Ross GWYNN -- Electrolyzed Physiological Saline vs Cancer -- Chlorozone

Biodynamics has been defined as "piecing together random research findings into a coherent picture of how and why drugs work" (The Drug Research Revolution by Norman Applwig, Chemical Week, 1 March 1972). The author goes on to point out that "Biodynamics gives researchers three advantages over the old ways:

(1) They can custom design synthetic compounds to do specific jobs.

(2) They can use the body's own chemicals to fight disease.

(3) They can deliver therapeutic agents directly to target organs."

While the advantages achieved through Biodynamics are individually and collectively of profound significance there is believed to be another, namely the ability to depart from conventional thinking and evolve new theories as to how the body functions in sickness and in health.

To one without formal medical education but having rubbed shoulders with many in the medical profession as patent attorney practicing extensively in areas of therapeutic development for the past 35 years and having read extensively in all fields of medical advance, a few unfortunate realities become apparent.

A. The practice of medicine to a large extent, and the conducting of medical research to a still greater extent is highly compartmentalized according to disease or affliction.

B. Individuals to a considerable extent lean toward an area of specialization early in their preofessional training with a limited amount of broad range experience.

C. In any area of specialization the amount of publication to keep abreast of is so voluminous that the individual, once committed to an area of specialization, has little time or energy available to folow progress in other areas.

The situation might be compared with exploration of a mountain range by ground crews before the coming of aircraft. No matter how much data was collected and compiled by such ground crews, it goes without saying that a later crew exploring by helicopter would develop information, data, and inter-relationships that had eluded the ground crews. Only as the findings of the ground and air crews are combined and correlated can a maximum understanding of the mountain range be achieved.

The writer has had the thrilling experience of being observer and collaborator in a "helicopter flight" piloted by Ross M. Gwynn in which, within a few short years, a new therapeutic agent and treatment has been used with remarkable success in treating several hundred human volunteers having a wide variety of ills and afflictions. What has been particularly noticeable in this experience is the number of times that response and reaction when treating one type of affliction has thrown light on seemingly unrelated afflictions.

The new therapeutic agent is physiological saline electrolyzed in a manner to generate about 65 ppm of active components comprising hypochlorite, a small amount proportion of ozone, and traces of free radicals, the active components being collectively referred to as "chlorine equivalent". This electrolyzed saline is most effectively administered by intravenous injection, and by intramuscular injection only when small amounts are neededm particularly wbe treating gastro-intestinal disorders, and extended bathing of the whole body or body parts, as when treating burns, ulcers, and the like.

In a publication by Ross Gwynn entitled "Bioelectrolysis In Man" he has summarized this clinical work and presented some interesting new theories in an attempt to explain the beneficial results obtained with a broad range of ills and afflictions. In essence the new theories can be summarized as follows:"

I. The common denominator to many human ills appears to be hypoxia, general or local ( deficiency of oxygen).

II. In every individual there appears to be a supplemental or booster oxidant function, variably produced by electrical charges generated in the body as by bone flexing and in brain waves of the alpha and higher voltage level, capable of counteracting such hypoxia.

III. The severity of an illness or injury can overtax the individual's ability to generate sufficient of the supplemental or booster oxidant function, creating a 'deficiency' situation.

IV. Also contributing to the creation of such a deficiency situation, even with a seemingly healthy person, would be poor bioelectrolysis performance induced by curtailed physical activity, or an extended period of anxiety, frustration or depression, or a combination of these.

V. Injected Chlorozone appears to provide an equivalent supplemental or booster oxidant function in unlimited amount to aid the natural healing or recovery process during the period of such deficiency.

In his book Ross Gwynn has commented in page 51: "In the book entitled HYPOXIA by Van Leere and Stickney, published by the Univ. of Chicago Press in 1963, it was pointed out that the state of hypoxia can be so far-reaching as to affect the mobility, and hence the availablity of amino acid. This one factor alone has implications o far-reaching as to link hypoxia to the onset of many major disorders. Furthermore, they have noted various other body chemicals and functions whicjh are altered during the state of hypoxia."

These effects of hypoxia on the balance of essential body chemicals when thought of at the cellular level have profound implications when considering cancer, which is now generally recognized as being initiated by an accidnet or distortion of a single cell, and the proliferation of such distortion in succeeding cell divisions.

The key to cell division os the separation of the strands of the chromosomal DNA and the building onto the separated strands A and B the chemical 'building blocks' to form two identical DNA molecules having strands AB' and A'B. When a proper chemical balance is present in the cell environment, and all the building blocks to form strans B' and A' are available as needed, the DNA replication and cell division can proceed smoothly providing normal, healthy cell division and tissue regeneration.

Much has been published concerning the role of viruses, and various chemicals as triggering the type molecular accident that leads to cancer; but it is considered that these may in reality be contributing to a state of chemical imbalance also influenced by local hypoxia, and that it is the hypoxia, whether augmented by a virus or chemical carcinogens, or induced primarily by the individual's poor bioelectrolysis performance, that is the proximate cause of a cancer producing cellular accident.

[ ... ]

In Ross Gwynn's work with cancer patients, most of whom have unfortunately been in the terminal stage before receiving his treatment, there have been clear indications that the injections of his electrolyzed physiological saline Chlorozone are capable of causing remissions in the cancerous growth. In one patient with a rapidly advancing malignancy involving an entire upper quarter arm, chest, back, neck and face plus internal growth which was of unknown scope and beyond reach, the follwoing progress was observed.

A. Local IM injections along a line of advance would halt that advance and cause it to retreat.

B. Injections into and around several isolated tumors caused these to disappear within about 48 hours -- and there was no sign of their recurrence during the patient's remaining lifetime.

C. On two occasions when the patient's throat became so closed as to prevent eating and impair breathing, injections deep into the neck and throat caused enough of a retreat to clear the throat for eating and free breathing.

D. In the center of a mass of chest tissue that was the consistency of cardboard, and from which insertion of needles drew no blood, prolonged infusions of EPS on two successive days caused an island of normal appearing, normal feeling tissue to develop, in which the insertion of a needle would again draw blood, and this apparently restored tissue persisted for the remainder of the patient's life.

Ross Gwynn's work with advanced cancer patients did not permit any planned comparative studies, but in one instance fate provided a situation which afforded meaningful comparison.

A doctor in Athens had at the same time two patients with advanced abdominal cancer and general metastasis. The conditions of both patients had deteriorated to the point where death, for both, was expected within about one week. The doctor decided to let Patient A receive Ross Gwynn's Chlortozone treatment, but withheld them from Patient B. Patient B died, as expected, in about one week.

Patient A, on the other hand, responded very well to Chlorozone injections, was able to resume a moderately active life, and lived on, relatively free of pain for 7-1/2 months. During this period he received Chlorozone injections totaling 27,371 cc. This long survival strongly suggests an arresting or retarding of the cancerous growths, with apparent local remissions; and it raises a question as to possible benefits of even larger, or more frequent or prolonged injections of Chlorozone.

The one, early-stage cancer treated by Ross Gwynn as the patient's primary affliction was lip cancer, for which the diagnosis had been confirmed by biopsy test at a cancer clinic in Athens. At the start of Chlorozone injections the lip was about twice its normal size and discolored. After three IV injections of Chlorozone totaling 750 cc over a two week period, the lip had returned to normal size and color, and the cleft (surgical) that was made on the inside during the biospy was filling up with healthy tissue. An additional 200 cc IV injection was given at this time, and two weeks later, one month after the start of Chlorozone injections, reexamination at the clinic which made the original diagnosis showed no signs of a tumor.

