WATER POLLUTION CONTROL RESEARCH SERIES 16080 DVF 02/72
TECHNICAL EVALUATION OF
PHOSPHATE-FREE
HOME LAUNDRY DETERGENTS
U.S. ENVIRONMENTAL PROTECTION AGENCY
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WATER POLLUTION CONTROL RESEARCH SERIES
The Water Pollution Control Research Series describes the
results and progress in the control and abatement of
pollution in our Nations waters. They provide a central
source of information on the research, development, and
demonstration activities in the water research program of
the Environmental Protection Agency, through inhouse
research and grants and contracts with Federal, State, and
local agencies, research institutions, and industrial
organizations.
Inquiries pertaining to Water Pollution Control Research
Reports should be directed to the Chief, Publications
Branch (Water), Research Information Division, R&M,
Environmental Protection Agency, Washington, i D C. 20460.
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TECHNICAL EVALUATION
OF PHOSPHATE-FREE HOME LAUNDRY DETERGENTS
by
Helmut G. Reilich
IIT Research Institute
Chicago, Illinois 60616
for the
Office of Research and Monitoring
ENVIRONMENTAL PROTECTION AGENCY
Project No. 16080 DVF
Contract No. 14-12-937
February 1972
For sale by the Superintendent of Documents, U S Government Trniling Office, Washington, D.C 20403 - I'ncc &l 25
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EPA Review Notice
This report has been reviewed by the Environmental
Protection Agency and approved for publication. Approval
does not signify that the contents necessarily reflect
the views and policies of the Environmental Protection
Agency, nor does mention of trade names or commercial
products constitute endorsement or recommendation for use,
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ABST RACT
Evaluation studies were carried out on a number of phosphate-
free home laundry detergent formulations. These formu-
latioris were based on surfactants developed during the
previous investigation sponsored by the Federal Water
Quality Administration. These surfactants were selected
because of the potential hard ion chelating properties
and/or immunity to hard water effects. During the current
program, they were also found to be non-toxic to marine
life and to be biodegradable.
Separate series of formulations with each of three sur-
factants were evaluated. All formulations were aimed at
the eventual development of a 100% solids, powdered
product and contained 20% of the selected 5urfactant arid
2% carboxymethylcellulose. The remainder of the formu-
lations was varied using a number of known and safe
conventional and unconventional components in various
concentrations and combinations.
During the course of the project a combined total of 123
new formulations were evaluated. In addition, the original
15 formulations were reevaluated using a different type of
cloth. The detergency effectiveness of these formulations
was evaluated on two commercially produced, artificially
soiled cotton test cloths. The effectiveness of 20
selected formulations was also evaluated on dacron/cotton
wash-and-wear fabrics both with and without permapress
finish. The detergency data compared favorably to that
obtained with a standard phosphate containing detergent
formulation supplied by the Association of Home Appliance
Manufacturers (AHAM) and to a widely popular commercial
brand.
This report was submitted in fulfillment of Project
Number 16080 DVF, Contract No. 14-12937, under the
sponsorship of the Office of Research and Monitoring,
Environmental Protection Agency.
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CONTENTS
Section Page
I Conclusions 1
II Recommendations 3
III Introduction 5
IV Synthesis of the Surfactants 7
V Biological Testing 11
VI Evaluation of Detergent Formulations 13
VII Acknowledgments 55
VIII References 57
IX Appendices 59
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TABLES
No. Page
1 Formulations for All Compounds 19
2 Formulations for Compound 112A 20
3 Formulations for Compound ll2Bl 22
4 Formulations for Compound 212 24
5 Formulation Components 27
6 Normalization of UST Cloth Data 34
7 Detailed Performance Ranking of ll2A
Formulations UST Cloth 38
B Detailed Performance Ranking of ll2A
Formulations - EMPA Cloth 40
9 Detailed Performance Ranking of 112A
Formulations - Combined Cloths 42
10 Summary of Performance Ranking of
Compound ll2Bl Formulations 44
11 Summary of Performance Ranking of
Compound 212 Formulations 46
12 Whiteness Retention ll2A Formulations 52
13 Whiteness Retention - 212 Formulations 53
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FIGURE S
No. Page
1 Regular vs Combined Washing
IHAM in 50 ppm Hardness Water 16
2 Regular vs Combined Washing
AHAM in 135 ppm Hardness Water 17
3 Regular vs Combined Washing
i - RAM in 300 ppm Hardness Water 18
4 Comparison of Two Batches of ENPA Cloth 29
5 PRAM on UST Cloth
50 ppm Hardness Water 30
6 PRAM on UST Cloth
135 ppm Hardness Water 31
7 PRAM on UST Cloth
300 ppm Hardness Water 32
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SECTION I
CONCL US IONS
The results obtained during the course of this project
indicate that effective phosphate-free home laundry
detergents can be formulated using specific anionic
surfactants and builders which are relatively safe and non
polluting. The results also show that these formulations
can be effective over a considerable range of water hard-
ness. Indications also are that several nearly equally
effective formulations can be developed.
Two of the three surfactants investigated, sodium dodecyl-
benzenesulfonamidoethyl sulfate (C12H 25 -C6H 4 -SO 2 NHCH 2 CH 2 -
OSO3Na, 112A) and methyl 3-dodecylbenzoyl3(2)(sodium
sulfonato)propionate (C1 2 H 25 -C 6 H 4 COCH(SO 3 Na)CH 2 CO 2 CH 3 ,
212)1 are about equally capable of yielding detergent
formulations which show high promise of being acceptable
substitutes for the current high-phosphate products. The
third surfactant, sodium dodecylbenzenesulforiamidoethyl
sulfone (C 12 H 2 r-C 6 H 4 -SO 2 NHCH 2 SO 3 Na, 112B1), although
promising, yie ded no formulation during the current
project which were competitive with those obtained for the
former two compounds.
All formulations evaluated contained 20% of the selected
surfactant and 2% carboxymethylcellulose (CMC). The CMC,
a well known soil suspending agent, was used ad hoc on the
basis of its well-established properties, and no attempt
was made to investigate possible substitutes or to determine
the optimum use level. Although the point was not pursued
as a specific end, indications are that the use of these
surfactants may lead to detergent formulations of lower
basicity than those currently in use rendering them safer
and less corrosive. Most of the formulations tested had a
pH of about 10 but a few which were tested at about pH 9
performed quite well.
Of the several potential builders investigated sodium
acetate, sodium citrate and sodium gluconate had the
greatest beneficial effect, especially when used in combi
nation with each other. Electrolites, such as sodium
chloride and sodium sulfate, also contributed to the
effectiveness of some of the formulations. Sodium
carbonate, on the other hand, had only a relatively minor
effect in improving the performance of these surfactants.
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The formulation of choice (112A-121), had good overall
detergent properties performing well under all the test
conditions used and is essentially free of potentially
polluting substances.
Limited biological testing of the candidate surfactants
indicates their safety relative to fish toxicity and their
lack of algae stimulating properties. Their biodegrad-
ability had already been established under the previous
project.
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SECTION II
RECOIVIMENDAT IONS
The ability of the surfactants under consideration to
produce phosphate-free detergent formulations has now been
demonstrated on the basis of laboratory evaluation. A
further evaluation of a number of other factors is now
indicated. These factors include (1) thorough biological
and safety testing, (2) consumer acceptability, (3) potential
effect of large scale use on the environment, (4) further
optimization of product efficiency, (5) feasibility of
using these surfactants in developing phosphate-free
dishwasher detergents, and (6) economic considerations.
Although preliminary investigation shows that the surfactants
112A and 212 are safe, fullscale biological and safety
testing should be undertaken. Since these surfactants
have not been used for this purpose before and their
behavior is not well established, such testing is
imperative. Fully built candidate formulations should be
included in these tests to insure that no untoward
synergistic effects are manifested.
Consumer acceptability testing and the potential effect of
large scale use of these detergents should be assessed.
