United States Patent (19) 11 Patent Number: 4970,015

Garcia 45) Date of Patent: Nov. 13, 1990

(54) RADIATORCLEANINGCOMPOSITION AND 4,199,469 4/1980 Walzer ................................ 252/46
METHOD OF MANUEFACTURE THEREOF 4,250,048 2/1981 Leveskis ... ... 252/142
4,477,364 10/1984 Garcia ................................. 252/42
75 Inventor: Silverio M. Garcia, Louisville, Colo. 4,569,779 2/1986 Jabalee ........................... 252/79.4 X
73 Assignee: Chem Shield, Inc., Denver, Colo. Primary Examiner-William A. Powell
21 Appl. No.: 456,983 Attorney, Agent, or Firm-Donald W. Margolis; John L.
Isaac
22 Filed: Dec. 22, 1989 57 ABSTRACT
51 int. Cl......................... C09K13/06; C11D 7/08; An acidic solution for use as a radiator cleaning compo
C23G 1/02; B44C 1/22 sition includes an aqueous solution of from about 1-8
52 U.S. C. ................................ 252/079.4; 252/79.2; weight percent an ethylene glycol base, and about 2-45
252/142; 156/655; 134/22.1; 134/3; 134/40 weight percent hydrochloric acid. In addition, approxi
58 Field of Search ..................... 252/79.2, 79.4, 142, mately 2-45 weight percent of an aqueous hydrochloric
252/146; 156/664, 655, 656; 134/2,3,22.1, acid-based composition is included, which composition
22.11, 22.14, 34, 40, 41 has a pH of less than about 1.0 yet is substantially non
56 References Cited reactive with compounds having low oxidative states,
U.S. PATENT DOCUMENTS
including human skin tissue.
4,181,622 1/1980 Gavin ................................. 134/3 X 42 Claims, No Drawings
 4,970,015
1. 2
closely with caustic residue left inside the radiator
RADATOR CLEANING COMPOSITION AND tubes.
METHOD OF MANUFACTURE THEREOF As a result of the above, radiator shops have had to
deal with expensive fuel consumption, exposure to dan
BACKGROUND OF THE INVENTION 5 gerous, hot caustic solutions, and long working proce
1. Field of the Invention dures when trying to clean radiators. Nonetheless, this
The present invention relates to cleaning composi has still not accomplished the desired degree of cleanli
tions and, more particularly, to strong acid-based clean ness, and bead blasting and wire brushing end up, in
ing compositions. Specifically, the present invention many cases, as the only alternative to a truly clean radi
relates to a radiator cleaning composition having a pH 10 ator. Consequently, there is still a need for an effective
value of less than 1.0, yet is nonreactive and nonirritat cleaning solution particularly applicable to radiators,
ing to human skin tissue. such cleaners having requirements different from those
2. Description of the Prior Art of cleaning agents for other types of surfaces and appli
Numerous compositions and processes have been cations. Such a cleaning composition need not be abra
employed in the past for the purpose of cleaning and 15 sive, and should be effective in removing corrosion
removing corrosion products, rust, mineral deposits and products, rust, mineral deposits, scaling, grease and the
scaling, grease, and oil residue from radiators that are like, while also being non-corrosive as well as non-reac
used in cooling systems of automobiles, motorcycles, tive with human skin tissue to permit easy and safe use.
trucks, buses and other vehicles as well as in heavy 20 SUMMARY OF THE INVENTION
equipment such as compressors, pumps, turbines and Accordingly, it is one object of the present invention
the like. Some of these cleaning processes include, but to provide an effective radiator cleaning solution.
are not limited to, sand and bead blasting, wire brush It is another object of the invention to provide an
ing, power washing and muriatic acid cleaning. Other acid-based cleaning solution for radiators used in a vari
techniques include dipping the radiators in baths con 25 ety of cooling systems, the solution having an extremely
taining extremely caustic solutions with pH values low pH capable of highly effective cleaning in the re
greater than 12.5 and, in the great majority of cases, moval of corrosion products, rust, mineral deposits,
heated to as much as 190 F. Moreover, there are other scaling, grease and residue.
processes that use ultrasonic cleaning devices in baths of It is a further object of the present invention to pro
caustic solutions heated from about 145 F. to 175 F. 30 vide an acid-based cleaning solution as described above
Examples of acidic compositions which have been which is also non-reactive to healthy human skin tissue
utilized for a wide variety of cleaning applications in and other compounds having low oxidative states to
clude U.S. Pat. Nos. 4,675,120, 3,514,407, 3,630,933, permit ease of handling.
4,116,713, 4, 81,622, 4,199,469, and 4,250,048. While To achieve the above and other objects and advan
many of these referenced patents are not specifically 35 tages of the present invention, an acidic solution for use
designed for cleaning radiators and the like, they do as a radiator cleaning composition is disclosed. The
disclose acid-based compositions for the purposes of solution includes an aqueous solution of from about 1-8
cleaning a wide variety of different types of surfaces. weight percent of an ethylene glycol base and about
One unfortunate and significant disadvantage of many 2-45 weight percent hydrochloric acid. To this solution
of these acid-based cleaning compositions is that while 40 is added an additional 2-45 weight percent of an aque
they are effective cleaning agents, they can be ex ous hydrochloric acid-based composition having a pH
tremely corrosive and highly reactive with human skin less than about 1.0, yet substantially non-reactive with
tissue as well as other compositions having relatively compounds having low oxidative states including
low oxidative states. U.S. Pat. No. 4,477,364 discloses human skin tissue.
