuted for the first time.
Desired active substances need not yet be present in oxidic form during the infusion, but may be produced in the sintered layer during or after the heat treatment and/or the sintering operation, by an additional after treatment.
As a result of this treatment there is obtained, on a valve metal base, a compound material, i.e. a metal/- metal or a metal/ceramic combination. This is a mechanically strong, yet porous, crystallographically identical, well adherent valve metal carrier layer containing the active substances in well anchored form. This layer, which in part displays cermet characteristics, is characterized in that the active substances are built into a carrier skeleton having the same crystalline structure as the base metal, thus forming one unit with the base metal. Therefore, the electrical conductivity through this activated carrier layer is primarily of a metallic nature. Although sintered layers have a greater electrical resistance than solid parts of the same metal, the basic valve metal body can be dispensed with if the mechanical strength is adequate and the sintered body alone may be used, this sintered body containing the activating substances counteracting passivation. In addition, the sintered layer permeating the active substances protects them from mechanical and, to a certain extent, also chemical attacks. As an additional advantage, a considerable lesser amalgam sensitivity is attained.
This represents an unequivocal improvement over the conventional platinized titanium anodes in which, in case of a short circuit with the mercury cathode, a part of the platinum layer, which is kept very thin for price reasons, is removed by amalgam formation, thereby making the anode inactive after a short period of time. If, on the other hand, the platinum layer is accommodated within the sintered layer according to the invention, then, due to the great surface tension of the mercury, a contactbetween the mercury and the noble metal is hardly possible and no wear due to amalgam formation needbe anticipated.
It has hitherto been necessary for active layers applied to the anode to be of relatively great strength and thus to be resistant to mechanical stresses. This eliminated a number of materials for use in practice right from the start, although they would have been of inter est from an electrical and economical standpoint. For example, cover layers on spinel bases could not be used technically until now on a valve metal base because the adhesion of the spinels to the bare or oxidized metal base is insufficient. This is also confirmed by a test in which a titanium sheet, coated with an iron-chrome spinel, was destroyed after an operating period of twenty-seven days in a laboratory cell at a current density of l A/cm while the same spinel, infused into the sintered layer, resulted in an extension of the life span to roughly 250 days. Similar results were obtained with the oxides and oxide mixtures of lead, manganese, iron, cobalt, nickel and tungsten.
Due to the great porosity of the sintered layers and the greater anode surface area resulting therefrom, a lesser true anode current density than with conventional metal anodes is actually attained under the same load. This expresses itself in an additional voltage economy of several tenths volt.
The following examples are given solely by Way of example, and not in a limiting sense:
EXAMPLE 1 A titanium sheet, whose dimensions are 100 X 100 X 1 mm, was pickled for 30 minutes in a percent by weight boiling hydrochloric acid, washed with water, and rinsed with propanol. A mixture of titanium powder, polyglycol 6000 and hexanol was sprayed on the thus prepared sheet by means of a compressed air operated spray gun. After a 20 minutes drying period at 120C in a drying oven, the titanium powder coating was sintered on in an induction furnace at a heating rate of 300C/h and an end temperature of 1 100C.
The thus produced basic body was soaked in a 1- molar ruthenium-chloride solution, to which was added some wetting agent known as Erkantol. This was followed by a heat treatment at 450C for minutes. The process was repeated three times in an identical manner.
The anode thus produced, as compared to an anode coated with the same solution in a known manner, namely without a sintered coating, has a much greater active surface, resulting under the same load, in a small true anode current density and, consequently, in a lower cell voltage. In addition, the anode embodying the invention is also considerably more amalgam-proof and short-circuit-proof.
EXAMPLE 2 A titanium rod 400 mm long and 3 mm in diameter was pickled for 30 minutes in a boiling 20 percent by weight hydrochloric acid, washed with water and rinsed with propanol. By means of a carbon mold, and by sintering in a tubular furnace at 1200C, a titanium sinter coat 1 mm thick was applied to the thus prepared rod. The sintered rod was repeatedly impregnated with a solution containing Mn(NO and AgNO in a 1:1 ratio, and dried in air. For activation, the rod was left for five minutes in the vapor chamber of a boiling 20 percent by weight hydrochloric acid. Finally, there followed a baking operation lasting from minutes to 5 minutes at temperatures between 200 and 450C.
EXAMPLE 3 A fine-mesh, commercially platinized titanium mesh of expanded metal. was pulled through a titanium-tantalum powder mixture made pasty by a higher alcohol. and sintered in a continuous furnace. Due to the higher melting point of the noble metal, sintering occurred mainly at the areas of the basic valve metal body which are free of noble metals.
The greatest possible protection of the platinum layer is attained by this sintered valve metal coating.
From the foregoing, it will be clear that the invention opens up, to the electrochemical industry, a multiplicity of the most varied electrode materials, which are far superior to the electrode material used hitherto as regards price, durability and economy in operation.
The theories mentioned above are intended only to be of an explanatory nature and to describe the operating mode of the electrode according to the invention, and are by no means to be considered as binding or limiting the application of the electrode in any way.
While specific embodiments of the invention have been shown and described in detail to illustrate the application of the principles of the invention, it will be understood that the invention may be embodied otherwise without departing from such principles.
What is claimed is:
1. In an anode, for electrolytical processes, particularly for chlorine-alkali electrolysis, having a solid core of valve metals selected from the group consisting of titanium, tantalum, niobium, zirconium, hafnium, tungsten. molybdenum, and alloys thereof, and having a covering layer containing activating substances counteracting passivation of the anode, selected from the group consisting of metals and oxides of the platinum metal group, mixed oxides of noble and ignoble metals, and oxides of ignoble metals alone: the improvement in which the activating substances are anchored in a porous covering layer consisting of powdered valve metal which is sintered to the solid valve metal core of the anode.
2. An anode, as claimed in claim 1, in which the active substances, in combination with the sintered covering layer form a compound material of valve metal/noble metal.
3. An anode, as claimed in claim 1, in which the active substances, in combination with the covering layer form a cermet-like compound material of valve metal ceramic.
4. An anode, as claimed in claim 3, in which the ceramic portion of the compound is composed of noble metal oxides.
5. An anode, as claimed in claim 3, in which the ceramic portion of the compound is composed of oxide mixtures of noble and ignoble metals.
6. An anode, as claimed in claim 3, in which the ceramic portion of the compound is composed solely of oxides of ignoble metals.
7. An anode, as claimed in claim 1, in which said porous covering layer comprises titanium.
8. An anode, as claimed in claim 1, in which said porous covering layer comprises tantalum.
9. An anode, as claimed in claim 1, in which said porous covering layer comprises a valve metal alloy.
10. An anode, as claimed in claim 1, in which said porous covering layer comprises a mixture of different valve metals.