These two studies can be carried out simultaneously by
placing a selected formulation in a relatively isolated
community which has its own sewage treatment plant. A
large scale production of one or more formulations should
be undertaken and the product offered for use by all the
households in the selected community for a period of
several months. A good estimate of consumer acceptance
could be derived from opinions of the people using the
product. Monitoring the effluent waters from this community
both before and after treatment would provide insight both
into the effect of the removal of phosphate from laundry
detergents as well as the specific impact on the ecology
of using the candidate surfactant. Such a study would be
doubly useful since it would also provide data relative to
the need to possibly consider the removal of other sources
of phosphate, e.g., automatic dishwasher detergents, in
order to effectively counteract eutrophication.
The formulation which we are recommending for the br3ad
range study is 112A12l. This formulation is not the only
effective formulation developed during this program nor do
we intend to imply that it is necessarily the best possible
formulation which can be developed using these .nionic
surfactants. This is particularly true si ice one of the
most promising formulation components, nitrilotriacetate
(NTA) , was not evaluated because its use in detergents was
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in serious doubt during most of the time during which this
program was in effect. Further efforts towards the
optimization of effectiveness of formulations based on
these surfactants is therefore indicated. This effort
should be extended to both compounds 112A and 212. Data
indicates that the latter can yield detergent formulations
at least as efficient as the former.
Considering that the number of automatic dishwashers in use
in our society is rapidly increasing and that most
detergents designed for use in these machines contains an
exceedingly high amount of phosphates, up to 90%, some
thought should now also be given the potential thread of
phosphate pollution from this source. It is therefore
recommended that a similar study to determine the
feasibility of using these or analogous surfactarits for
formulating phosphatefree dishwasher detergents be under-
taken.
Since these surfactants are not now in commercial pro-
duction, a study to estimate their potential cost should be
undertaken. The economic impact on the market of builders
used in the proposed formulations is also merited. Such
cost data would be useful in promoting, by the government,
the production of these phosphate-free home laundry
formulations to industry.
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SECTION III
INTROD JCTION
Eutrophication of the Nations lakes and rivers has become
a major problem causing great concern to government,
industry and the public. Phosphates in particular have
been singled out as being to a large extent responsible for
this eutrophication. Detergents, of which phosphates are
a major component, are among the main sources of the phos-
phates which reach our waterways. Much pressure has there-
fore been exerted to urge government and industry to find
detergent formulations which are free of phosphates and
other polluting substances. While it has been suggested
that an alternate solution, namely, the building of vast
tertiary sewage treatment plants, capable of removing the
phosphates from the sewage be initiated, the elimination
of the sources of pollution still remains the most logical
approach.
During a previous project 1 we demonstrated the feasibility
of formulating home laundry detergents using a novel
series of surfactants which have the ability to avoid the
interference from the hard water ions to which the
conventional surfactants and soaps are susceptible. This
immunity to hard water effects eliminates the need for
strong chelating agents which is one of the major functions
of phosphates. The other functions usually attributed to
the phosphates, solids suspension by deflocculatiori and
reserve alkalinity could then be provided by the judicious
selection of other components used to make up the fully
built horns laundry detergent formulation.
Work on the previous project indicated that three of the
several surfactants investigated had definite promise for
the successful formulations of phosphate-free laundry
detergents. These compounds were sodium dodecylbenzene-
sulfonamidoethyl sulfate (112A), sodium dodecylbenzene-
sulfonamidoethyl sulfonate (11261) and methyl 3 dodecyl-
ben .oyl-3(2)-(sodiurn sulfonato)propionate (212)
This project then, consisted of formulation and evaluation
of phosphatefree detergents, using the above surfactants,
which would be acceptable substitutes for conventional home
laundry products.
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SECTION IV
SYNTHESIS OF THE SURFACTANTS
The synthesis of the candidate surfactants was discussed
in detail in the previous report. 1 Efforts during the
second year of this project were aimed primarily at up-
grading the yields and at defining the parameters for
scaling up the reactions to eventual pilot plant size
production of the selected compound. The synthesis of the
three surface active agents selected for further develop-
ment is reviewed in the following paragraphs which include
also some pertinent experiments to defining the parameters
for the optimization of the reactions.
Synthesis of Surfactants 112A and ll2Bl
It had become apparent that on the basis of NMR spectra
these two surfactants, as used in the earlier evaluations,
were only about 60% pure, the remainder of the titratable
surfactant being LAS. The reaction conditions for the
sulfonation of the alkylbenzene were studied critically.
It appeared that the reaction took place readily at room
temperature either in the absence or presence of chlori-
nated hydrocarbon. Primarily, for reasons of ease of
handling it was found useful to add a fair amount of
dichioroethane which markedly reduces the viscosity of the
product. Using this approach, t was observed that the
reaction mixture after standing for at least 4 hrs at room
temperature or overnight settles out a very dark lower
layer of spent sulfuric acid. The density of this lower
layer is approximately 1.8 which is close to that of
sulfuric acid. In this manner, we were able to remove
about 7075% of the sulfuric acid formed during the course
of the following reactions:
R- + 2 HC1SO 3 R_O_S0 3 c]. + HC1 χ H 2 S0 4
Running the sulfonation at a higher temperature did not
affect the yield but caused a marked darkening of the
organic layer which made the separation of layers much more
difficult.
It had been assumed that the sulfonyl chloride formed in
the above reaction would decompose quite readily in water
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or alkali which, however, turned out not to be the case.
The sulfonyl chloride when stirred with aqueous sodium
hydroxide at 80°C did not decompose to any significant
extent. Upon addition of DMSO hydrolysis did occur,
requiring about 1/2 hr at 800C. The relative stability
of the sulfonyl chloride and the use of a mutual solvent
appeared to be a key to improving the yield of the product.
None of the spectra of the product show any significant
amount of hydrocarbon so that it can be assumed that the
sulfonation with chlorosulfonic acid is a reasonably
quantitative one. The conversion to the sulfonyl chloride
is not entirely quantitative. By dispersing the sulfonyl
chloride in water and neutralizing this suspension 4ith
sodium hydroxide, we would presumably convert all unreacted
sulfonic acid to LAS. On the basis of a cationic titration,
che crude sulfonyl chloride proved to contain abcut 6%
unreacted sulfonic acid.
In order to expedite the conversion to the sulfonamide
surfactants 112A and ll2Bl, we found the u3e of DMSO to be
of some advantage. One disadvantage of using DMSO was later
found in the scaled up experiments where it was extremely
difficult to completely remove this solvent from the pro-
duct. The reaction proceeds best if carried out at room
temperature. The synthetic procedures for the two sur-
factants are entirely analogous as outlined in the
following sections.
Synthetic Procedure
47.2 g of dodecylbenzene (Continental Oil Nalkylene 500)
were dissolved in 50 ml of dichioroethane. 51.3 g of
chiorosulfonic acid were added slowly at room temperature
while cooling with a water bath. The mass was then
transferred to a separatory funnel and allowed to settle
for 4 hrs. The mass became cloudy after about 2 hrs and a
darker layer of black sulfuric acid settled on the bottom.
After 4 hrs this bottom layer of 16 g was discarded. 27 g
of sodium hydroxide were dissolved in 125 ml of water and
the solution cooled to room temperature. 15 ml of DMSO
were then added followed by 28 g of aminoethyl hydrogen
sulfate. After all or most of the latter had dissolved
at room temperature, the sulfonyl chloride solution was
added slowly to this solution with good cooling with an
ice or water bath in order to maintain the temperature at
or below 25°C. Stirring was continued without further
cooling. After about 2 hrs, the initially milky white
reaction mass turned somewhat more translucent and
yellowish and the viscosity of the mass increased
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substantially. The pH dropped rapidly to 8. Occasionally,
a pH drop to 5 occurred in which case a few pellets of solid
sodium hydroxide were added to bring the pH back to 8-9.