an acidic glass cleaning composition which has a low 45
DETAILED DESCRIPTION OF THE
pH value for cleaning yet is relatively innocuous to skin
tissue. However, this particular disclosure is directed to PREFERRED EMBODIMENTS
the specific challenges relating to the cleaning of glass By way of background, acids are hydrogen-contain
surfaces and is so limited thereto. ing substances which dissociate in water to produce one
As mentioned above, prior art bath cleaning tech 50 or more hydrogen ions. The concentration of hydrogen
niques include heating the bath to extremely dangerous ions in a solution is known, of course, as the pH. In
temperatures. This procedure consumes great amounts aqueous solutions, hydrogen ions (H) bond to one or
of energy and becomes a hazard to use because it can more water molecules, and the ion formed when one
cause both temperature burns and chemical burns. hydrogen ion bonds to one water molecule is called the
Workers involved in this type of work must wear pro 55 hydronium ion (H3O). In dilute aqueous solutions, all
tective clothing, eye protection, rubber gloves and strong acids donate a proton to water and are essentially
boots at all times. These processes are also time consum 100% ionized to produce a solution containing hydro
ing, do not do an effective cleaning job on heavy corro nium ions plus the anions of the strong acid.
sion and scaling, and eventually destroy the buildings According to the principles established in the Bron
where they are housed due to the hot and caustic fumes stead-Lowry Theory, the acid dissociation reaction of
generated by the process. each acid is different. This creates both strong acids and
Once these radiators have been cleaned through any weak acids which in turn have conjugate bases that are
one of these prior art processes, a stage called "rod correspondingly weak and strong, respectively. Also,
ding' has to be performed. This process consists of a by combining a weak acid with its conjugate acid salt,
technician lancing each radiator tube with a metal rod 65 an acid solution is created which shows a moderate pH
to remove any remaining corrosion build-up or sedi value at equilibrium.
ments from inside the radiator tubes. This procedure is When strong acids are mixed together, a great num
a very time consuming job and involves working very ber of hydrogen ions are released and become available
 4,970,015
3 4.
for further chemical reaction. If these strong acids are grease and oil residue from radiators that are used in
then further mixed with weak acids in the presence of cooling systems of automobiles, motorcycles, trucks,
water, the conjugate bases of the weaker acids that are buses and other vehicles as well as in heavy equipment
formed in the reaction then serve as strong bases and such as compressors, turbines, pumps and the like. The
function as regulators of the hydrogen ions produced by preferred solution comprises from about 2-75 weight
the strong acid combination. percent of an aqueous (preferably distilled water) solu
When hydrochloric acid (HCl), a strong acid, is tion containing 1-8 weight percent of an ethylene gly
mixed with water, HCl virtually completely ionizes in col base, from about 2-45 weight percent of hydrochlo
dilute aqueous solution. The reaction between hydro ric acid, and from about 2-45 weight percent of an
chloric acid and water produces a high hydronium ion O aqueous hydrochloric acid-based composition having a
concentration, and the total hydronium ion concentra pH value of less than about 1.0, which is substantially
tion in this reaction comes from two sources: first, from non-reactive with compounds having low oxidative
the hydrochloric acid dissociation, and second, from states including human skin tissue.
the self-ionization of the water. The concentration of The aqueous acid-based composition of the end prod
hydronium ions due to self-ionization of water is almost 15 uct, which is formed from selected inorganic and or
negligible but is quite substantial due to the hydrochlo ganic acids, possesses unique properties. Specifically,
ric acid dissociation. This is also the case with virtually the aqueous acid-based composition has strong acid
all strong acids, and it is therefore customary to neglect properties, i.e. a pH value of less of about 0.91, and yet
the self-ionization concentration from all calculations. is substantially inert to healthy human skin so that
When this ionization of strong acid occurs, it is virtually 20 contact of the aqueous acid-based composition with a
impossible to distinguish among the strengths of the user's skin does not result in burns or even irritation to
strong acids such as sulfuric acid, hydrochloric acid, the skin of the user.
HI, etc., when dealing with them in aqueous solutions. The end solution of the preferred embodiment is a
All of these aqueous solutions contain the same strong product of mixing a very strong acid with a plurality of
acid, namely the hydronium ion. 25 weaker acids in the presence of water in such a manner
Water, under these circumstances, functions as a lev that the conjugate bases of the weaker acids function as
eling agent on the strengths of all very strong acids, and strong bases to control the production of hydronium
their acidities are reduced to the level of the hydronium ions in the strong acid. The main source of hydronium
ion present in solution. The water increases the ioniza ions in the solution is the hydrochloric acid as it dissoci
tion disbursements and is the carrier for the entire elec 30 ates in water. This dissociation is virtually uncontrolled
trolysis system. One of the advantages of this approach and requires the other weaker acids to create the conju
is its emphasis on the competitive nature of acid-base gate strong bases to bring this production of hydronium
equilibrium in protonic solvents. Since the solvated ions under control. The composition of the end product
hydrogen ionis the strongest acid that can exist in these can vary widely and will be dependent on a delicate
solvents, the conjugate base of each acid competes for 35 balance of the hydrochloric acid and the aqueous acid
it. The strongest base reacts with the hydrogen ion to based composition. In cases where distilled water can't
form the weaker undissociated acid. be found, regular tap water can be substituted as long as
It has been found that by changing the combinations its hardness is either controlled or an increase in the
of acids and their concentrations, the behavior of the volume of hydrochloric acid would become necessary.