It is realized that these case history summaries do not, by themselves, prove anything concerning the effectiveness of Chlorozone in treating cancer. They are believed, however, to provide an indication that Chlorozone injections provide some benefit worthy of careful and contrrolled investigation.

Furthermore, the fact that these case histories embrace several different types of cancer as apparently responding to Chlorozone injections, would seem to suggest that, whatever the action of Chlorozone, it must be taking place at the molecular or cellular level, i.e., at a level which would provide a common denominator for the type disorder which cancer appears to be.

The theory earlier discussed, which realtes cancer to a particular type of error or accident in DNA replication, provides such common denominator; and makes plausible the benefits observed in the three case histories described. The theory is of course advanced in a macro sense, i.e., that the chemical imbalance setting the stage for the DNA accident is induced by hypoxia and that correction of the DNA accident hinges on eliminating the state of hypoxia.

The oxidant function of injected Chlorozone is obviously quite different from supplemental oxidant produced by an individual having good 'bioelectrolysis performance', but the similarity of beneficial effects points the way to interesting new areas for investigation, i.e., just what are the biochemical paths and reactions for overcoming hypoxia? And does the apparent rapid change of cancerous tissue to normal tissue somehow involve a partial breakdown of cancerous tissue normal tissue to collagen and other 'building blocks' which can then be reassembled as normal tissue?

To the extent that the latter question is a valid one, it must be recognized that conventional techniques which remove (surgically) or destroy (by x-ray and other radiation, and by toxic chemicals) the cancerous tissue may be impeding recovery by eliminating 'building blocks' essential to recovery.

For this reason it is urged that those who may be stimulated by this presentation to undertake evaluation of Chlorozone in the treatment of cancer be guided by the following principle:

1. All experimental techniques should be devised or modified to accomodate the theories here presented.

2. In all instances where cancer is being originally diagnosed and not previously treated, insist on an introductory period ( a few days to about 2 weeks) of treatment with Chlorozone alone, prior to the start of any conventional surgery or radiation or toxic chemcial techniques.

3. In instances where conventional cancer treatments have already been employed, they should be discontinued during a period of cChlorozone treatment as 'incompatible' with the theory of Chlorozone's effectiveness.

4. Supplement Chlorozone treatments by whatever means available to stimulate the patient's bioelectrolysis performance, particlarly in the area of stimulating alpha, and higher voltage brainwave activity. If religious faioty, meditation, etc, are not applicable to a particular patient, biofeedback techniques can be used to train the patietn in alpha and higher voltage brain activity.

The interesting thing about this Biodynamic Approach to Cancer is that in addition to providing and explaining what appears to be a safe and effective therapeutic treatment of cancer patients, it also provides a plausible explanation of waht may bring about the 'natural remissions' reported in the medical literature.

What is presented here is far from any 'final answer or solution' to the problem of cancer. The theory advanced does, however, recognize the wondrous ability of the body, given a chance, to heal itself; and it is hoped that among the readers there may be those in a position to do so, who will undertake some of the controlled studies and evaluations, known to be needed, to confirm or disprove the theory.

Inventor(s): MERTON GWYNN ROSS; THEMY TIM
Classification: - international: C01B13/10; C02F1/467; (IPC1-7): C01B13/04 - European: C01B13/10; C02F1/467B
Also published as: GB 1279020 // FR 2015050 // CH 533424 // CA 923071

BACKGROUND OF THE INVENTION

The generation of chlorine by electrolysis of sodium chloride brines at an applied potential of 3.5 to 7 volts has been practical for many years in the commercial production of chlorine gas. In such production of chlorine gas the products released at anode and cathode are separately removed from the cell. The chlorine in each instance is removed as a gas while the sodium released at the cathode is recovered in different ways. In the so called mercury cell employing a mercury cathode the sodium combines with the mercury as amalgam. In other type cells such as the diaphragm type or bell jar type the released sodium in the cathode compartment reacts with water to liberate hydrogen, which is separately collected, and form sodium hydroxide which is drawn from the cell as fresh brine is added.

More recently there have developed procedures for electrolyzing sodium chloride brines and other readily dissociating chlorides including aqueous hydrochloric acid by passing the electrolyte between spaced anode and cathode, without any attempt to separate the products released in the electrolysis. When operating in the range of 3.5 to 7 volts with a constant flow of brine between the electrodes the amounts of electrolysis products liberated are generally sufficiently low to be dissolved or dispersed in the discharged electrolyte. Furthermore there is some interreaction of the chlorine with the components released at the cathode to form hypochlorite.

Adaptations of such flow-through electrolysis of brines have found considerable use in the chlorinating and hypochlorinating of waters in swimming pools, urban water supplies and the like; and by special controls to enhance the formation of hypochlorite, the basic process has been adapted to the commercial production of bleaching solution and the like.

When chlorinating water supplies the practice has generally been to treat a concentrated brine to develop therein a relatively high chlorine concentration and to blend this with water to provide the 1 to 5 p.p.m. or other chlorine content required for the intended purification. In swimming pool chlorination a practical approach has been to add sodium chloride to the pool water to provide about 2,500 to 3,000 p.p.m. of NaCl. Then in the recirculating and filtering system for the pool a portion of the recirculating water can be diverted through a cell, electrolytically fortified with chlorine, and returned to the recirculating stream. Such a system can be operated continuously or intermittently, and the voltage and/or flow rate adjusted to meet the needs of a particular size pool and the number of pool users.

One of the limitations on the more extensive use of electrolytic chlorinating in pools, water supplies, and the like has been the sensitivity of electrodes to damage and deterioration under the corrosive conditions that characterize the flow through of electrolyte between closely spaced electrodes. The anode, in particular, is sensitive to attack leading to both loss of efficiency and eventual destruction of the anode. Even electrodes carrying an electroplated deposit of platinum have poor resistance to the corrosive environment, apparently due to a porosity in the electroplated deposit; and if voltage across the cell is increased to about 10 volts the breakdown of such electroplated electrodes is quite rapid.

This problem has been solved by an improved electrode developed by applicants, and fully disclosed and claimed in the pending application Ser. No. 520,596 filed Jan. 14, 1966, now U.S. Pat. No. 3,443,055. The improved electrode comprises a laminated body of a platinum metal foil on a substrate or backing of a metal such as titanium, tantalum, or niobium (also known as columbium) which is highly resistant to electrolytic oxidation, the bonding being effected by high localized pressure and thermoelectric heat. The new electrodes have found extensive use in swimming pool chlorination, and while they have not been in use long enough to determine their actual durability in the field, they are believed, on the basis of accelerated aging tests, to have a useful life of more than 5 years when used daily for 10 to 12 hours per day.

THE INVENTION

The development of the new electrodes above mentioned has not only provided for more efficient practicing of known chlorinating processes, but it has also removed the equipment imposed limitation on voltage to be employed, since the new electrodes can withstand extended operation at 100 volts and even higher.

It has now been found that in the electrolysis of sodium chloride brines and other electrolytes providing chloride ion there is a significant change in the nature of the electrolysis products when the voltage is increased above about 10 volts, and particularly when it is above about 14 volts. The full nature of this change is not understood, but it appears to involve the generation of free radicals and/or charged or ionic species of varying stability which appreciably modify and extend the biocidal activity of the cell effluent.

Among the free radicals which may be generated are Cl@. Cl3 @. , OH@., HO2 @. and ClO@. . Most of these are quite short lived but apparently give rise to the formation of highly oxidizing species such as O3, C10 2 and H2 02 which may be considered in the nature of stabilized free radicals. There is the further indication that chlorite and chlorate ions (C102 @- and C103 @-) and/or superoxide ion (02 @-) may be formed which in turn may generate additional free radicals and stabilized free radicals.

