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rexresearch.com
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,
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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.
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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
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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
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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
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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.
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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##
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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.
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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
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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.
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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
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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
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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
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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,
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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
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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.
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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.
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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
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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:
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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.
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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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