strong acid can be controlled, and the amount of avail 40 Also, with hard water, a balance in the amount of the
able hydrogen ions can be increased or decreased to ethylene glycol base must be achieved.
accelerate or slow down the reaction. When this is The second essential ingredient of the solution of the
done, acid solutions with extremely low pH values and present invention is the aqueous acid-based composition
high amounts of free hydrogen ions can be formulated. having a pH value of less than about 1.0. The unique
These solutions are found to be non-corrosive to metal, 45 aqueous acid-based composition is prepared by a pro
innocuous to skin and capable of providing enormous cess wherein the ingredients are believed to be critical.
amounts of hydrogen ions that, when combined with Moreover, the specific order of addition of the ingredi
other acids, provide an excellent environment for effec ents used in the formulation of the aqueous acid-based
tive performance in cleaning, disinfecting and prepara composition is also critical, and especially desirable .
tion of all kinds of surfaces. m 50 results have been obtained when the aqueous acid-based
For example, when we add hydrochloric acid to composition is prepared in accordance with the proce
these solutions, the resulting formula exhibits the pH of dure described below.
the totally ionized HC1. The hydrogen ion becomes More particularly, the hydrochloric acid-based com
bound, and the solution subsequently releases it in pro position includes an aqueous hydrochloric acid solution
portion to the oxidation state of the substance with 55 admixed with an effective amount of at least one weak
which it comes in contact. acid to produce strong conjugate bases to control the
As explained above, the weaker acids in the aqueous dissociation production of hydronium ions by the hy
acidic solution function as strong bases that hold the drochloric acid in solution. A more preferred embodi
hydrogen ion in shifting electron sharing. The presence ment includes a solution of hydrochloric acid and phos
of compounds of a higher oxidative state de-stabilize the 60 phoric acid admixed with an effective amount of at least
hold and free the hydrogen ions. If, in turn, the solution one weak organic acid to produce strong conjugate
comes in contact with compounds that have extremely bases.
low oxidative states, such as unbroken human skin or The preferred embodiment is an acidic solution
even sclera of guinea pigs or rabbits, there is little or no wherein the 2-45 weight percent aqueous hydrochloric
reactivity at all. 65 acid-based composition includes an aqueous mixture of
The present invention provides an improved acidic about 5-20 weight percent hydrochloric acid with
solution for use as a radiator cleaner for removal of about 5-20 weight percent phosphoric acid admixed
corrosion products, rust, mineral deposits and scaling, with approximately 1-5 weight percent of any suitable
 4,970,015
5 6
hydroxy carboxylic acid and approximately 1-5 weight aqueous acidic mixture are the amounts required to
percent of a suitable dicarboxylic acid. In preferred provide from about 1 to about 5 weight percent of the
form, the hydroxy carboxylic acid may be selected from hydroxy carboxylic acid and from about 1 to about 5
any one of the group including citric acid, tartaric acid weight percent of the dicarboxylic acid in the aqueous
and malic acid, although the preferred embodiment 5 acid-based composition.
includes citric acid. Moreover, the dicarboxylic acid of Any suitable hydroxy carboxylic acid may be em
the solution may be selected from any one of the group ployed in the preparation of the aqueous acid-based
consisting of oxalic acid, malonic acid, succinic acid, composition of the solution of the present invention.
glutaric acid, and adipic acid, although the preferred Typical of such hydroxy carboxylic acids are citric
dicarboxylic acid is oxalic acid. The hydrochloric acid 10 acid, tartaric acid, malic acid, and the like. However,
based composition may further include 1-3 weight per especially desirable results have been obtained wherein
cent of a poly methyl amine which is preferably se the hydroxy carboxylic acid added to the aqueous
lected from hexamethylenetetramine, hexamethylenedi acidic mixture is citric acid.
amine and hexamethyleneamine, although hexamethy Any suitable dicarboxylic acid may be employed in
lenetetramine is the preferred embodiment. 15 the preparation of the aqueous acid-based composition
The most preferred composition as a radiator clean of the solutions of the present invention for controlling
ing material includes approximately 48% by weight. hydronium ion production. Typical of such dicarbox
distilled water, 2% by weight of butyl ethylene glycol ylic acids are oxalic acid, malonic acid, succinic acid,
base, and 25% by weight of the hydrochloric acid-based glutaric acid, adipic acid, and the like. Desirable results
composition as described above that has a pH of less 20 have been obtained when the dicarboxylic acid added
than about 1.0. to the aqueous acidic mixture is oxalic acid.