As earlier stated, it is not yet known just what combination of free radicals or other oxidizing components are produced in the high-voltage operation. It does appear, however, that appreciable amounts of ozone are generated and that the ozone persists, at progressively reducing levels, for a sufficient time to exert a supplementary biocidal action comparable to or even exceeding that of the chlorine and hypochlorite which normally would provide the biocidal activity.

It can be demonstrated, however, that high-voltage electrolysis of dilute NaCl solutions leads to production of at least 1 mole of free radicals for each 10 to 100 moles of chlorine; that ozone is present in the cell effluent in the proportion of about 2 to 5 parts (and occasionally as high as 20 parts) for each 100 parts of chlorine, and that the ozone persists in the cell effluent for an extended period.

In order that the reader may better visualize these factors typical test procedures and determinations will be described.

DETERMINATION OF THE EXISTENCE OF FREE RADICALS

An electrolysis unit is employed having electrodes of platinum foil bonded to a titanium metal base (by the method disclosed in said application, Ser. No. 520,596 ). The electrodes measure 2.25 .times.6 inches and are supported in a plastic (methyl methaerylate) frame with the exposed platinum surfaces measuring 2 .times.6 inches and appropriately 0.64 cm. apart. The solution to be electrolyzed is introduced at the bottom and removed at the top of the cell.

Saline solutions used are Palo Alto California tap water containing 3,000 p.p.m. of C.P. sodium chloride (approximately 0.05 molar NaCl). The solution is fed at approximately 35 ml./sec. while applying a potential of 15 volts and current of 25 amperes to the electrodes, and quantities of effluent are collected for testing. Under these conditions the effluent solution contains approximately a 10@-@5 molar chlorine concentration.

For detection of free radicals a Varian, Model V-4502 electron paramagnetic resonance (X-band) spectrometer was used. This instrument, hereinafter referred to as the EPR apparatus is supplied by Varian Associates of Palo Alto, Calif.

As free radicals are of very short duration, being used up rapidly in forming more stable species, a free radical indicator or stabilizer is used, in the form of a 0.02 molar aqueous solution of 2,2,6,6-tetramethylpiperidine, hereinafter referred to as TMP. This solution is tested prior to use in the EPR apparatus and treated with hydrazine until no signal could be detected, and is incorporated in the saline solution or effluent in the proportion of about 10 ml. per liter.

The following test procedures were then followed with the noted results.

a. With the cell operating as described a sample of cell effluent was collected and transferred to the EPR apparatus. No signal was detected, indicating that free radicals which may have been present were consumed before reaching the EPR apparatus.

b. A 200 ml. sample of effluent collected in a beaker containing 2 ml. of the TMP solution. when this was tested in the EPR apparatus it gave a weak signal indicating a free radical concentration of about 10@-@8 molar. The point of collection of the sample, however, was at the end of a cell outlet tube about 3 meters long, and in passage through the tube free radicals could have been consumed. Therefore the following additional tests were made.

c. A mixture of 1 liter of the saline solution and 10 ml. of the TMP solution were run through the cell under the same flow and current conditions. A sample of the resulting effluent, when tested in the EPR apparatus gave a strong triplet signal indicating a free radical concentration of about 10@-@6 molar.

d. To be sure that the TMP did not itself generate free radicals as it passed through the cell, a fresh quantity of saline solution was electrolyzed and TMP solution, at approximately one-tenth the flow rate through the cell, was introduced into the effluent at the juncture of the cell and discharge tube. A sample of the effluent mixture, when tested in the EPR apparatus, showed the same strength of signal as in "c" above, indicating a free radical concentration of about 10@-@6 molar.

Bearing in mind that the chlorine concentration is approximately 10@-@5 molar the molar ratio of free radical: chlorine is approximately 1:10.

DEMONSTRATION OF EXISTENCE OF OZONE IN THE CELL EFFLUENT

Ozone is extremely difficult to detect and quantitatively determine in the presence of chlorine because most tests responsive to an oxidizing function will respond similarly to these two materials. An ozone detecting apparatus has been developed, however, which is specific to ozone and does not respond to chlorine. This apparatus, which utilized a chemiluminescence method, has been described in an article entitled "Rapid Ozone Determination Near an Accelerator" by Niderbragt, van der Horst, and van Duijn which appeared in NATURE, Apr. 3, 1955, at page 87. This apparatus cannot detect ozone or the amount thereof in an electrolyte but it can detect the presence and approximate concentration of ozone in the air above an electrolyte, which is an indirect demonstration of the presence of ozone in the electrolyte.

Stationary (no-flow) tests were conducted using electrodes of the size and spacing described above, filling the cell (about 750 ml.) with solution to be tested, and turning on the current at the voltage and amperage levels indicated below for a period of 30 seconds, with the ozone detector apparatus supported with its inlet about 10 ml. above the liquid level. A solution containing 3,000 mg./1. of NaCl (0.0513 molar) was first tested, and other solutions of approximately 0.0513 molar concentration were tested for comparative purposes. The results are tabulated below: ##SPC1##

This data indicates the special effect of chloride ion and increase in voltage on ozone production. The fact that NaOH gave no ozone was to be expected in view of the known instability of ozone under alkaline conditions.

Similar tests were run with Palo Alto tap water (5mg./1. NaCl) and solutions containing 100 mg./1. and 200 mg./1. of NaCl with the following results: ##SPC2##

This data further indicates the importance of chloride ion concentration and voltage in obtaining ozone production. It has separately been determined that significant amounts of ozone can be generated with as little as 20 p.p.m. of NaCl by operating at about 100 volts or higher. Furthermore, the transcient presence of ozone can be demonstrated by the increase in oxygen level upon electrolysis of a complex system containing chloride ion. An example of this is as follows:

A series of tests were run on Palo Alto sewage which contains about 100 mg./l. or 100 p.p.m. of NaCl. Sewage and diluted sewage (4 1. diluted to 20 1. with water to which 25 ml. of KH2 PO4 buffer was added) were passed through a cell having the electrode size (2.times.6 inches) and spacing (0.64 cm.) as above described at a flow rate of one liter per 24 seconds employing current at the different voltages and amperage shown below: ##SPC3##

A composite sample of all electrolyzed samples showed a BOD of 82 mg./1. compared with 230 mg./1. for the raw sewage control.

The build up of the dissolved oxygen concentration is considered to reflect the increased generation of ozone with the voltage increases, which ozone reacts immediately with the organic soil to release oxygen.

METHOD OF ANALYSIS FOR CHLORINE AND OZONE

Having thus demonstrated that substantial amounts of ozone are formed in high voltage electrolysis of aqueous media containing chloride ion, it becomes possible to measure quite accurately the amounts of chlorine and ozone in a cell effluent by the following two-stage method of analysis which is based on a procedure outlined in Scott's Standard Method of Chemical Analysis 5th Edition.

a. To an aqueous sample, suitably about 100 ml., containing chlorine and ozone is added 2 g. of KI crystals and a slight excess of acetic acid (to pH 3.0 to 4.0 ). Titrate the liberated I2 with 0.1 normal (or other known normality) Na2 S2 03 until the yellow color becomes very pale. Then add starch indicator and titrate until the blue color entirely disappears.

Calculate the total Cl2 +O3 as Cl2 equivalent by the following formula in which N is the normality of the Na2 S2 03.

b. The same procedure is followed with a second sample to which NaOH has been added to raise the pH to 10 to destroy the ozone, followed by acidification to below pH 7 with acetic acid. This titration measures the Cl2 alone.