Stirring at room temperature was continued until no further
pH drop was observed for at least 30 mm. Then 10 ml of
dichioroethane and 30 ml of isopropanol were added where-
upon the viscosity dropped substantially. The reaction
mass was then heated to 60°C and placed in a separatory
funnel. A lower aqueous layer amounting to 7580 ml was
drawn off and discarded. The top layer was placed in a
rotary evaporator to remove the chlorinated solvent. A
small part of the resulting geletanous mass was dried
further for NMR analysis. The remainder was usually
dissolved in a mixture of 30% isopropanol in water since it
was easier to use in this form for most of our test
formulations. A conversion of about 80±5% was obtained by
this procedure.
Surfactant ll2Bi an sy hesized in exactly the same manner
a:5 above except that 25 g of taurine were used i..-i place of
the aminoethyl hydrogen sulfate. In this case, the
conversion also amounted to 85+5%.
No difficulties were encountered in scaling up t: e synthesis
of these two surfactants. Batches using more than ten
times (3 moles) the above quantities were successfully made
in the laboratory. It is not expected that pilot plant
and larger production of these compounds should present any
significant problems provided that proper corrosion
resistant equipment is used.
Synthesis of Sulfopropionate Surfactant 212
The acrylic acid intermediate was prepared as follows:
49 g (0.5 M) of maleic anhydride was mixed with 110 g of
dry dichloroethane in a 3-neck flask equipped with a
thermometer, magnetic stirrer, dropping funnel and a
ref lux condenser which was topped with a drying tube. The
anhydrous aluminum chloride (120 g, 0.9 M) was added with
cooling and, after ten minutes of stirring, 118 g (0.5 M)
of dried dodecylbenzene (Continental Oil Company,
Nalkylene 500. MW 23) was added slowly while maintaining
the temperature at 20°C. After stirring at room tempera-
ture for one hour, the viscous :3rk brown mixture was
poured into a b ker containing 450 g of ice, 50 ml of 66%
sulfuric acizI and 15 ml of isopropyl alcohol. After
thorough mixing, the bright yellow mixture was allowed to
stand and the upper layer was separated and washed twice
with 70 ml portions of 66% sulfuric acid which coiitained
10 ml of isopropyl alcohol. The unsaturated keto acid
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solution in dichioroethane was heated to 70°C to remove
a water layer. For the purpose of infrared and PMR
spectra, the organic layer was stripped of solvent under
reduced pressure, leaving a viscous amber liquid Basic
titration of this material required 2.75 meq/g. The
theoretical value for the acrylic acid intermediate is
2.91 meq/g.
The solution was then esterified with 19.2 g of methanol
(0.6 M) and 5 ml of concentrated sulfuric acid (or 2 g of
toluenesulfonic acid). The solution was heated at reflux
for 3/4 of an hour, the lower aqueous layer was separated
and discarded and an additional 12.8 g (0.4 M) of methanol
and 2 ml of concentrated sulfuric acid (or toluene
sulfonic acLd) were added. After refluxing for an
additional 1 1/2 hours the organic layer was separated
and the solvent was removed under reduced pressure.
Titration of the residual oil with standardized
ethanolic potassium hydroxide solution showed the acid
content to be less than 4%.
Conversion of the acrylate to the desired surfactant, 212,
was accomplished by the addition of sodium bisulfite
across the double bond. A Parr pressure reactor was
charged with the ester and 52 g (0.5 M) of sodium bi.-
sulfite in 140 ml of water. The mixture was heated in the
sealed container with stirring for 3 hours at 110120°C.
The yellow mixture was removed and dried in a vacuum oven
at 55°C/13 torr. The anion content of this material was
typically 2.01 meq/g as determined by cationic titration.
The theoretical value for the surfactant is 2.23 meqJg,
inferring Ca. 90% purity.
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SECTION V
BIOLOGICAL TESTING
While the full range of biological testing of our sur
factants was not within the scope of the current program,
preliminary fish toxicity tests and algae stimulation
tests were carried out. During the previous years I
program the biodegradability of these compounds had already
been established to be of the same order as that of the
linear alkylbenzenesulfonates widelj uc ed in todays
phosphate containing detergents. The tolerance limit
median (TLm) study using fingerling fathead minnows and
the provisional algae assay procedures (PAAP) on the
three candidate.surfactants and a control sample of LAS
were performed under subcontract by Biometric Testing Inc.,
Englewood Cliffs, New Jersey. Their report, describing
in detail all the methods used, is appended hereto.
The 96 hr TLrn values, as reported by Biometrics, were
somewhat lower for the three candidate surfactants than for
the two aliquots of the same lot of LAS. The 96 hr dynamic
phase Thm values were 2.0 ppm for surfactant 11Th, 6.0 ppm
for ll2Bl, and 3.2 ppm for 212 as compared to values of
12.0 ppm and 9.5 ppm for the two samples of LAS: Dissolved
oxygen values for all compounds during these tests ranged
from 7.0 ppm to 10.5 ppm.
r-ze r. salts of the PAAP test using the alga a & n . trum
capricornuturn compared favorably with those obtained with
LAS. The increases in the number of algae cells between
the 5th and 7th day for LAS over the increase in the cell
count for the corresponding control were by factors of
1.13, 1.41 and 1.37, respectively, for concentrations of
5.0 ppm, 0.5 ppm end 0.05 ppm LAS. These increases were
by factors of 1.16, 1.33 and 1.20 for concentrations of
3.0 ppm, 0.3 ppm and 0.03 ppm of surfactant 11281; and
1.11, 1.55 and 2.16 for concentrations of 1.8 ppm, 0.18
ppm and 0.018 ppm, respectively, of surfactant 212.
Surfactant ll2A showed a slight apparent iihtbition effect
where cell counts between the 5th day and the 7th increased
to a somewhat lesser degree than those for the correspond-
ing control. At concentrations of 1.4 ppm, 0.14 ppm and
0.014 ppm, compound ll2A gave factors of 0.47, 0.77 and 0.68,
respectively.
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sE::TI0N VI
EIALUATION OF DETERGENT FORWJLATIONS
Test Procedures
The advantages to using a laboratory benchscale device
capable of simulating the action of a washing machine over
the use of an actual full-scale cornrtercial machine are
manyfold, especially -where rapid evaluation of a large
number of formulations is required. The expense and time
consuming gathering and processing of large numbers of
full-sized laundry bundles is avoided and a test can be
run in about 20 mm instead of 12 hrs. Further savings
in cost and time result from the fact that only relatively
small quantities of the test formulations need be made up
and the use of a full scale washing machine almost pre-
cludes the testing at water hardnesses other th ri that
normally available locally. Finally, wherL correlation
of a large number of comparative data is req .iired for
critical evaluation of formulation components, the bench
scale equipment permits the necessary control of the
conditions to be used.
All of the evaluations on this project were therefore carried
out using a benchscale simui ted washing m chmne. The
machine used was a Tergotometer Model 7243 manufactured
by U. S. Testing Co. of Hoboken, New Jersey. This instru
nient permitted the close control of the wash water
temperature, detergent concentration, speed and timing of
the -wash and rinse cycles. In addition, this model has
four separate washing stations so that it was possible to
run four samples or :oncentrations simultaneously. The
conditions used for all tests were a machine speed of 150
rpm and wash water temperature of 120°F. The wash cycle
was 15 minutes and the rinse cycle 2 minutes. The tests
were run at three water h rdness levels of 50, 135 and
300 ppm. The 135 ppm level presents the nominal hardness
of Chicago tap water which was used directly. The 50 and
300 ppm waters were made up by adding to appropriate amounts
of calcium and magnesium chlorides to distilled water or to
tap water, respectively.
The soil as well as the cloth used for testing the
effective-iess of detergents is of critical importance. A
grsat nuther of investigations have been reported in the
literature on the significance of these two parameters and
a number of soil compositions ranging from iron compounds, 2
ClayL 3 clayoleic acid combinations 4 to vacuumed carpet
soi1 ha- -2 been developed and proposed as being more or
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less representative of the soil found in normal laundry
bundles. Several companies, both in the U. S. and abroad,
provide pre-soiled test cloths on a commercial basis. The
soils used for these cloths vary with the manufacturer
and the purpose for which the cloths are intended.