The initial step in the preparation of the preferred The aqueous acid-based composition so produced
aqueous acid-based composition of the solution of the will preferably contain from about 40 to about 90
present invention comprises admixing from about 5 to weight percent water, and more preferably from about
about 20 weight percent hydrochloric acid with about 5 25 47 to 87 percent water. Thus, depending upon the
to about 20 weight percent phosphoric acid in a vessel amount of hydroxy carboxylic acid and dicarboxylic
for an effective period of time to provide a substantially acid added to the aqueous acidic mixture, as well as the
homogeneous acidic mixture. Because strong funes are amount of water initially added to the acidic mixture
emitted upon mixing the hydrochloric acid and the formed by the hydrochloric acid and the phosphoric
phosphoric acid, care should be exercised in the mixing 30 acid, it may be desirable to further dilute the aqueous
of the two components to insure that the mixing step is acid-based composition with an effective amount of
carried out in a well ventilated area or hood. The time water to insure that the concentration of water in the
required to mix the hydrochloric acid and phosphoric aqueous acid-based composition is from about 40 to
acid so as to provide a substantially homogeneous acidic about 90 weight percent, and preferably from about 47
mixture can vary widely and will generally depend 35 to about 87 weight percent. In those instances where it
upon the rate of addition of the two components, is determined that the amount of water present in the
amounts of the two components, the rate or speed of aqueous acid-based composition is less than the speci
agitation and the like. However, approximately 10-20 fied amount, the aqueous acid-based composition is
minutes mixing time will generally produce a homoge admixed with an effective amount of water so as to
neous mixture. 40 provide the aqueous acid-based composition of the solu
The homogeneous acidic mixture formed from the tion with the desired amount of water.
hydrochloric acid and phosphoric acid is then admixed When the weak acids added to further control the
with an effective amount of water, preferably distilled dissociation reaction are oxalic and citric acids, in the
water, to provide an aqueous acidic mixture. The presence of water, the oxalic acid also provides a sec
amount of water employed in the formulation of the 45 ondary source of hydronium ions and is of extreme
aqueous acidic mixture can vary widely, but is generally importance in regulating the pH of the end product.
an amount sufficient to provide from about 47 to about The more oxalic acid added to the formulation, the
87 weight percent water in the aqueous acidic mixture. lower the pH and the more active the solution becomes
The aqueous acidic mixture is thoroughly stirred to with respect to the removal of oxides and carbonates
insure substantially complete dispersion of the homoge 50 from bathroom radiator installation surfaces. The citric
neous acidic mixture of the hydrochloric acid and the acid provides the final controller of excess hydronium
phosphoric acid into the water and to provide a substan ions that might have been created by the addition of
tially uniform aqueous acidic mixture. oxalic acid. If more oxalic acid is added to the solution,
This aqueous acidic mixture is then agitated, and more citric acid must be added. Otherwise, the solution
from about 1 to about 5 weight percent of a hydroxy 55 may lose its ability to remain innocuous and inert to skin
carboxylic acid and from 1 to about 5 weight percent of and other organic materials of low oxidative states.
a dicarboxylic acid are then preferably admixed there The aqueous acid-based composition used in the solu
with. These weak acids are added to further control the tion of the present invention is a substantially colorless
dissociation reaction and production of hydronium ions. liquid having an appearance substantially similar to
As indicated above, the hydroxy carboxylic acid and 60 water. Further, the aqueous acid-based composition
the dicarboxylic acid are both critical ingredients in the prepared as set forth hereinbefore, has a pH value of less
formulation of this preferred aqueous acid-based com than 1.0, i.e. about 0.91 and as low as 0.2, and is substan
position. The amount of hydroxy carboxylic acid and tially inert to healthy human skin and other organic
dicarboxylic acid incorporated into the aqueous acidic materials having low oxidative states.
mixture of the hydrochloric acid and phosphoric acid 65 Once the above mixture is accomplished, an effective
can vary widely within the ranges set forth herein minor amount of a poly methyl amine may be selec
above. However, the optimum amounts of hydroxy tively admixed with the aqueous acid-based composi
carboxylic acid and dicarboxylic acid admixed with the tion to provide an amine-containing aqueous acid-based
 4,970,015
7 8
composition. When this is done, the concentration of mixture while keeping the solution under constant mix
acids in the solution can be increased without generat ing to provide a homogeneous solution.
ing excess gases. In order to more fully describe the present invention,
The effective minor amount of the poly methylamine the following examples are set forth. However, it is to
incorporated into the aqueous acid-based composition be understood that these examples are for illustrative
used in the formulation of the amine-containing solution purposes only and are not to be construed as limiting the
can vary widely, but will generally range from about 1 scope of the present invention as defined in the ap
to about 3 weight percent. Further, any suitable poly pended claims.
methyl amine compatible with the aqueous acid-based
composition may be employed. Typical of such poly 10 EXAMPLE I
methyl amines are hexamethylenetetramine, hexameth Preparation of Aqueous Acid-based Composition
ylenediamine, hexamethyleneamine and the like. How
ever, desirable results have been obtained where the 72 pounds of hydrochloric acid and 42 pounds of
poly methyl amine is hexamethylenetetramine, and the phosphoric acid were added to an acid-resistant con
hexamethylenetetramine is incorporated into the aque 15 tainer, and the acids were stirred to produce a substan
ous acid-based composition in an amount to provide tially homogeneous acidic mixture. During the mixing
from about 1 to about 3 weight percent of the poly of the hydrochloric acid and the phosphoric acid, fumes
methyl amine in the amine-containing solution em were generated. Thus, the mixing was carried out in a
ployed. well ventilated area.