By subtracting the values in titration "b" from the value in titration "a" the difference represents the quantity of ozone in terms of mg. Cl2 (equiv.)/liter. This value multiplied by the factor 48/70.91 (or 0.677 ) provides the approximate mg./1. of 03. It is quite possible that other oxidizing species may be present along with the ozone and also inactivated by the alkaline treatment, in which event the approximate mg./1. of 03 as thus determined could be somewhat higher than the true 03 concentration.

Ozone may also be determined directly and much more accurately by the spectrophotometry method described by P. Koppe and A. Muhle in z. Anal. Chem. 210(4), 214-256 (1965 ).

COMPARATIVE PRODUCTION OF CHLORINE AND OZONE FROM DIFFERENT SOURCES

Using the no-flow procedure above described in which 750 ml. of test solution is electrolyzed for 30 seconds at the indicated current and potential, a number of different solutions were treated and then analyzed for Cl2 and O3 by the method above described. Pertinent data on these tests are tabulated below. Solution temperatures were approximately 23 DEG C. (73.4 DEG F.) at the start unless otherwise indicated. ##SPC4##

The foregoing data indicates that:

a. Halide solutions other than chloride suppress or inhibit ozone formation, and that the presence of another halogen can reduce or prevent the ozone production even though a preponderant amount of chloride ion is present.

b. Significant amounts of ozone are produced when other soluble metal cations are substituted for the sodium.

It is well known that ozone is a very active biocidal agent, more active in most instances than chlorine. Thus the ability to generate useful amounts of ozone along with chlorine in electrolysis of chloride containing solutions is in itself a highly advantageous development for many disinfecting, sanitizing and other biocidal purposes. Furthermore, the ozone-chlorine-free radical environment created by the high-voltage electrolysis appears to prolong or regenerate available chlorine activity. In a sense the chlorine-ozone association, possibly influenced by unidentified free radicals or other active species, provides a synergistic biocidal action substantially exceeding that which could normally be attributed to the chlorine and ozone separately.

Turning now to the practical adaptations of the present invention, they are as numerous as the various known needs for biocidal activity. Furthermore they involve several different procedural approaches depending on factors such as availability of chloride ion in the water to be treated, the quantity of medium to be treated, whether continuous operation or intermittent operation is called for, and closely related thereto, whether equipment cost or operating cost is the more important economic factor. While the procedural approach may be widely varied to meet particular needs, most adaptations of the invention will fall in one of the following categories.

a. Flow through electrolysis of the total volume of a natural chloride containing medium such as domestic water or central water supply containing at least 10 p.p.m. of Cl@-, raw sewage containing at least 100 p.p.m. of Cl@-, and other naturally occurring media such as blood and sea water.

b. Flow through electrolysis of the total volume of a chloride enriched medium such as swimming pool water having 2,500-3,000 p.p.m. of NaCl, for preparing heavy duty sanitizing and disinfecting solutions and/or bacterial warfare decontamination agents.

c. Flow through electrolysis of a diverted portion of a chloride containing medium, particularly as a modification of the procedure described in "b" above for treating swimming pool water.

d. Flow through electrolysis of a diverted portion of a medium with controlled addition of chloride to the diverted portion prior to electrolysis, and return of the diverted portion to the main body of medium after treatment.

e. Flow through electrolysis of a separate, high chloride (1,000 to 35,000 p.p.m. NaCl) medium for controlled addition to a medium to be treated.

f. Flow through electrolysis of a body of chloride solution to build up a desired C12 and O3 level while introducing brine and withdrawing enriched solution at a relatively slow rate.

g. Modification of procedures "a" to "e" conducted on a no-flow basis with a given volume of static or agitated medium with residence time, or duration of current flow, providing control of chlorine generation.

Typical uses for one or more of these procedures include, with limitation:

1. Swimming pool treatment.

2. Treatment of domestic or community drinking water.

3. In hospitals, doctors offices, and in the home for preparing sanitizing and disinfecting solutions of selected chlorine and ozone content.

4. Treatment of sewage.

5. Pollution control in rivers and harbors; and algae control in lakes.

6. Treatment of air conditioners cooling waters to control algae.

7. Preparation of agricultural disinfectants such as egg wash, and dairy equipment sterilization.

8. Industrial sanitation and/or sterilization in laundries, restaurants, food processing industries and the like.

The following examples will show specific adaptions of the invention in each of the procedural categories above mentioned, but it is to be understood that these examples are given by way of illustration and not of limitation. In these examples the electrodes in each instance are of platinum foil bonded to a titanium substrate according to the disclosure of said pending application, Ser. No. 520,596. In certain of the examples cells may be identified as 3 A, 6 A, 9 A, and 18 B cells. In such event they are cells of the type disclosed in applicants' pending application, Ser. No. 642,951 filed June 1, 1967 now U.S. Pat. No. 3,479,275, wherein the electrodes are so supported in a plastic (methyl methaerylate resin) frame that more than 99 percent of the flow through the cell, from bottom to top, passes between the electrodes, and the space outside the electrodes is occupied by an essentially static body of the circulating medium. The sizes and electrode spacings of these electrodes are: ---------------------------------------- -

Length Width Spacing

__________________________________________________________________________

3 A 3" 2" 0.64 cm.

6 A 6" 2" 0.64 cm.

9 A 9" 2" 0.64 cm.

18B 18" 2" 1.28 cm.

__________________________________________________________________________

In the examples values are sometimes given for both chlorine and ozone yield in the cell effluent. In other instances the yield is expressed as chlorine equivalent by thiosulfate test. While such yields are primarily chlorine, it is to be understood that small amounts of ozone and other oxidizing species are also present and react with the thiosulfate to give a reading which is somewhat higher than the chlorine per se. As the ozone and other oxidizing species have bacteriacidal action comparable to or greater than that of chlorine, the recording of the combined oxidizing species as "chlorine equivalent" permits realistic evaluation of the cell effluents.

EXAMPLE I

In a domestic water system, suitably containing a holding tank where treated water can be stored for use as delivered from a well or other source providing water containing at least 20 p.p.m. of NaCl, a 9 A cell as above described is installed in such delivery line. The cell will handle a flow of up to 6 gallons per minute. In order to provide 1 2 p.p.m. of chlorine equivalent by thiosulfate test in the treated water, assuming a water feed of 4 gal./min. and a water temperature of 50 DEG-55 DEG F., the proper current based on NaCl in the water can be estimated from the following table: ---------------------------------------- -

Salinity Volts Amps
__________________________________________________________________________

50 p.p.m. 100 11

100 p.p.m. 45 9

150 p.p.m. 22 5

__________________________________________________________________________

Example II

In a city water supply having a flow of 300 gal./min., and containing 150 p.p.m. of NaCl an electrolytic cell is installed in the feed line having platinum coated electrodes as above described measuring 4.times.18 inches and spaced 2 inches apart. The flow rate between the electrodes is about 12.5 feet per second. At a water temperature of 50 DEG-55 DEG F., and with a potential of 200 volts and current of 2 amps applied to the electrodes the treated water will contain 1 to 2 p.p.m. of chlorine.

EXAMPLE III

As an alternate method of treating the water supply described in example II a salt solution at 50 DEG F. containing 5,000 p.p.m. of NaCl is fed through a 9A cell at a rate of 0.75 gallons per minute at a potential of 22 volts and current of 180 amps. A test of the cell effluent shows 300 p.p.m. of Cl2 and 15 p.p.m. of O3. Blending this effluent with the city water at the rate of 1 gal. per 300 gallons provides a desired chlorine level of 1 p.p.m. and about 0.05 p.p.m. of ozone.