Basically, these soils are compositions of several commonly
found materials including vegetable and/or mineral oil,
starches, proteinaceous derivatives and other organic and
mineral components. Carbon (lamp black) is added to these
soils to provide a constant coloricig which may be used for
the optical evaluation. The soil is transferred onto the
cloth by either cloth dyeing or printing methods capable
of providing a reasonably consistent product. Here again,
the choice of using commercially available soiled cloth over
soiled cloth made in our own laboratories was dictated by
two main considerations. The availability of large quanti-
ties of soiled cloth of sufficient consistency to yield
readily correlatable detergency data gathered over a pro-
tracted period of time was essential. Producing such
quantities of cloth on a laboratory scale is extremely
cumbersome and requires an inordinate expenditure of time
if strict quality control is to be exercised.
The soiled cotton cloth supplied by U. S. Testing Co. (UST)
which had been used during the previous years work was
again utilized during this project. In addition, a second
soiled cotton cloth, EI A-lOl, was used for all of the Lest
formulations produced during the pres nt program and many
of the previous formulations were retested on this cloth.
This cloth is produced in Switzerland for the
E d j. -tossischema erialprufunganstalt (EMPA) and supplied
in the U. S. by Testfabrics, Inc. Selected formulations
were further tested on two types of dacron/cotton (65/35)
shirting made by Testfabrics, Inc., New York, New York.
One of these fabrics had a permapress finish while the
other was without finish.
During the earlier work using only a single type of test
cloth three 4 1/2 x 51 swatches were placed in the Tergoto-
meter container and washed in 750 ml of detergent solution.
After the addition of a second type of cloth to our testing
program, the method was changed to enable us to run both
cloths simultaneously thus allowing us to evaluate the
same number of formulations in a given time as with the
single cloth method. This procedure had been investigated
in connection with another project and proved suitable for
us ere. This method combines the washing of both the
UST and the EMPA cloths in a single run. Three swatches
of each are placed in the same Tergotorneter container and
washed together instead of making a separate washing for
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each type of cloth. The size of the swatches was reduced
to 4 x 4 arid in order to partially compensate for the
increased amount of material to be washed, the amount of
detergent solution used was increased from 750 ml to
1000 ml. Although the overall results obtained by this
meLhod are generally lower than those obt:ained when the
cloths are washed separately. the resulting curves are,
for all practical purposes, parallel and differences
between the t ffectiveness of the various formulations re
similar. The results for AHAM are illustrated in Figures
13.
In order to be able to monitor the test procedures and to
permit normalization of data where two different lots of
cloth yielded significantly different detergency results,
two commercially formulated detergents were used for
reference purposes. One was a standard detergent formu
lation provided by the American Home Appliance Manufacturers
Association under the label AT-LNV1_2A. The other was a
popular home laundry product purchased at the local super
market. This widely used high phosphate brand also
provided us with performance data which we felt we should
attempt to match in order to insure potential cor sumer
acceptance of our non-phosphate formulations.
Formulation
Since the prime objective of the present program was to
develop one or more phosphate-free detergent formulations
which could readily be substituted for the high phosphate
products now in use, it was desirable to aim for a solid,
powdered formula of the general type of those common today
; nd in the use of which the housewife is familiar with.
An extended, built formulation was preferable since, in the
opinion of many experts, detergent concentrates have, in
the past:, always encountered an undue degree of consumer
resistance. Finally, a powdered detergent, due to the
design of most existing washing machines, is more easily
and safely handled than a liquid formulation.
For these reasons, all of our experimental formulations
were formulated with a view toward eventually building a
100% solids pioduct. The percentage values given for the
various components in Tables 1 to 4 and in the following
discussion are on the basis of partially built formulations
with the balance in oa h case being ater. Thus, all
formulations contained 20% surfactant, 2% carboxymethyl-
cellulose (CMC), the given percentages of other components
plus, in most cases, water. The actual percent total
solids is given in the line below the ingredients of the
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50
REGULAR WASHING
COMBINED WASHING
40
EMPA*I
3o---- -
20
UST#7
0 I I I
0.1 0.2 0.3 0.4 0.5
% AHAM in Wash Water
Figure 1
REGULAR VS COMBINED WASHING
PJIAM in 50 ppm Hardness Water
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50
REGULAR WASHING
COMBINED WASHING
40
EMPA I
30 _ _
20
0 I I I
0.1 0.2 0.3 0.4 0.5
% AHAM in Wash Water
Figure 2
REGULAR VS COMBINED WASHING
AHAM in 135 ppm Hardness Water
17
-------
50
Figure 3
REGULAR VS COMBINED WASHING
ABAM in 300 ppm Hardness Water
-a
a)
U
(U
4-,
U
4- 1
a)
- -I
U
U
U
U
4 - 1
4- 1
-1
40
30
20
10
001
0.2 0.3 0.4 0.5
% AHAM in Wash Water
18
-------
Table 1
FORMUI&rTr 15 .()fl hit.
Components A A A A C CC H 1L. _L.. _L. _!L.. ..A.. S. S. S. _Q
sixicateb 14.1 10.1 10_i 10.1 10_i 10.1 10.1 10.1 10.1 10 1 2.8 10_i 10.1 10.1 8 4 9.4 9.4
C.arboxymethylceiluiose 2.0 2.0 2.0 2.0 2 0 2 0 2.0 2.0 2 0 2 0 2 0 2.0 2.0 2 0 2 0 2.0 2.0
Cocodiethanolamide 20 2.0 2.0 2.0 2.0 2.0 2.0 2.0 20 2.0 20 20 20 20 2.0 2.0 2.0
Sodsu inAcetate 30 - - - 30 30 22 22 20 20 20
SodiuznCitrate - 17 - - - -
SodiumCarbonate 40 10 - - - 10 -
SodiumChlorida - - - - - 10 - - - - - - - - - -
Sodium Sulfate - - - - 10 40 - 15 10
Trisodiuin Nitrilotri
acetate (NTA) - - - - 17 17 17 - 17
Tergitol - - - - - -
seqiane - - - - - - - - - - - - -
Sod iuni cluconate - - - - - - - - - - - - - - -
GantresAN 119 - - - -
Weston - - - - - - - - - - - - - - - -
Total Sot idsC 1 ..JL. ...IL. .iZ.. 11. ..ii. !n4
Ranking for 112A Fonnulationsd
US? Cloth (63) 41 29 47 18 28 30 52 49 38 33 45 50.5 43 48 39 53 59 51 44
Et4PAC Ioth(59) 6 1 4 7 19 40 2 14 1] 8 58 55 5 47 59 49
Combined Cloths (59) 11 1 14.5 3 24 38 21 29 19 - 20 58 57 28 56 59 54
Ranking for 1128 pormuiationsd
US? Cloth (57) 48 27 50.5 11 44 13 56 34 22 32 50.5 52 41 40 39 47 49 57 45
EMPA Cloth (56) 1 4 25 12 14 9 S 3 10 52 2 8.5 33.5 18 16 39 56 41
Combined Cloths (56) 1 7 34 13 19 4 18 5.5 9 55 2 35 36 23 27.5 47 56 45
Ranking for 212 Formu lationsd
US? Cloth (53) 32 35 45 5 24 31 48 41 40 27.5 34 27.5 26 46.5 29 50.5 37 53 46.5
EE4PA Cloth (47) 3 1 16 34 11 12 6 2 25 33 13 8 17 36 47 45
CombinedCleths(47) 2 1 18 19 11 12 13 3 27 39 17 9 25 45 47 46
aAll formuiatins contain 20% surfactant.
b star silica a. except as otherwise noted.
CTotal solids nclude 20% surfartant; balance = water.
dweighted rank values; figures in parentheses indicate total number of samples ranked Ln sat: 1 = worst, highest value = best.
-------
Tible 2
R)1LLAl IONS FUR COMPA ND i i 2A
CcmDonent . I L I L. _&_ .1?.. .IL it. At. S. S.. .1k. .1L. .IL it.. _ 2_ ..SL S. .21. ..fl_ AL. .2k.. ._22_ -2k..