Through experimentation, it has been found that the 330 pounds of water were then placed into a second
final end product, when in combination with other acids container, and 114 pounds of the hydrochloric-phos
including up to 50% by volume in certain cases, pro phoric acid mixture were added to the water in the
vides the user of these acidic solutions with a plurality second container. The resulting aqueous acidic solution
of products that can be used in radiator cleaning and was thoroughly mixed. Thereafter, 22 pounds of pow
rejuvenation while retaining the safe handling proper 25
ties of the original product, including that of being dered citric acid and 15 pounds of powdered oxalic acid
innocuous to skin and other organic materials. All mix were admixed into the aqueous acidic mixture to pro
ing and storage containers employed in the production duce an aqueous acidic composition.
of the acidic compositions of the present invention are The aqueous acidic composition was then diluted by
preferably fabricated of a substance that is acid resis 30 admixing 481 pounds of the aqueous acidic composition
tant, such as stainless steel, plastic, Fiberglass, glass, and with 330 pounds of water in a third container. The
the like. It is also preferred that all containers used in aqueous acidic composition and water were thoroughly
the process of the present invention be provided with stirred and provided approximately 97 gallons of an
covers for safety reasons and to keep foreign materials aqueous acid-based composition having a pH value of
out of the product, especially the container in which the 35 about 0.49, which composition was non-reactive with
hydrochloric acid and the phosphoric acid are mixed. healthy human tissue despite the extremely low pH.
The aqueous acid-based composition produced as set The mixing and storage containers employed were.
forth above is an essential ingredient in the formulation formed of materials substantially acid resistant. Further,
of the radiator cleaner compositions of the present in all containers were covered for safety reasons and to
vention. In the preparation of the acidic radiator 40 prevent foreign materials from being injected into the
cleaner, about 2-45 weight percent of hydrochloric acid aqueous acid-based composition.
(HCl, d = 1.19 g/cc) is admixed with the aqueous acid
based composition in a well-ventilated area until a sub EXAMPLE II
stantially uniform mixture is obtained. It is to be noted Preparation of an Amine-Containing Aqueous
that the aqueous acid-based composition is preferably 45
Acid-Based Composition
maintained under constant agitation during the mixing
of the radiator cleaner solution so that the resulting In the preparation of an amine-containing aqueous
acidic composition is a substantially homogeneous solu acid-based composition, the same steps and procedures
tion. set forth in Example I for the preparation of the basic
The time required to thoroughly mix the hydrochlo 50 aqueous acid-based composition were carried out. Fol
ric acid with the aqueous acid-based composition to lowing the dilution of the aqueous acid-based composi
form the radiator cleaner composition can vary widely, tion described above, 17 pounds of hexamethylenetetra
and the mixing time and period will generally depend mine were admixed into about 811 pounds of the aque
on the rate of addition of the hydrochloric acid to the ous acid-based composition, and mixing continued until
aqueous acid-based composition, the amount of hydro 55 a substantially homogeneous colorless liquid was
chloric acid employed in the formulation, and the rate formed. Approximately 100 gallons of the amine-con
of speed of agitation of the aqueous acid-based composi taining aqueous acid-based composition was formed
tion during the addition of the hydrochloric acid. using this procedure, and the amine-containing aqueous
Once the hydrochloric acid has been added, an equal acid-based composition had a pH value of about 0.91
amount of distilled water must be admixed to the above
resulting acidic composition containing the hydrochlo and was innocuous when put into contact with human
ric acid. Again, care should be exercised when adding skin tissue.
the acidic composition to the water, and the rate and As in the preparation of the aqueous acid-based con
time of mixing may vary greatly. The mixing should be position of Example I, all mixing and storage containers
maintained continuously and done thoroughly so that a 65 employed were acid resistant containers. Further, each
homogeneous solution can be maintained. Once the of the containers was covered for safety reasons and to
above is accomplished, the preferred 1-8 weight per prevent foreign materials from being introduced into
cent butyl ethylene glycol base is added to the above the product.
 4,970,015
9 10
EXAMPLE III half (3) hours for Radiator Two, and six and a half (6)
hours for Radiator One. Moreover, the additional labor
Preparation of a Radiator Cleaning Solution and materials required for Radiator One added substan
After the 100 gallon amine-containing aqueous acid tially to the expense of cleaning it as compared to the
based composition in Example II above was mixed, 100 expense of cleaning Radiator Two using the present
gallons of hydrochloric acid (d=1.19 g/cc) was ad invention.
mixed therewith until a substantially homogeneous, EXAMPLE V
colorless liquid was formed. The resulting 200 gallons
of the aqueous acidic solution now showed a pH value Test with Standard Automobile Radiators
of 0.41. O
Again, the mixing and storage containers employed In this Example V, two similar radiators from two
were formed of materials that are basically acid resis 1984 Ford LTD's, 302 engines (model 362-cross flow
tant, and all containers were covered for safety reasons radiators with eleven (11) fins per inch and including
and to prevent foreign materials from entering into the transmission oil coolers) were tested as in Example IV
resulting aqueous acidic component. 15 above.
5 gallons of butyl propylene glycol base (butyl E.B.) Again, Radiator One was dipped in the caustic solu
were then added to the 200 gallons of the above aque tion while Radiator Two was dipped in the improved
ous acidic solution. This admixing was continued until a acid composition of the invention as described in Exam
homogeneous solution was obtained. At this stage, there ple III above.
were about 205 gallons of an aqueous acidic composi- 20 Radiator One took one (1) hour to clean in the caustic
tion of a pH value of about 0.49. This aqueous acidic solution, while Radiator Two took only fifteen (15)
composition was then diluted with about 200 gallons of minutes in the acidic composition of the present inven
distilled water to form roughly 400 gallons of the final tion. Both radiators were then tested and repaired ac
aqueous acidic radiator cleaning composition that was cordingly, and both were then rodded as a precaution
used in all of the tests that were run on the radiators 25 and re-tested again. In this instance, neither one needed
described in the Examples that follow. additional repairs. The time elapsed until the radiators
EXAMPLE IV were ready for installation was one and a half (1) hours
for Radiator One and forty five (45) minutes for Radia
Test with Heavy Duty Radiators tor Two.