EXAMPLE IV

A sample of raw sewage at 50 DEG F. containing about 100 p.p.m. of NaCl was fed through a 9A cell with applied potential of 15 volts at the rate of 1 gal./min.

Data was collected on the input and output fluid on 12 test runs and the values averaged as follows: ---------------------------------------- -

Input Output Units
__________________________________________________________________________

Dissolved Solids 104 70 p.p.m.

B O D 114 105 mg./1.

Coliform 1,524,000 400,000

organisms

Dissolved O2 0.85 1.65

p.p.m.
________________________________________________________________________

In this series of runs the current flow was so low as to not register on the available ammeter. The tests indicate, however, that the applied voltage, even with negligible current flow, has a marked effect upon the sewage.

EXAMPLE V

A 30,000 gal. swimming pool has a recirculating system with a flow of about 60 gal./min. (equivalent to a complete change of water every 8 hours). In the line between the filter and the pool and 18B cell is installed to carry the full flow of water. Salt is added to the pool water to provide a 3,000 p.p.m. NaCl concentration. With a water temperature of about 78 DEG F. the cell is operated at 17 volts and 25 amps. The return water to the pool tests at 3 p.p.m. of chlorine equivalent. After about 6 hours of operation with little or no organic load the pool reaches a level of about 1 p.p.m. chlorine equivalent. This level is readily maintained by operation of the cell 12 to 20 hours per day depending on the extent of use and/or the amount of contaminates being introduced into the pool.

The procedure in this example has the drawback of exposing the electrodes to excessive wear particularly due to large quantity and rapid flow of the circulating water. This problem is eliminated by the modified procedure of the following examples.

EXAMPLE VI

In a pool setup similar to that described in example V about 5 percent of the fluid flow leaving the filter is diverted to a branch line containing a 6 A cell, the discharge from the cell rejoining the main stream at the intake side of the circulating pump. When this cell is operated at 17 volts and 18 amps with a flow rate through the cell of about 3 gal./min. and water temperature of about 78 DEG F. the cell effluent is found to contain 25 p.p.m. of chlorine equivalent. After an initial buildup in the pool a chlorine level of about 1 p.p.m. is maintained throughout the pool by operating the cell 12 to 20 hours a day, depending on the swimming load. The circulation of the cell effluent through the filter prior to return to the pool has the beneficial effect of lowering the contamination on the filter. If the cell were located between the filter and the pool the chlorine level of the pool could be maintained with less operation of the cell, but more frequent backwashing of the filter would probably be required.

EXAMPLE VII

A pool of the size described in example V, and having a similar circulating system, but without the 3,000 p.p.m. of added salt in the pool water, is provided with a branch line between filter discharge and the suction side of the pump to carry about 5 percent of the fluid flow. Into this branch line is metered a concentrated brine, and the mixture is passed through a 6 A cell conveniently located in said branch line. The mixture entering the cell contains about 3,000 p.p.m. NaCl. A flow of brine through the cell at 17 volts and 18 amps at the rate of 0.75 gal./min. provides an effluent containing 100 p.p.m. chlorine equivalent. As this effluent is delivered to the main recirculating stream it is reduced to about 3 p.p.m. chlorine equivalent, and a pool level of about 1 p.p.m. chlorine can be maintained by operating the cell 12 to 20 hours a day depending on the extent of pool use.

When a particular chlorine level such as 1 p.p.m. has been established in the pool by any of the methods described in examples V and VII it has been found that if the pool is not used by swimmers the chlorine level may hold for 36 to 48 hours, or even longer with very little change. Possibly this is due to the lingering effect of traces of ozone or more active species acting to liberate available chlorine from other chlorine containing species.

EXAMPLE VIII

An air conditioning cooling tower for recirculating water over which the water is circulated at the rate of about 30 gallons per minute developed algae deposits on the cooling racks at the rate of 1 inch or more per week requiring shut down and removal of algae deposits every 2 to 3 weeks.

The warm water line to the tower was provided with a branch line diverting about 10 percent of the flow and concentrated brine was metered into this branch line to provide approximately 3,000 p.p.m. of NaCl. This mixture was passed through a 9 A cell inserted in the branch line and the cell was operated at about 17 volts and about 10 amps. The cell effluent when recombined with the recirculating water stream provided in said stream a chlorine equivalent of about 2 p.p.m. By passing this chlorine enriched water to the tower during all periods of operation the formation of algae was completely eliminated.

This procedure will gradually cause a buildup of NaCl in the circulating water and as this buildup progresses, smaller amounts of brine will be needed to provide 3,000 p.p.m. of NaCl in the solution entering the electrolytic cell. In fact, when the salt content of the recirculating water has risen to about 3,000 p.p.m. the supplemental feed of brine can be eliminated. In most installations a salt concentration of the order of 3,000 p.p.m. is not sufficient to cause any corrosion problem in equipment (generally a salt concentration of about 6,000 p.p.m. or higher is required to cause a significant corrosion problem). On the other hand, if in a particular situation a salt concentration of 3,000 p.p.m. in the circulating water would be considered excessive, the system can be made to generate comparable amounts of chlorine equivalent at a substantially lower salt concentrations by operating the cell at higher voltage.

EXAMPLE IX

A small 3A cell can provide saline solutions of widely varying chlorine and ozone concentration in practical quantities for home use, doctor's and dentist's offices, and the like. A few typical solutions are prepared as follows: ##SPC5##

It will be understood that effluents of lower, higher, or intermediate chlorine concentration can be obtained by suitable adjustment of the salinity, applied voltage, and flow rate through the cell. Furthermore the effluents can be used full strength or diluted to suit particular disinfecting and sanitizing needs. They can also be stored for extended periods in closed containers, solutions stored for several weeks showing little loss of activity.

The uses to which the effluents, or suitable dilutions thereof, can be put are as varied as the needs for sanitizing or disinfecting treatment of people and things around home, doctors' and dentists'offices, hospitals and the like. By way of illustration solutions having a chlorine equivalent of 25 to 100 p.p.m. have been effectively used as gargles, solutions for the cleaning of wounds including irrigation of abdominal wounds, and sterilization of the transfer tissue and graft site in skin grafting. At higher concentrations of 300 to 1,000 p.p.m. of chlorine equivalent, solutions are effectively used for sterilization of instruments, sterilization of the hands in preparation for and during surgery and related purposes where high bactericidal action is required. Even at the 1,000 p.p.m. concentration, the solutions are surprisingly nonirritating.

Bottled quantities of solution are practical for travelers, campers, or the like. For example, a solution of 100 to 300 p.p.m. chlorine equivalent concentration provides a versatile solution for full strength or diluted use in meeting the needs for germicidal and disinfecting action when traveling or camping. An ounce of 100 p.p.m. solution added to a quart of water of questionable purity would provide a chlorine content of about 3 to 5 p.p.m., thus assuring the safety of questionable water. In this connection, it is significant to note that no taste of chlorine in the treated water can be detected until the chlorine equivalent level reaches about 3 p.p.m. This is in distinct contrast to water treated with chlorine gas in which the chlorine can generally be tasted at concentrations as low as 0.3 or 0.5 p.p.m.

Both the absence of taste below concentrations of 10 p.p.m. chlorine equivalent and the nonirritating nature of solutions having as high as 1,000 p.p.m. chlorine equivalent, serve to emphasize the unique nature of the cell effluents when subjecting sodium chloride solutions to high voltage electrolysis.

