An Approach to Control of the DNA
Accident which Causes Cancer
by Howard E. Thompson, Jr
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 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.
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
(2) They can use the body's own chemicals to fight disease.
(3) They can deliver therapeutic agents directly to target
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
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
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
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
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
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
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
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
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
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
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.
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
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
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 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
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
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
In order that the reader may better visualize these factors
typical test procedures and determinations will be described.
DETERMINATION OF THE EXISTENCE OF
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
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
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:
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
METHOD OF ANALYSIS FOR CHLORINE
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
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
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
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
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
Typical uses for one or more of these procedures include, with
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
4. Treatment of sewage.
5. Pollution control in rivers and harbors; and algae control in
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
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
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.
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.
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
Dissolved O2 0.85 1.65
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.
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.
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
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
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.
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
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
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
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
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
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.
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
This invention is concerned with improvements in or relating to
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
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
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
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
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
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
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:
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
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
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
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.