Two similar heavy duty Flyer brand radiators, with 30 EXAMPLE VI
five rows of tubes each, were utilized in this test. These
radiators had been in service for approximately 12 Test with a Plastic and Copper Radiator
months, installed in buses servicing the San Mateo, The radiator of an 1987 Honda Prelude automobile
California County Transportation District, and were 35 (110 c.c. engine) with automatic transmission and air
tested simultaneously as indicated below. conditioner was tested in the solution of Example III
Radiator One was dipped in a bath of caustic solution above. This radiator was a down flow type radiator,
with a pH of 13.5 and heated to 180° F. as in traditional with plastic top and a Modine brand model 933 copper
cleaning. Radiator Two was dipped in a bath of chemi CO3.
cal solution of Example III above. The pH of this solu As an historic background, if this radiator would
tion was 2.0 and its temperature was 68' F. have arrived before the improved acidic solution of the
After a period of two (2) hours, both radiators were invention was in use, the cleaning process would have
removed from their respective baths and checked for had to be done by hand with a pressure washer, because
cleanliness. It was found that Radiator One (dipped in this type of radiator cannot be dipped in a caustic solu
the caustic solution) still needed considerable cleaning tion nor can it be cleaned via an ultrasonic device be
and had to be re-dipped in the solution for an additional 5 cause the chemical reactions that occur are violent and
two (2) hours. Radiator Two, in the meantime, was cause severe damage to the core.
observed clean and ready for repairing after the initial
two (2) hours. Since the improved acidic solution started to be
Once the radiators showed similar cleanliness (Radia tested, these type of radiators were effectively cleaned
tor One after four (4) hours, Radiator Two after two (2) 50. in fifteen (15) minutes or less.
hours), they were then flushed with clean water and EXAMPLE VII
tested at 20 psi for leaks. Both radiators showed minor Test with a Plastic and Aluminum Radiator
leaks and were repaired accordingly. Once the repairs
were completed, the radiators were again tested at 20 Prior to the present invention, aluminum radiators
psi. 55 could only be cleaned utilizing expensive and time con
At this time, Radiator One showed the need for "rod suming ultrasonic techniques. However, when such
ding', that is the tubes were still obstructed and needed aluminum radiators were treated with the solution of
to be lanced. Radiator Two, however, showed clean the invention as provided in Example III above, they
tubes and no need for rodding.
Radiator Two was then dried and painted while Ra- 60 age tocleaned
were
the
in eight (8) minutes or less, without dam
aluminum parts of the radiator.
diator One was being rodded. After this traditional
rodding process, Radiator One was again tested, and EXAMPLE VIII
additional leaks were found. These leaks were repaired, Test with a Heavily Corroded Radiator
and the radiator was then tested a fourth time, whereas
Radiator Two had been tested only twice. 65 The radiator of a seven (7) month old Toyota brand
After this final test, Radiator One was dried and fork lift was treated in this Example. It showed ex
painted. The period of time elapsed until both radiators tremely heavy build-up of corrosion, carbonates and
were ready for installation and reuse, was three and a silicates, inside of the radiator. This radiator was im
 4,970,015 12
11
mersed in its entirety in the boil-out tank for a period of embodiments and modifications and examples thereof, it
eight (8) hours in a caustic solution showing a pH of should be understood by those skilled in the art that the
12.5 and 165 F. using traditional techniques. foregoing and other modifications are exemplary only,
After the eight (8) hours, the technician tried to flush and that equivalent changes in form and detail may be
the radiator to remove all the loose material from inside 5 made therein without departing from the true spirit and
but was unsuccessful in three (3) attempts to do so. The scope of the invention as claimed, except as precluded
rodding process was also unsuccessful because over by the prior art.
75% of the tubes could not be lanced due to blockages The embodiments in which an exclusive property or
of the corrosion materials. privilege is claimed are defined as follows:
Because a new radiator for this fork lift costs over 10 1. An acidic solution for use as a radiator cleaning
$400.00, the owner agreed to let the radiator be tested composition comprising an aqueous solution of from
utilizing the improved acidic composition shown in about 1-8 weight percent of an ethylene glycol base,
Example III above. The results of this test were out about 2-45 weight percent hydrochloric acid, and about
standing. After only fifteen (15) minutes in the tank the 2-45 weight percent of an aqueous hydrochloric acid
radiator was taken out and flushed completely. It was 15 based composition having a pH of less than about 1.0,
also rodded in its entirety without any problems and yet substantially non-reactive with compounds having
was put back in service within one and a half hours (1) low oxidative states including human skin tissue.
from the time it had been dipped in the improved acidic 2. The acidic solution of claim 1, wherein said hydro
composition of the present invention. chloric acid-based composition comprises a dilute,
It should be noted that prior to the development of 20 aqueous hydrochloric acid-based solution admixed with
the improved acidic composition of the present inven an effective amount of at least one weak acid to produce
tion, no radiator cleaning job could be completed by strong conjugate bases to control the disassociation
closing time at 5:00 p.m. if the radiator came into a shop production of hydronium ions.
after 2:30 p.m. Using the present invention, jobs can be 3. The acidic solution as claimed in claim 2, wherein
started as late as 3:30 p.m. and be completed with as 25 said hydrochloric acid-based composition comprises a
much as one (1) hour to spare. This new procedure and dilute aqueous solution of hydrochloric acid and phos
composition allows for a much more effective use of phoric acid admixed with an effective amount of at least
time and increases production levels by as much as one weak organic acid to produce strong conjugate
75%.