It 1. N U ii U
10.1 10.1 10.1 10.1 5.0 10.1 10.1 0 9 6 10.1 10.1 10 1 0 10.1 0 0 10.1 to_i s.c s.o o 0
Cerboxy nathy1cel1u1cse 2.0 2.0 2.0 2.0 2.0 2.0 2 0 2 0 1 9 2.0 2 0 2 0 2.0 2.0 2 0 2.0 2.0 2.0 2 0 2.0 2.0 2.0
Cocodietbanc lamide 2.0 20 2.0 2.0 20 2.0 2.0 20 19 20 2.0 20 2.0 20 2.0 2.0 0 0 20 2.0 2.0 2.0
Sodiuma,cetate - 20 20 20 20 20 20 20 192 - 20 20 20 20 20 - - 20 20 20 20
SodiurnCjtrate 3.7 1) 17 17 17 2811 17 17 17 17 17 - 30 30 50 30
Sodium Carbonate - - 10 - 10 - 10 - - - - - - - - 10 - 10
Sodium Chloride 10 10 10 - - - 10 - 9. - - 10 - 10 - - . -
Sodium Sulfate 10 10 - - - 9.6 - - - - - - - -
Trisc.dlw, Ultrilotr I
acetate ( 1ITA) - - - - - - - - - -
Tergitol - - - - - - - - - - - - S -
Seqiene - - - - - - 10 10 - -
Sodium Gluconate
GantretAM 119 - - - - - - - -
Weston - - - - - - - - - e - - -
C pUB . p 1 17
total SoltdsC Jj_ 74 74 71 (.5 JL S. .21 1Q2_ .2L S.. .2 k .. St . 1k. .1k. SL . 1k .21- . 12... .21.. .2i. . 1k..
Rank: 6 lIST Clork (63) 13 19 42 14 24 25 37 46 20 36 27 31 5 31.5 15 22 2 58 35 11 6 9 1
CMPA cloth
(59) 17 38 37 45 45 35 12 33 20 13 25 22 29 24 25 51 3 56 43 57 Cl
Conbined
Cloth (59) 7 45 22 43 45 31 25 33 27 10 32 26 13 17 2 55 6 49 23 52 16
-------
T .ble 2 (Cent.)
Com o e ts 79 80 81 103 104_ ) Q !IL ILL ilL lii .. 1fl fl fl A 1 12P_ j .1L ILL IlL. 121.. ilL. 1LQ 122.
b N N N N N N N N N N
Silicate 10.1 10.1 10.1 5.0 5.0 5.0 5.0 10.1 10.1 10.1 1.0.1 10.1 5.0 0 0 10.1 10.1 10 1 10.1 10 1 5.0 5.0
Carboxylnethylcellulose 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2 0 2.0 2.0 2.0 2.0 2 0 2 0 2 0 2 0 2.0 2.0 2 0
Cocodiethanelamide 2.0 2.0 2.0 2.0 2.00 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Sodium Acetate 20 - 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20
Sodium Citrate 17 20 20 30 30 -. 30 30 30 20 - 20 20
Sodium Carbonate - - - - 10 10 - - 10 - - - - - - 10 - - - - -
Sodium Chloride - 10 - - 10 10 10 10 10 10 10 10 10 10 -
Sodium Sulfate - 10 10 - - - 10 - - - - 10 10 10 10 -
Trisodiuzn Nitrilotri
acetate (NTA) - - - - - -
Tergitol - - 5 - - - - -
Seqiene - - - - - 10 - - - - - - - - - - -
Sodium Gluconate 10 10 10 10 20 10 - 10 10 10 17 20 20 20 20 - -
Gantrez-Nl 119 - - 1.0 - - - 1.0 1.0 - - 1.0 5.0 - -
Weston - - - - - - - - - 10 10
Total SO1IdSC _IL _ .i _ .I _21_ 2 .. _2 .L . . . 2_ _2L_ _ LL i _ 2_ . .i _ i2 _ 1L _il_ i _ L j2_ jL 1L 12_ _J 7_ Brand
Rank:d UST 56 57 5 12 17 7 15 63 50.5 60 55 62 23 10 3 26 34 54 40 21 8 4 61 44
£MPA 10 30 34 21 50 36 52 18 48 23 9 28 53 27 25 54 42 15 32 31 39 44 59 49
Combined 34 50 14.5 5 42 8.5 36 39 53 41 12 47 48 8.5 4 51 44 35 39 5 30 18 31 59 54
aMl formulations contain 20% surfactant.
b star silicate, except as otherwise noted.
CTt1 solids include 20% surfactant; balance = water.
6 Weighted rank values; Pigures in parentheses indicate total number of samples ranked n set: 1 = worst, highest value = best.
eTitrated i-c p147 with citric acid.
-------
T.btr
FO COI 0UND i1281°
.ic . _A _ _LL .1t. .J.L -IL - --SQ. . - .L .. .tL ..±&. . . I_ ..Jt.. IL ..22_ ..2A_ .AL J1
N N Ii
10.1 10.1 9.8 10 1 10 1 10 1 10 1 10.1 10.1 10 1 30.1 0 0 10.1 10.1 10.1 10.1
C.rbo thyiee11%&1o.e 2 0 2.0 1 8 2.0 7 0 2C I 2 0 2.0 2.0 2 0 2.0 7.0 2.0 2.0 2.0 2.0
cocod1.th.t 1 e . 1de 2.0 2.0 1 8 2.0 2.0 2.0 2 Z 2 C 2 0 2 0 2.0 7 C 2.0 2.0 0 0 0 0
5odLi Acetete - - - - 20 20 - 20 23 20 23 - 20 20 - - 20 20
Sodt, Citrete - - - - - 20 20 7: 20 7C 23 2 20 20 20
Sodiwt Carbonate - 40 3C - - - - - - - - - - - - -
Sodiom Chloride - - 10 IC - 10 10 IC - 13 - - - 10
Sedi c Sulfate 20 20 3.8 10 IC - - - 10 - - - - - - -
?risodL iLl triloti-
acetate ($TAJ - - 15 - - - - - - - - - - - - -
?srgitoi - - - S S S
$s lene - - -
Sodi Gluconate - -
Oantrez-AN 119 - - - - - -
Weston - - - -
Thtal SoildaC 5 ii - 6 _).L. . .J2_. _2i_. . 2_
Renk:d UST Cloth (53) 7.5 3 21 39 36 20 22 9 3.2 19 23 33 6 16 38 17 4 2
A Cloth (471 27 28 42 43 Ii 22 30 37 26 14 15 24 9 46 39
Combined Cloth
(473 33 32 41 43 2 15 29 36 31 7 10 26 6 44 30
-------
Thole 3 (cont.)
88 2L L 2 2Q iQL !Q2 !2 i L IQL ! 2
sijicateb 10 1 10_i 10.1 10 1 2 5 10.1 tO 1 10 1 10.1 10 1 10 1 10 1 10.1 10 1 10.1 10.1
Carboxymethylcellulose 2 0 2 0 2 0 2.0 2 0 2.0 2.0 2.0 2 0 2 0 2 0 2.0 2.0 2 0 2.0 2 0
Cocodiethanolamide 2 0 2 0 2.0 2.0 2 0 2.0 2.0 2 0 2.0 2 0 2 0 0 0 0 (1 0
Sodium Acetate - - 30 20 20 20 - 20 20 20 - 20
Sodium Citrate - - 20 20 20 20 30 30 - 20 20 -
Sodium Caroonate - - - - 20 - - - - - - - - - - -
Sodium Chloride - 10 - [ 0 - - - 10 - - 10 - - - - -
Sodium Sulfate 25 20 15 25 25 25 10 -
Trisodium Nitrilotri-
acetate(L4TA) - - - - - - - - -
Tergitol - - - S - - - - -
Seq lene 10 10 - - - - - - - - - 10 10 10 - -
Sodium Gluconate - - 10 10 - - - - -
GantrezM4 119 - - - - - - 1 1
Weston
rj
Total SolidsC 44 54 44 54 76 99 99 99 79 89 99 62 82 92 33 S3 Brand AHAM
Rank:d UST 43 42 44 30 25 13 1 18 14 10 ii 50.5 7.5 15 49 52 53 46.5
EI A 18 7 4 5 29 23 10 35 38 41 44 20 32 40 21 19 47 45
CombLned 21 14 8 5 23 16 4 24 28 34 38 37 20 40 35 42 47 46
aAll formulations contain 20% surfactant.
b,,st., silicate, except as otherwise noted.
