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Dr Ross GWYNN

Electrolyzed Physiological Saline vs Cancer

Excerpts from :

An Approach to Control of the DNA Accident which Causes Cancer

by

Howard E. Thompson, Jr

1983

8. A more positive indication that the DNA accident associated with cancer

may be reversible is the clear evidence from some of the case histories

reported in Ross Gwynn's book "Bioelectrolysis in Man", that when enough of


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his electrolyzed physiological saline can be introduced to a cancer site the

replication of cancerous tissue ca revert to the replication of normal tissue in

a period of about 72 hours.

9. Because the active components of the Electrolysed Physiological Saline

referred to in (8) are simple oxidants, it can be assumed that an oxidant

function at the molecular-cellular level is responsible for the favorable

change, and that a contributing factor to the onset and persistence opf the

cancer accidnet must be hypoxia at the molecular-cellular level.

Excerpts from :

A Biodynamic Approach to Cancer

by

Howard E Thompson, Jr

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."


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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 medicalresearch 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 theground 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


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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,


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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 chromosomalDNA 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.


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[ ... ]

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 anyplanned 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


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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 takingplace 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


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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.


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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, biofeedbacktechniques 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.

USP 3616355

METHOD OF GENERATING ENHANCED BIOCIDAL ACTIVITY IN THE

ELECTROYLSIS OF CHLORINE CONTAINING SOLUTIONS AND THE RESULTING

SOLUTIONS

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


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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 thecell. 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 sodiumchloride 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


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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 12hours 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 100volts 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


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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 to100 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


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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 10ml. 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


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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


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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 forcomparative 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


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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 andozone 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 maybe 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


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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 metalcations 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-ozoneassociation, 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


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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 approachmay 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.


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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 anddisinfecting 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,


20/40

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 thespace 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 chlorineequivalent 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.


21/40

EXAMPLE I

In a domestic water system, suitably containing a holding tank where treatedwater 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


22/40

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 thevalues 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


23/40

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


24/40

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 aflow 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.


25/40

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 anycorrosion 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##


26/40

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 transfertissue 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.


27/40

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-flowoperation.

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 forcleaning 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


28/40

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) thepH 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 higherozone 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.


29/40

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 theelectrolyte 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 astemperature, 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


30/40

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 inthe 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 understoodthat they constitute part of the present invention.

GB 1274242

ELECTRODE FOR ELECTROLYTIC USE

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


31/40

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


32/40

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 inengagement 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 andsubstrate 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 samemethod 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,


33/40

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 theelectrode, 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 abovedescribed 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 metalsubstrate 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 platinumgroup 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


34/40

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 eachcycle 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 offrom 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.


35/40

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.


36/40

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 foroperation 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


37/40

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, asthis 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:


38/40


39/40

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 resistantresin, 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 thesubstrate 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 platinummetal 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.


40/40

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 areincreased, 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 titaniumsubstrate 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.

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