Another aspect of the present invention is that of 30 bases to further control hydrochloric acid disassocia
safety. On several occasions in the past, the gas pilot in tion production of hydronium ions.
the burner of a caustic boil-out tank would blow out 4. The acidic solution as claimed in claim 3, wherein
during the night, and in the morning gas fumes and odor said hydrochloric acid-based composition comprises an
would be very noticeable in the shop. In the past, the aqueous mixture of about 5-20 weight percent hydro
hot fumes from the boil-out tank would damage the 35 chloric and about 5-20 weight percent phosphoric acid
metal structure of the building and roof, would cause admixed with approximately 1-5 weight percent of an
burns in the skin of the technicians and destroy uniforms hydroxy carboxylic acid and approximately 1-5 weight
and tools. Using the present invention, the boil-out tank percent of a dicarboxylic acid.
is eliminated, great energy savings are realized, and all 5. The acidic solution as claimed in claim 4, wherein
other problems related to this situation have been 40 said hydrochloric acid based composition further com
greatly reduced or completely eliminated. prises about 1-3 weight percent of a poly methyl amine.
Finally, "fine seepers' or very small leaks in radiators 6. The acidic solution as claimed in claim 4, wherein
that could not previously be detected are now discov said hydroxy carboxylic acid is selected from the group
ered the first time around and can be properly corrected consisting of citric acid, tartaric acid, and malic acid.
immediately. This capability practically eliminates radi 45 7. The acidic solution as claimed in claim 6, wherein
ators from coming back time after time due to this very said hydroxy carboxylic acid is comprised of citric acid.
annoying problem. 8. The acidic solution as claimed in claim 4, wherein
As can be seen from the above, the present invention said dicarboxylic acid is selected from the group con
provides a highly effective radiator cleaner composition sisting of oxalic acid, malonic acid, succinic acid, glu
which has as a basis for cleaning an acidic solution with 50 taric acid and adipic acid.
a very low pH. The advantage of the present invention, 9. The acidic solution as claimed in claim 8, wherein
as clearly seen from the above, is that while the pH of said dicarboxylic acid comprises oxalic acid.
the solution is very low to provide highly effective 10. The acidic solution as claimed in claim 5, wherein
cleaning, the pH is not so toxic as to cause damage to said poly methyl amine is selected from the group con
the radiator or surrounding areas. Moreover, due to the 55 sisting of hexamethylenetetramine, hexamethylenedi
unique nature of the present invention, the low pH amine and hexamethyleneamine.
acid-based composition of the invention is innocuous to 11. The acidic solution as claimed in claim 10,
human skin tissue as well as being non-reactive with wherein said poly methyl amine comprises hexamethy
other organic compositions of low oxidative states. This lenetetramine.
is substantially different from strong caustic cleaning 60 12. The acidic solution as claimed in claim 4, wherein
solutions presently on the market which require very said solution further comprises approximately 2-3
special handling and which can create toxic fumes ei weight percent of an acid thickening agent.
ther during use or during the mixture thereof. Finally, 13. The acidic solution as claimed in claim 1, wherein
the present invention is readily biodegradable so that it said ethylene glycol base comprises butyl ethylene gly
may be flushed down the drain without any environ 65 col.
mental concerns or toxicity problems. 14. The acidic solution as claimed in claim 13,
While this invention has been particularly shown, wherein said aqueous solution includes approximately
described and illustrated with reference to preferred 2-75 weight percent distilled water.
 4,970,015
13 14
15. The acidic solution as claimed in claim 1, wherein 27. The process as claimed in claim 23, wherein said
said solution comprises an aqueous solution of approxi acid-based composition is further admixed with a poly
mately 50 weight percent of said aqueous hydrochloric methyl amine.
acid-based composition, and approximately 50 weight 28. The process as claimed in claim 21, wherein said
percent glycol and hydrochloric acid solution. 5-20 weight percent phosphoric acid functions as a
16. The acidic solution as claimed in claim. 15, controller for hydronium ion production by the disasso
wherein said hydrochloric acid-based composition ciation of hydrochloric acid in water, and wherein said
comprises an aqueous mixture of about 5-20 weight hydronium ion production is further controlled by add
percent hydrochloric acid and about 5-20 weight per ing an effective amount of yet another weak acid.
cent phosphoric acid admixed with approximately 1-5 O 29. The process as claimed in claim 28, wherein said
weight percent of an hydroxy carboxylic acid and ap weak acid comprises hydroxy carboxylic acid, and fur
proximately 1-5 weight percent of a dicarboxylic acid. ther comprises the step of adding yet a third weak acid
17. The acidic solution as claimed in claim 16, to control hydronium ion production created by the
wherein said hydroxy carboxylic acid is selected from 15
disassociation of hydrochloric acid in water as well as
the group consisting of citric acid, tartaric acid, and created by the addition of said hydroxy carboxylic acid.