CTt1 solids include 20% surfactant; balance = water.
dweaghted rank values: Figures in parentheses indicate total num3ez of samples ranked in set: I worst, highest value best.
e3.ltrated to pH7 with citric acid
-------
Table 4
}ORI4ULAT1ONS FOR COMPOUND 21 2 a
.2g .. ... .. L L _ii. .ii 4L L .4L J8 L 4_ . S7 68 9 74 89 90
b N N N N
Silicate 10_i 10.1 10.1 10.1 9.7 8.8 20.2 20.2 20 2 20 2 20.2 10 1 10 3 10 1 0 0 L0.1 10 1 4.2 5.0 5 0
Carboxy thyLce11u1ose 2.0 2.0 2.0 2.0 1.9 1.7 2 0 2 0 2 0 2 0 2 0 2 0 2.0 2.0 2 0 2.0 2 0 2.0 1 7 2.0 2 0
CocodiethanoL ide 2.0 2.0 2.0 2.0 1.9 1.7 2.0 2.0 2.0 20 20 2 0 2.0 20 20 2 0 0 0 1 7 0 0
Sodium Acetate 30 - 28.8 26.3 - 30 30 - 30 30 30 30 30 .. - 21 25 25
Sodium Citrate 17 17 17 - 17 17 30 17 17 168 25 25
Sodium Carbonate - 10 10 38.5 35.0 10 - - - - - - - - - - - 29.4 10 10
Sodium Chloride - 10 - 10 - 8.8 - 10 - 10 - - 10 - - - - - 8 4 10 10
Sodium Sulfate - - - - - - - - - - - - - - - - - - - - -
Trisodium Nitrilotri
acetate (eTA) - - - - - - - - - - - - - - - -
Tergito l - - - - - - - - - - - - - - - - - 5 - - -
Seqiene - - - - - - - - - - - - - - - - - - - - -
Sodium Gluconate - - - - - -
Gantrez-AN 119 - - - - - - - - - - - - - - -
Weston - - - - - - - - e - - - -
p 1 4? p i9+
Total SolidsC 81 61 61 54 100 100 54 54 74 84 44 81 91 94 73 71 3_ .J.L 122... .11.. .. i.
Rank:d US? Cloth (57) 4 7 6 2 18 31 14 17 28 38 3 36 30 8 5 21 1 10 25 46 43
E WA Cloth (S6) 35.5 22.5 32 11 30.5 35 26 6 5 6.5 22.5 28.5 27 30.5 36 18 24 20 18 49.5 44 38
Combined Cloth
(56) 20 14 25 3 22 33 21 5.5 10 9 16 24 305 26 11 7 12 15 43 49 42
-------
Table 4 cont.)
Co , onent s 91 92 9! )4 jS .. ...2L ilL il .. JJ2_ JL. UL lli Lli.. L L. i L lU.. UL
siit .t,b 10.1 10.1 10 1 10.1 10.1 10.1 5.0 10.1 10.1 5.0 10.1 10.1 10.1 10.1 10.1 10.1 10.1
Carboxymethylcellulose 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.C 2 0 2.0 2.0 2.0 2.0 2.0 2.0
Cocod lethano lanUde 2 0 2.0 2.0 2.0 2.0 2.0 0 0 0 0 0 0 0 0 0 0
Sodiw I.cetate - - 20 - - 20 20 - 20 20 30 30 20 - 20 20 20
Sodiwr CLtrate - 3C - 30 30 70 - 20 20 30 20 70 - 20 70 20
Sc.dium Cerbo-iste - - - - 10 10 - 10 - - 10 -
Sodium Chloride - 10 - - - - - - 10 - - - - - - -
SodiumSu l f ate - - - -- - - - - - 13 - - - -
Trlsodi.w Nitrilotri
acetate (NTA
Tergitol
Leqi ene
Sod1 cr Cluconete
GentrerAZI 119
WestOn
44 1L - 2i - 22 L 2L !L !L !L 2L - .IL 2L sn4
54 55 15 20 19 36 37 53 33 42 26 35 29 9 12 23 24 57 45
13 15 37 a 43 4 7 46 21 Sq 49.5 48 51 53 42 40 5 45 56 41
27.5 30.5 37 6 40 48 46 32 54 53 44 52 50 39 38 51 41 Sό 45
CAll jonru LatLons contain 20% surfactant. -
b_star_ silicate, except as otherwise noted.
CTOtI solids Include 20% surfectant; balance water.
4 weighted rank va1 es Figures in pertr.theses indicate t ta1 number of samples ranked in set: 1 worst, highest value best.
eTitreted to pHi with citric acid.
I )
U,
10 10 10 -
- - - 1 7 10 10 15
Total So1
RCOJ;d o
Combined
15 10 -
1.0 1.0 1.0
- 10 - - - 10
1.0 - - - -
- - 10 10 10 10
-------
tables. The lettered formulations listed in Table 1 were
used with each o the three surfactants while the numbered
formulations in Tables 2-4 were used only with the parti-
cular surfactant indicatea in the head ng. Table 5 gives
the sources and grades of the formulation components used.
Detergency Evaluation
The relative effectiveness of the formulations was
determined on the basis of measuring the reflectivity of
the soiled cloth surface before and after washing. A
Hunterlab Model D40 ceflectometer with green phototube was
used Eor this purpose. The instrument was calibrated
against a standard grey tile before each series of measure-
ments. Tests showed that use of the green sensitive photo.-
tube avoided interference from the optical brightener
contained in the commercial detergeflt brand used as a
reference standard, so that it was unnecessary to use an
ultravioleL filter in the light path. Two readings, taken
at right angJ.es to each other relative to the warp of the
cloth, were made and the detergency values calculated as
the average of all the readings taken on the three
swatches of the cloth used in the test. In the case of
the combined washings, the two types of cloth were
evaluated se arate1v.
All the ietergency data cited in this report is in re-
flectance units (RU) expressing the difference in re-
flectance ( RL.of the c1 th before and after washing.
This deparLure from the previously followed practice of
reporting detergency in terms of percent soil removal
(%SR) was made for two reasons. It was desired to have as
sensitive as possible a means of differentiating between
the relative effectiveness of tha various formulations but
the calculation of the %SR, which involves a multiplication
by a factor of 100, tended to magnify any small errors
and lack of precision inherent in the method. Secondly,
it was realized that, since there is no simple, direct 1:1
relationship between the change of reflectivity and the
actual amount of oii removed, the expression of %SR, as
previously calculated according to the equation
%SR = (R -R /R -Rj x 100
w S 0
where
Rw = Average reflectance of the washed cloth
R = Average reflectance of the unwashed soiled loth
26
-------
Component
Carboxymethyl-
cel ulose
Cocodiethariol amide
Sodiun siJic te
SodLuM cetaLe
Table 5
FO RM(JLATION COMPONENTS
Source
hercules Inc.
Stepan Chemical Co.
Philadelphia Quattz
Co.
Celariesc Chemlcdl Co.
(a15 o I &A}
F{ itp hi re Chemical Co.
n&
3& A
E &
B&A
Lσr oco
Lqion C rhid
Pf r j hl Lsb .
Ptar tieh1 Lets.