While the foregoing examples have been based primarily on flow-through operation in which saline solution is passed between electrodes of a cell, it will be understood that comparable results can be achieved with limited volumes of salt solution in a stationary cell and with the extent of electrolysis controlled by the duration of the applied current. The following example will serve to illustrate a practical adaptation of such stationary or no-flow operation.

EXAMPLE X

A small cell having platinum coated electrodes of the type described approximately 0.75 inch wide, 1.75 inches long and spaced apart by 0.75 inch provides a chamber between the electrodes having a capacity of approximately 1/2 fluid ounce. The electrodes are connected to a suitable plug for insertion in the conventional automobile cigarette lighter socket. When salt solution is placed in the cell and the plug inserted in the lighter socket, fed by a 12 volt battery, electrolysis readily takes place as evidenced by the bubbling of the solution between the electrodes.

If salt solution of about 5,000 p.p.m. concentration (which is slightly salty to the taste) is placed in the cell and electrolyzed for about 30 seconds, this develops in the solution a chlorine equivalent of approximately 100 p.p.m. The resulting half ounce of chlorinated solution could be used directly for cleaning and dressing of a wound or could be put to other disinfecting uses. For example, addition of the half ounce of solution to a pint of questionable water would make it safe for drinking without creating any objectionable chlorine taste.

The unit above described is therefore a practical unit for the traveler or camper. Furthermore, it would be apparent that fixed cells of somewhat larger size could be practical for the home or even for doctors' and dentists' offices and the like.

In examples I to X no attempt has been made to measure active species other than chlorine and ozone. It is to be understood, however, that the presence of detectable amounts of ozone is an indication of a substantial free radical generation in the electrolysis. It had been clearly demonstrated that this free radical and ozone production results from employing a potential of at least 10 volts and preferably at least 14 volts in the electrolysis.

The minimum voltage required to produce useful quantities of ozone varies with the salinity or the chloride ion concentration. Within the fractional normality range of about 0.0003 N to 0.6N NaCl it has been found that there should be a potential of at least 100 volts for 0.0003 N solution or chloride ion concentration of about 10 p.p.m., and at least 10 volts for a 0.6 N solution or chloride ion concentration of about 21,000 p.p.m. The following table will more clearly indicate the general relationship between minimum voltage and chloride ion concentration. ##SPC6##

Increasing the voltage above the minimum value for a given chloride ion concentration will increase the yield of both chlorine and ozone, and will generally increase the ozone:chlorine ratio. Thus at a voltage about 25 percent above the minimum value for a particular chloride ion concentration, and at favorable pH and temperature conditions as hereinafter described, the ozone to chlorine ratio is generally in excess of 1 part ozone to 20 parts chlorine, and at a voltage 50 percent above such minimum this ratio may be as high as 1 part ozone to 5 to 10 parts chlorine.

The pH of a medium is also an important factor and for production of useful amounts of ozone (i.e., at least 1 part by weight per 50 parts of chlorine) the pH should be within the range of 6 to 8.5. When seeking an ozone:chlorine ratio of the order of 1:20, the pH range should be narrowed to about 7 to 8, and for maximum ozone production a pH of 7.2 to 7.8 is preferred. Chlorine production, however, is favored by a slightly lower pH, and adjustment of pH is therefore a practical way to vary the chlorine:ozone ratio in a cell effluent.

Temperature of the electrolyte in and leaving the cell has an important influence on the amount of ozone generated. While temperatures within the range of about 55 DEG to 95 DEG F. can be employed, substantially higher ozone yields are obtained if the effluent temperature is in the 60 DEG to 75 DEG F. range; and at a temperature in excess of about 66 DEG F. and pH of 7.2 to 7.8 the proportion of ozone may be as high as one part by weight to each 5 to 10 parts by weight of chlorine.

Depending on the chloride ion concentration, the cell size, flow rate and applied voltage and current, small to relatively large amounts of heat can be generated within the cell, but in any flow-through operation the fluid input temperature is a major factor in determining the effluent temperature. It is sometimes desirable, therefore, to preheat the input water or solution, particularly if its temperature is below about 55 DEG F. Warming the electrolyte increases ion mobility and hence conductance, particularly at the more dilute saline concentrations.

Thus it appears that temperature and pH, as well as the voltage applied to a solution containing chloride ion within a cell are closely related or interdependent factors in creating the high incidence of free radicals and advantageous yields of ozone which characterize the methods herein disclosed.

Compared with a typical hypochlorite cell, the method of the present invention electrolyzes a much more dilute brine or saline solution, i.e. a solution having a much lower chloride ion concentration, at a much higher voltage, obtaining lower conversions and current efficiencies. Usually the current density is less than 5 amperes per square inch, or less than 3 amperes per square inch with more dilute brines. With more concentrated brines, i.e., those approaching 21,000 p.p.m. of chloride ion, current densities somewhat higher than 5 amperes per square inch can be practical, since maximum current density increases with the saline, or chloride ion, concentration, while voltage decreases.

The practical variations in voltage and amperage are considered to be those variations which provide a watt density of 10 to 100 watts per square inch of electrode surface. Within this range the lower values apply primarily for the more dilute brines, while the higher values e.g., 30 to 100 watts per square inch apply primarily for the more concentrated brines. It will be understood, however, that voltage, current density, and watt density in any particular installation can vary substantially with changes in other variables such as temperature, flow rate, or fluctuations in the chloride ion concentration of the medium being electrolyzed.

It should be emphasized that the practical utilization of the methods herein disclosed is dependent on employing spaced electrodes, with the exposed surface of at least the anode having a continuous surface of a platinum metal. In systems intended for periodic reversal of electrode polarity it follows that both electrodes must have such continuous surface of a platinum metal. On the other hand, when polarity is not to be reversed the cathode can be formed of nickel, stainless steel, or other conventional cathode material. In adapting the invention to different uses it has been indicated in the foregoing examples that the size and spacing of electrodes can be varied to accommodate the quantity of electrolyte to be treated. It is to be understood, however, that the invention also contemplates the use of two or more cells for the simultaneous (parallel) and/or successive (series) treatment of brines and other electrolytes containing chloride ion.

Various changes and modifications in the procedures herein described will occur to those skilled in the art, and to the extent that such changes and modifications are embraced by the appended claims, it is to be understood that they constitute part of the present invention.

We, Ross MERTON GWYNN AND TIM THEMY, citizens of the United States of America, of 4724 Donnie Lyn Way and 5735 Hesper Way, respectively, Carmichael, State of California, United States of America, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:

This invention is concerned with improvements in or relating to electrodes.

In the electrolysis of salt solution, particularly in chlorinating and hypochlorinating processes, considerable difficulty has been experienced in providing electrodes which will perform effectively for extended periods of time By way of illustration in the chlorinating of swimming pools it is desirable that electrodes should perform satisfactorily for a period of 3 to 5 years, but most electrodes used for this purpose in the past have lost efficiency or broken down completely in less than a year of operation.

Materials which are advantageous in electrode construction bv virtue of their of chemical resistance and electric conductivity are the metals of the platinum group including in particular platinum, rhodium, iridium, ruthenium and alloys thereof.

These metals are, however, so expensive as to preclude their use as electrodes for most electrolytic processes unless they are applied as thin layers or foils on the surface of less expensive supporting materials.

Various methods have been proposed in the past for coating a substrate, such as tantalum, niobium, titanium, and alloys thereof, with metals of the platinum group.