malic acid, and wherein said dicarboxylic acid is se 30. The process as claimed in claim 29, wherein said
lected from the group consisting of oxalic acid, malonic additional weak acid comprises a dicarboxylic acid.
acid, succinic acid, glutaric acid and adipic acid. 31. The process as claimed in claim 21, wherein said
18. The acidic solution as claimed in claim 17, 20
glycol base comprises butyl ethylene glycol.
wherein said hydroxy carboxylic acid comprises citric 32. An acidic radiator cleaning composition compris
acid, and wherein said dicarboxylic acid comprises ing approximately 2-75 weight percent distilled water,
oxalic acid. about 1-8 weight percent of an ethylene glycol base,
19. The acidic solution as claimed in claim 18, approximately 2-45 weight percent hydrochloric acid,
wherein said hydrochloric acid-based composition fur 25
and approximately 2-45 weight percent of an aqueous
ther comprises about 1-3 weight percent of a poly hydrochloric acid-based composition having a pH of
methyl amine. approximately less than 1.0 and prepared by the steps
20. The acidic solution as claimed in claim 19, of:
wherein said solution further comprises approximately admixing from about 5-20 weight percent hydrochlo
2-3 weight percent of an acid thickening agent. ric acid with about 5-20 weight percent phos
21. A process for preparing an acidic solution for use phoric acid to produce an acidic mixture; and
as a radiator cleaning composition having a pH of less admixing said acidic mixture with an effective
than about 1.0 while being non-reactive with human amount of water to produce an aqueous acid-based
skin tissue, comprising admixing approximately 2-75 composition having approximately 47-87 weight
weight percent water and approximately 1-8 weight 35 percent water.
percent of an ethylene glycol base with approximately 33. A radiator cleaning composition as claimed in
2-45 weight percent of a hydrochloric acid, and further claim 32, wherein said aqueous acid-based composition
admixing this glycol-acid solution with about 2-45 is admixed with an effective amount of at least one weak
weight percent of an aqueous acid-based composition, organic acid to produce strong conjugate bases to con
said aqueous acid-based composition being prepared by trol hydrochloric acid dissociation production of hy
the steps of: dronium ions therein.
admixing from about 5-20 weight percent hydrochlo 34. The radiator cleaning composition of claim 33,
ric acid with about 5-20 weight percent phos wherein said aqueous acid-based composition is further
phoric acid to produce an acidic mixture; and admixed with approximately 1-5 weight percent of a
admixing said acidic mixture with an effective 45 hydroxy carboxylic acid and with from about 1-5
amount of water to produce an aqueous acid-based weight percent of a dicarboxylic acid.
composition having approximately 47-87 weight 35. The radiator cleaning composition as claimed in
percent water. claim 34, wherein said hydroxy carboxylic acid is se
22. The process as claimed in claim 21, wherein said lected from the group consisting of citric acid, tartaric
aqueous acid-based composition is admixed with an 50 acid, and malic acid.
effective amount of at least one weak organic acid to 36. The radiator cleaning composition as claimed in
produce strong conjugate bases to control hydrochloric claim 34, wherein said dicarboxylic acid is selected from
acid dissociation production of hydronium ions therein. the group consisting of oxalic acid, malonic acid, suc
23. The process of claim 22, wherein said aqueous cinic acid, glutaric acid and adipic acid.
acid-based composition is further admixed with approx 55 37. The radiator cleaning composition as claimed in
imately 1-5 weight percent of a hydroxy carboxylic claim 34, wherein said hydroxy carboxylic acid com
acid and with from about 1-5 weight percent of a dicar prises citric acid and said dicarboxylic acid comprises
boxylic acid. oxalic acid.
24. The process as claimed in claim 23, wherein said 38. The radiator cleaning composition as claimed in
hydroxy carboxylic acid is selected from the group claim 34, wherein said acid-based composition is further
consisting of citric acid, tartaric acid, and malic acid. admixed with a poly methyl amine.
25. The process as claimed in claim 23, wherein said 39. The radiator cleaning composition as claimed in
dicarboxylic acid is selected from the group consisting claim 32, wherein said 5-20 weight percent phosphoric
of oxalic acid, malonic acid, succinic acid, glutaric acid acid functions as a controller for hydronium ion pro
and adipic acid. 65 duction by the disassociation of hydrochloric acid in
26. The process as claimed in claim 23, wherein said water, and wherein said hydronium ion production is
hydroxy carboxylic acid comprises citric acid and said further controlled by adding an effective amount of yet
dicarboxylic acid comprises oxalic acid. another weak acid.
 4,970,015
15 16
0. The radiator cleaning composition as claimed in
claim 39, wherein said weak acid comprises hydroxy
claim 40, wherein said additional weak acid comprises a
carboxylic acid, and further comprises the step of add dicarboxylic acid.
ing yet a third weak acid to control hydronium ion 42. The radiator cleaning composition as claimed in
production created by the disassociation of hydrochlo. 5 claim 32, wherein said glycol base comprises butyl eth
ric acid in water as well as created by the addition of ylene glycol.
said hydroxy carboxylic acid.
41. The radiator cleaning composition as claimed in
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