_ ecifications
Type 7LT
Niriol 128
extra
1
C-,
i olut ior
ec n ceL
eaaC : L
ri/ . ::
nhyz ., reacerL
C y - a] s,
C- C O
Crc els,
r ec u
Slurry. C5 0
15 S -9
5. (j, Crv tals
Cp
Ti;odium cilrilo
ii- ec L ate
.cd iu carb rie
Sodi m chloride
oc.Lum SLJ f itr
odiint citrate
I..ir eaL- alkyl
3eo2eresu1±or. -e
Te c itoi
eq1ene
Sodi uin
d-q lucori ate
a
can trezT C AtI-j19
d
we tonT Bo -WaCner 70 S. powder
aT O crades were used: Scar SiO 2 / a 2 O ratio = 2.5 and N
S10 2 /Na 2 0 ratio = 3.2.
bFor purpose of formulation their weight percent was ca1c u1ate iJ
on the basis of the solid content of the so1ut cn.
Cweight percent of components containing water of hydratioti
were calculated in the formulations on the basis of their
anhydrous form.
dTdkd products were used as i arid no corrections
in the weight percent in the formulations was macye to
account for any moisture content.
27
-------
R = Reflectance of the unsoiled cloth
0
was somewhat misleading.
Although these commercial cloths gave reasonably consistent
results throughout each lot (usually 50 yards) purchased,
there was occasionally a significant difference in the
detergency behavior of different lots. 1hile the initial
reflectance values for the soiled cloth for the first two
lots of EMPA were very close, the detergency values obtained
on these two lots for the ? J-LAM and Brand reference standards
were significantly different. For example, at 50 ppm
hardness t.he performance of AHAM is strictly linear and
independent of concentration at 44.2 RU on bolt *2 while on
bolt *1 the maximum was 39.9 RU at 0.1% and decreased to
36.4 RU at 0.5% concentration. Similar differences are
found in the other two hardness grade waters. Figure 4
shows in bar-graph form the differences between these two
lots of EMPA cloths. Figures 5-7 show similar differences
for AHAM on 6 of the 12 different lots of UST cloth. This
variation of behavior of the same type of cloth from bolt
to bolt makes the evaluation of soil removal data .for the
various formulations rather difficult when the formulations
to be compared were run on different bolts. With such
large differences in soil removal for different lots of the
same cloth, it is obvious that both direct comparison of the
graphically represented data and the numerical detergency
values would be extremely misleading, since both of these
comparisons are dependent on the relative ease with which
a given bolt is cleaned. Thus, .Eor AHAM on ENPA, for
example, in the case illustrated above a detergency value
of 36.4 RU does not necessarily imply lower effectiveness
of AHAM than does a detergency of 44.2 RU if the first value
was obtained on bolt *1 while the second value was obtained
on bolt #2 but simply reflects tiie differences in the
soiled cloth itself.
Several statistically valid normalization procedures are
available and are frequently used in analytical evaluations
where certain data variability can be traced to the
presence of one or more non-controllable or non-uniform
conditions in the analytical system. The specific
technique used depends upon the nature of the data and the
kind of nonuniform condition for which data adjustment is
required. In our case, this non-uniformity for which data
adjustment is required appears to be due to variations in
the relative ease of removal of the soil from the cloth
which, in turn, is primarily a function of variations in
the manufacture of the cloth. The variations in the
results obtained with a standard detergent, such as AHAM
28
-------
FLaule 4
( t t A}(j D014 I? tWO HATChES O EM A C1 O 1H
U. U. 2 U. .ini 0. DeteL er; in Wa h V .4ter
29
ii
I,
U
C
a
U
V
S .,
tr
a)
U
C
4,
5 ,
.4 -
0
-------
Figure 5
AHAM OU UST CLOTH
50 ppm Hardness Water
ljJ
0
a)
U
U
a)
1-I
a)
cx
a)
U
a)
S - i
0
0.3
% AHAM in Wash Water
-------
20
Figure 6
P HAM ON UST CLOTH
135 ppm Hardness Water
(A)
a)
C)
-I- . .) ru
C)
a,
4 - I
a)
--I
a)
C)
10
a)
4-1
- - I
0.1
0.2 0.3 0.4 0.5
AHAIV1 in Wash Water
-------
20
Figure 7
? HA1 1 ON LJST CLOTH
300 ppm Hardness Water
L,)
w
C)
4 )
C.)
-I
4-1
a)
-I
a)
0
a)
10
4-1
l -l
0
% AHAT1 LL Wash Water
.)
-------
or Brand, can be used as an index to the variability of the
soiled cloth, since, all other things equal, the differences
found with the standard must then represent the differences
inherent in the cloth.
Most of the more sophisLicated statistical methods of data
fitting, such as the Least Mean Square Fit technique, have
the disadvantage that they require the use of all the
available data. Thus, the process would have had to be
repeated, and all previous data readjusted, each time data
from a new lot of cloth was added. A number of simpler
normalization techniques were therefore tested statistically
relative to the detergency data available on this project.
While none of the methods gave perfectly matching normalized
data, the one described herein yielded data adjustment
which was well within the limitations imposed by the
precision of the analytical procedure. Usually in such a
normalization, one set of control data is assumed as
representing base line data and the remaining sets of
control data are then adjusted relative to this base line.
Since a sufficient number of UST lots were available to
permit the derivation of a reasonable average, it was
decided to use this set of averages as base line data rather
than any one of the cloth lots arbitrarily. A normalization
factor was then calculated for each lot of cloth by dividing
the control values into the base line values thus:
Base Line Value = K
(lot x)
Control Value
(lot x)
Normalization of the test data was then carried out by
multiplying the test results by the applicable normalization
factor. It was found that, due to a sensitivity of some
cloth lots to both hardness as well as detergent concen-
tration, best data adjustment was obtained by separately
calculating the normalization factors for each concentration
at each water hardness. The comercial Brand was chosen
as the reference detergent, rather than AHAM, because the
larger numerical detergency values obtained with it are
inherently less affected by small errors in the method.
Table 6 illustrates the results of this normalization for
the AHAM data for the first nine lots of UST cloth showing
both the raw as well as the adjusted data.
A full statistical evaluation of the detergency data to
determine trends and specific effects of various formu-
lation components was not within the scope of this project.
A simple ranking procedure was, however, used to gain some
insight into the relative detergency performance of the
various formulations. The procedure used gave relative
33
-------
aData for 300 ppm hardness water.
Op ,i .f . - ..: IC I L C C
.0? m v(r) e of i -id ol for L.ot 18
hNormalization factors based ?J-1N 1 data.
Brar d Control
Concentration
Lot No. 0.1 0.2 0.3 0.5
Not vai1ab1eb
14.5 18.2 19.6 20.1
13.7 18.1 19.3 20.4
Norma1i aL on Fact .or
for Coric r ?Lr3tion
0.1 0.2 0.3 0.5
1
2
3
4
5
6
7
8
9
Average
-i-I l 2 aw i. 1u
Cor.c .t r&ior
01 0.2 0.3 0.5
0.924 0.966
0.800 0.911
0.820 0.891
0.981
0.950
0.944
Not Available 0
9.5 18.6 14.3
8.2 12.0 16.2
9.9 13.8 17.6
9.9 13.4 16.2
12.1 17.5 18.7
10.9 14.5 17.2
0.930
0.775
0. 799
0.995
1.10
1.33
1.11
1 . 10
0.901
N-L. -.M orma1ized
Conc nt ration
0 1 0.2 0.3 0 5
w
10.7 IL 14.3
12.5 13.5 14.6
Not. -va lab1e
18.5
18.1
19.5
18.9
20. 3
19 . 2
1 .09
1.24
1.21
1.04
1.09
0.823
9.9 10.8 13.8
9.7 10.8 13.3
Not aileb1e
1 02 0.975
1.19 1.06
1.08 1.04
0.989 0.990
1.07 1.03
0.914 0.946
10 1
9.4
76
89
8.9
11.5
99
8.8
8.9
10. 5
9.8
13.4
16.7
17 4
16.8
15.1
16.1
16.5
15.7
17.4
16.4
13.5
11.7
12.5
13.7
12.8
16.8
13.8
10.0
10.4
10. 1
9.9
9.9
10. 3
10.0
16.4
16.5
16.4
16.0
16.7
16.3
16.2
16.4
16.4
10.8
10.9
10.8
10.9
10. 7
11.7
10.8
L0.0 10.8
13.8
13.9
13. 5
13.5
13.7
15.3
13.8
CDat6AR is in ref1ectsruc un]tS.