For example in United States Patent No. 2 719 797 there is described chemical decomposition or electrolysis to form thin deposits of platinum group metals, in conjunction with heating to effect a bond with the substrate These methods, however, tend to produce uneven or incomplete coatings of the platinum group metal, and there is a substantial tendency for the heat treatment to effect the platinum group metal 50 and its electric conductivity, thereby reducing its effectiveness as an anode surface material.

It is pointed out in said United States Patent No 2719797 that "attempts to cover 55 the tantalum strip with a platinum metal foil to hold the metals together, as by sweating, rolling or hammering, have proved to be unsatisfactory because the platinum metal foil is held to the tantalum only by 60 mechanical contacts which is not sufficient to permit its use as an anode".

In our Patent Specification No 1,253,217 we have described a method of bonding a platinum group metal to a substrate such 65 as tantalum, titanium and niobium (also known as columbium) under the influence of pressure and local electrically generated heat which produces electrodes that are far superior to previously available electrodes 70 In particular there is described and claimed a method of making an electrode that comprises bonding a foil of a metal or an alloy of metal or an alloy of metals selected from the platinum group to a 75 compatible metal substrate as defined below which is highly resistant to electrolytic oxidation by applying a pressure of from to 300 pounds per inch length along a linear zone of contact between said foil 80 and a small diameter cylindrical member of hard conductive metal which is rotatable in a massive electric conductor, said pressure being between said cylindrical member and a second massive electric conductor 85 in engagement with said substrate, and further applying an electric current below 12 volts at an amperage to provide at least 3 kva per inch length of said linear zone of contact, while advancing said small 90 1 274 242 diameter cylindrical member in a directioi perpendicular to said linear zone of contac at a rate to provide a bonding heat sufficien to soften, without melting, the substrata surface.

By a compatible metal substrate as use( above we mean a substrate of a metal oi alloy which can be bonded at the interface of the metal foil and substrate when the substrate has been subjected to a bondinj heat sufficient to soften without melting itl surface Examples of such substrates an described in our Specification 1,253,217.

The bonding of the platinum group meta 1 in our Specification 1,253,217 is preferably affected at a pressure of from 50 to 15 C pounds per linear inch, employing a voltage of from 0 1 to 5 volts at an amperage to provide from 7 to 100 kva per inch length of said zone of contact.

The preparation of electrodes by the method described in our Specification No. 1,253,217 requires extreme precision in the pressure and rate of feed applied to the small diameter cylindrical member which forms the linear zone of contact with the workpieces Insufficient pressure or too rapid advance of the cylindrical member can result in incomplete or discontinuous bonding of the platinum group metal foil to the substrate, and too slow or uneven advance of the cylindrical member can cause rupture or burn-through of the foil The latter type of damage can usually be detected by visual inspection and remedied by spot patching with additional foil applied by the same method The incomplete or discontinuous bonding of the foil to the substrate is a more serious problem since it is difficult to detect by inspection.

It has been observed with many electrodes that such incomplete or discontinuous bonding does not interfere with performance of an electrode, so long as the overlying layer of platinum group metal remains sound and free of pores or microscopic breaks which might permit electrolyte to reach the substrate When such break does occur, however, the entire area of incomplete bonding can rapidly be stripped of the platinum group metal foil If the area is small and the electrode is operating at a low voltage such as from 6 to 8 volts the damage may not seriously impair the efficiency of the electrode, and electrodes with slight damage of this sort have been continued in use successfully for many months If more than about 5 To of the electrode surface is thus damaged its efficiency may be sufficiently reduced to warrant replacement If the voltage at which the electrode is operated is appreciably above 8 volts, however, any such rupture of an unbonded portion of the platinum group metal can lead to erosion of the surn rounding sounding bonded areas with prot gressive destruction of the entire electrode.

The problems due to incomplete or discontinuous bonding as above described have come into focus in extensive experiments which we have been conducting in which the electrodes bonded by local electrically generated heat have been operated at unusually high voltages for extended periods of time; and the surprising and unexpected results of such high voltage operation have indicated that there is a real need for eliminating the problem of failure due to incomplete or discontinuous bonding.

We have now found that the problems above described with electrodes having a platinum group metal foil bonded directly to a heavy metal substrate by local electrically generated heat can be overcome by employing in addition to the platinum group metal foil an intermediate metal foil which has a melting point appreciably higher than both the platinum group metal and the substrate The method of bonding is generally similar to the method disclosed in our Patent Specification No 1,253,217 differing somewhat therefrom in the optimum operating conditions as hereinafter described.

A preferred general purpose electrode has a titanium substrate, an intermediate layer of columbium or tantalum and an outer layer of a platinum group metal For unusually high voltage operation the substrate can be columbium, the intermediate layer tantalum and the outer layer a platinum group metal.

The key to the superior bonding attained with the three layer electrode according to the invention appears to be the use of an intermediate foil which has a substantially higher melting point than both the platinum group metal and the substrate.

This provides a greater concentration of heat at a location to permit more effective surface softening of the substrate and assurance of intimate contacting of the superimposed metal surface throughout the length of the small cylindrical conductor as it is pressed against and rolled along the assemblage This explanation of what is apparently taking place is based both on the intense orange glow which develops in the intermediate foil in alignment with the small cylindrical roller, and on the slight surface deformation of the bonded substrate and foils In fact the path of the cylindrical roller on the assemblage tends to assume a slightly rippled contour, indicating that the localized heating is so instantaneous and sensitive that the softening of the substrate surface varies slightly in each cycle of the current supply.

According to one aspect of the invention we provide a free component electrode comprising a substrate of titanium or A columbium, a surface layer of a platinum group metal and an intermediate layer of tantalum or columbium to which the substrate and the surface layer are bonded the metal of the said intermediate layer having a melting point higher than that of the substrate and the platinum group metal of the surface layer.

According to another aspect of the invention we provide a three component electrode for electrolytic use having enhanced resistance to damage when used at high voltages and comprising a substrate of titanium or columbium having an intermediate layer of tantalum or columbium bonded thereto by means of local electrically generated heat the said intermediate layer having a thickness of from 0003 to 01 inches and a higher melting point than the metal of said substrate, and an outer layer of platinum, rhodium, iridium, ruthenium, or an alloy thereof bonded to said intermediate layer by means of local electrically generated heat the said outer layer having a thickness of from 0003 to 005 inches and a melting point lower than the metal of said intermediate layer, the bonding being effected under sufficient electrically generated heat and pressure to cause visible surface deformation of said substrate and intimate adherence of said intermediate layer to the thus deformed surface of the substrate and intimate adherence of said outer layer to said intermediate layer.

The selection of metals to use in the substrate and foils should be made with reference to both the relative melting points and the type of use intended for the electrode The following tabulation of melting points will serve as a guide:

Metal Approx MP.

Outer Foil Platinum 17730 C.

Rhodium 19660 C.

Iridium 24500 C.

Ruthenium 24500 C.

Intermediate Foil Columbium 24150 C.

Tantalum 28500 C.

Substrate Titanium 17250 C.

Columbium 2415 C.

Bearing in mind that the intermediate foil should have a higher melting point than the outer foil and substrate it follows that if the substrate is titanium, the middle foil can be either columbium or tantalum; but if the substrate is columbium the middle foil will be tantalum Also, if the middle foil is columbium, iridium and ruthenium should not be employed as the outer foil except as lower melting point alloy forms.

In terms of intended use of the electrode an important factor is the voltage to be employed Titanium can withstand only 7 to 10 volts before showing signs of breakdown Columbium on the other hand, can withstand up to about 45 volts and tantalum about 130 volts Thus if an electrode is intended for operation in the 10 to 45 volt range a middle foil of columbium over a titanium substrate provides reasonable protection for the substrate in the event of damage to the platinum metal exposing portions of the middle foil For operation at voltages above about 45 volts such protection would best be provided by switching to a tantalum middle foil, and suitably also switching to columbium as the substrate.

The equipment employed in assembling the new electrodes is the same as that described in our Specification No 1,253,217.

The substrate can rest on a large massive conductor suitably in the form of a heavy plate of copper or highly conductive harder copper alloys A movable massive conductor grooved to receive a small diameter cylindrical roller of a hard conductive metal, such as tungsten, tungsten carbide, alloys of tungsten carbide, and stainless steel, is arranged above the first massive conductor in a manner to apply downward force against superimposed substrate and foils as the cylindrical roller is rotated to advance it over the workpiece assembly in a direction perpendicular to its axis. The cylindrical roller can be of a length to traverse the full width of the electrode substrate or it can have a portion of enlarged diameter (fitted within a recess in the upper massive conductor) which provides a line of contact substantially shorter than the width of the electrode, requiring a number of passes to fully bond the superimposed foils to the substrate.

In a large scale adaptation of the method the flat bed massive conductor can be replaced, as disclosed in our Specification No. 1,253,217, with a large diameter roller, driven in synchronism with the small diameter roller, and having a diameter of the order of 10 to 20 times the diameter of the small diameter roller.

The operating conditions for assembling the three part electrode are somewhat more severe than those described in our Speciiication No 1,253,217, for laminating platinum group metal foil directly to the substrate The pressure applied should be from 600 to 3000 pounds and preferably from 840 to 1440 pounds per linear inch of contact between the small diameter cylinder (or enlarged portion thereof) and the superimposed foils and substrate; and the roller is rotated to advance the line of contact at from 12 to 36 inches per minute.

The applied voltage should be less than 10 volts, and suitably in the 0 5 to 5 volt range, with the applied current providing at least and suitably from 40 to 100 kva per linear inch of contact of the small diameter roller (or enlarged portion thereof)-when 1 274 242 using relatively thin substrate and foils As the thicknesses of substrate and foils, anc particularly the intermediate foil, are increased, the kva can be increased to as much as about 500 kva per linear inch.

It is important that the applied pressure and the speed of rotation of the small diameter roller advancing the same over the workpiece assembly be maintained essentially constant, and that the electric current be turned on and off while the pressure is applied and the roller is in motion There is no harm in going over a previously bonded area provided these limitations are adhered to; in fact when using a roller with an enlarged portion which contacts only part of the width of the electrode substrate it is important to overlap the previously bonded portion slightly when making the next pass in order to assure overall bonding of the superimposed foils Any stopping of the forward movement of the roller while the current is on must be avoided, as this may cause a burn-through of one or both of the superimposed foils.

The substrate metal can be of any desired thickness to provide the desired rigidity in the electrode For electrodes from 2 to 3 inches wide and from 6 to 12 inches long a thickness of from 03 to 25 inches is generally suitable The middle foil may be from 0003 to 01 inches thick and preferably from 001 to 0015 inches thick; and the outer platinum metal foil may be from 0003 to 005 inches and preferably from 0003 to 0006 inches thick.

The following examples will serve to more fully demonstrate how typical electrodes in accordance with the present invention are assembled, but it is to be understood that these examples are given by way of illustration and not of limitation:

EXAMPLE I

Electrodes are prepared by bonding to flat sheets of titanium measuring 2 inches by 6 inches by 06 inches thick an intermediate foil 0 0015 " thick of tantalum and an outer foil 0 0005 " thick of platinum In the bonding operation the titanium plate is placed on a large copper alloy bed providing one terminal of an electrical circuit.

A hand held copper electrode forming the outer side of said circuit has a transverse groove in the lower end thereof which receives a rotatable tungsten carbide cylinder about O 5 inches in diameter having a central enlargement about 0 75 inches in diameter, and having an axial length about 0.25 inches, with a slightly rounded surface contour The end of the cylinder is provided with an offset crank to facilitate controlled rotation along the foils as the same slidably rotates in the hand held electrode.

While applying a downward pressure of about 80 pounds to the superimposed foils and titanium plate (providing about 800 pounds per linear inch at the line of contact between the roller enlargement and the platinum foil) the crank is turned at a rate to advance the line of contact at the rate of about 12 inches per minute With the pressure thus applied and motion initiated a foot switch is accuated to apply current between the conductors from a 25 volt power source capable of delivering 5000 amperes This amount of power provides about 125 kva per linear inch along the line of contact of the roller enlargement with the platinum foil When approaching the end of the titanium plate the foot switch is released to cut off the power supply and only then is the application of pressure and rotation of the roller terminated.

As observed from the side the heat generated by the applied current provides a bright orange glow, apparently concentrated primarily in the tantalum foil in a small area directly aligned with the line of contact established by the roller enlargement. The steps above described are repeated along a second path in which the line of contact with the roller enlargement slightly overlaps the first path, and the sequence of steps is repeated a number of times until the superimposed foils have been bonded to substantially the entire area of the titanium plate.

Overhanging edges of the foils are cut off slightly beyond the edges of the titanium plates, folded around the titanium plate, and bonded to the reverse side thereof by inverting the assemblage on the conductor base and repeating the bonding procedure along the folded over portions of the foils. Terminal posts are then welded to the reverse side of the titanium plate, and the reverse side and edges of the assemblage are encased in a resistant resin, suitably a polyacrylic resin such as methyl methacrylate polymer to insulate and protect portions of the assemblage not covered by the superimposed foils.

In the paths made in the bonding operation there are slightly visible ripples quite uniformally spaced along each path which are caused by fluctuations in the alternating current supply There are also slight ridges at the overlap between successive bonded paths When an electrode is torn apart to separate the foils from the substrate these ridges and ripples appear in the substrate in exact conformance with the surface appearance indicating a progressive softening and displacement of the surface metal which provides the desirable overall bonding of the superimposed foils to the substrate.

Electrodes prepared as above described are extremely durable in chlorinating operations at from 10 to 40 volts, and current densities ranging from a trace to 5 amps/ sq in of electrode surface, and such electrodes have an estimated useful life, based on 10 to 12 hours per day of operation, in excess of five years.

At these voltages the electrodes have operated successfully for long extended periods at current densities as high as 30 amps/sq in of electrode surface Furthermore the electrodes have shown remarkable stability at potentials as high as 220 volts and current density of the order of 1 amp/ sq in of electrode surface.

In the foregoing example it is to be understood that tantalum and platinum metal foils can be bonded to the reverse side of the electrode, if desired, by repeating the procedural steps described with the previously bonded surface bearing against the copper alloy bed For many uses and adaptations of the electrodes, however, such coating of the reverse side of the electrode is unnecessary and would be uneconomical in view of the cost of the foil materials.

The procedure as described in the foreging example can readily be adapted to the bonding of substrate and foils of different thickness or different composition In general the applied pressure and the kva of current per linear inch should be increased as the thicknesses of the substrate and foils are increased, and decreased as these thicknesses are decreased Alternatively, the amount of heat generated along the line of contact of the pressure roller wih the assemblage can be increased or decreased by respectively slowing or increasing the rate of advance of the line of contact, while holding the applied current constant.

If the tantalum intermediate foil in the foregoing example is replaced by the same thickness foil of the lower melting columbium the same operating conditions will nevertheless apply. On the other hand, if the titanium substrate is replaced by the higher melting columbium somewhat higher current or slower advance of the line of contact so of the pressure roller is required to provide the same degree of softening of the substrate surface.