-------
rank scores for each of the formulations and could be
applied to determine relative performances at any one test
condition or overall at any desired combination of test
conditions.
The ranking was based on the detergency values which were
previously normalized to eliminate differences due to
variations in the different lots of cloth. The standard
Brand values, which were used as reference data in the
normalization step, were included in the data set to be
ranked. The formulation having the lowest detergency was
ssigried a rank value of 1, the next highest d rank of 2,
etc. Formulations having identical detergency values were
assigned equal rank thus:
Formulation Detergency Rank
Lowest 1
XA 10.0 15
XB 10.3 16.5
XC 10.3 16.5
XD 10.5 18
XE 10.7 20
XF 10.7 20
XG 10.7 20
10.3 22
XZ Highest N
where
N total number of samples ranked
This procedure permitted the assignment of equal rank
num rs to equal performing formulations while still main-
taining the relative positions of the other formulations
within the matrix so that the highest ranking sample always
had a rank value equal to the total number of samples in the
set.
35
-------
The formulations were ranked separately for each of the
12 test conditions, i.e., 4 concentrations at 3 water hard-
ness levels, used. This gave us an idea as to the relative
performance of each formulation with respect to concen-
tration at the different hardness levels.
In order to obtain an approximation of the overall per-
formance of the formulations at each of the 3 hardness
levels, the rank values for the 4 concentrations were
summed. The formulations were then again ranked on the
basis of these sums, thus giving an average rank value for
the performance of each formulation with respect to water
hardness. Alternatively, the detergency values could have
been summed and the ranking done on the average
detergencies, but the results would have been just about
the same.
Similarly, to obtain the relative overall performance
covering all test conditions used, the individual rank
values were again summed for each sample and the formu-
lations ranked on the basis of these sums.
The weighted ranking was done by dividi g the rank values
at each concentration by the appropriate factor: 0.1% = 1,
0.2% = 2, etc., then summing the values and ranking the
sums as for overall performance.
A combined cloth ranking was done to get a rough idea
about the average performance of our formulations relative
to the different kinds of soil provided by the two standard
cloths. For this, the corresponding detergency values for
the two cloths were added before the ranking step was under-
taken.
While this ranking system did provide some insights into the
relative merits of the various formulations, it should be
pointed out that the actual rank values are somewhat less
significant than had been hoped. This is particularly true
of the rankings of the detergency data for the UST cloth
where the performance of most formulations fell within a
relatively narrow range so that differences between large
numbers of these formulations were of rather little signifi-
cance. This fact led to low rank values for formulations
which nevertheless performed quite well compared to the best
ranking formulation. For this reason, it is recommended
that the rank data presented here be used with direct
reference to the actual detergency data for proper compari-
son of performance of the formulations.
36
-------
Results and Discussion
No great benefit can be derived from discussing separately
the results of each of the formulations tested during the
course of this project. Also, it would be presumptuous to
draw any farranging conclusions concerning the true
practical detergency of these formulations on the basis of
bench scale testing on either or both of the particular
artificially soiled cloths used for the majority of our
evaluations. The following discussion, therefore, is
limited to general considerations demonstrating the utility
of the candidate surfactants in the development of phos-
phate-free detergents of a type that avoids many of the
problems and hazards of non-phosphated formulations
dependent on conventional surfactants.
The weighted overall rank values are included in the tables
giving the composition of the formulations (Tables 15)
and detailed ranking of compound 112A is shown in Tables
79, while Tables 10 and 11 give summaries of the rankings
for Comp. 11281 and 212. Detergency values are shown in
bar graph form in Figures 8-31 in Appendix A. Figures
8-25 show the performance of the formulations at all the
concentrations tested, while Figures 26-43 show the per-
formance at the critical 0.1% concentration which is the
use level we would prefer to recommend.
Two events occurring just prior to and shortly after the
start of the current program greatly influenced the
approach to detergent formulation taken during this
project. One was the appearance on the market of several
brands of non-.phosphated detergents and the other was the
suspension of the use of nitrilotriacetate (NTA).
Experience with the nonphosphate products then available
pointed up some of the problems encountered with these
proprietary formulations. Aside from their high alkalinity,
which is undesirable for safety reasons, he high carbonate
content of many of these products caused, after several
washings, stiffening and/or roughening of the cloth, due
to the deposit of the insoluble calcium and magnesium
carbonates. We therefore deliberately limited the
concentration of sodium carbonate used in our formulations
to a maximum of 10% or avoided its use entirely. In fact,
e found that with our surfactants a high concentration of
carbonate was unnecessary. This is demonstrated by
formulations C and CC which contained 40% and 10%
carbonate respectively. For all three surfactants the
difference in performance of these two formulations is
small. Furthermore, ranking of the formulations indicated
37
-------
Table 7
DLFAILED PERPO824ANCE RA1IICINO OF 112.. EDRI4ILATIONS
1ST Cloth
NO. of
Samples L8ss N1& 1 2_. _&_ _&_ k &_. S . JL i_ -IL - 1_.k. A JL ..P_ _!L_ L. S_.. ..2S.. .2 k .2k .2L .JL. .JS. ..IL _.i. .S. .i.L i.L . L .it.
SO pp.s Water Hardness
O 1% 63 51 41 25 5 27 33 5 22 19 49 30 5 33 5 48 28 32 29 3.. 5 37 39 1 . 13 5 19 41 :. 50 5 33 43 .6 25 5 46 38 5. 37
O 2% 63 62 45 42 36 57 38 39 26 61 49 5 27 S .2 56 37 5 42 54 5 51 63 59 19 32 49 5 23 30 27 5 35 33 16 40 34 22 25
O 3% 63 63 55 53 5 47 59 7 52 25 5 60 53 5 22 56 62 45 38 61 29 -.8 58 3. 1 5 27 5 46 55 36 5 31 5 42 36 5 39 23 5 12 9 5 15
O 5% 63 63 57 41 5 50 53 6 62 21 45 47 14 5 58 60 5 54 -.1 S 59 3 17 60 5 23 (0 35 5 32 31 38 .6 .9 5 48 5 10 4 19 5 7
135 p p ... Water Hardness
O 1% 63 25 5 14 7 5 16 23 5 3 44 17 18 50 11 5 13 55 29 10 27 5 31 47 5 2 I I 5 23 5 15 19 20 2.. 56 2 S 35 5 37 .6 .2
O 2% 63 50 33 51 5 31 46 5 25 23 20 62 5 57 3 43 5 27 36 62 5 19 32 54 49 30 21 7 5 39 24 33 28 5 37 10 5 6 .3 5 .5 25 1 5
O 3% 63 58 44 5 60 43 53 28 41 16 62 63 38 5 38 5 50 61 34 41 51 5 59 46 5 32 1.. 35 20 23 20 25 39 20 ., 5 49 17 15
0 5% 63 58 5 52 58 5 50 S 53 24 5 54 11 61 56 16 49 48 63 55 -.0 35 60 52 39 36 41 23 18 31 20 9 20 29 5 32 5 12 3 5
300 pp... water Hardness
0 1% 63 23 5 9 33 5 3 13 5 58 22 36 5 26 S 11 33 5 7 6 63 55 5 55 5 59 62 2 13 5 5 9 9 IS 5 38 .2 16 5 13 5 23 20 5
O 2% 63 18 5 1 44 2 16 54 6 5 .8 5 58 54 48 26 12 5 63 61 11 51 45 62 3 5 3 5 16 10 23 5 1-. 2 51 20 25 5 25 5 42 5 46 5
U ) 0.3% 63 46 16 5 59 21 40 S 31 5 28 5 60 58 St 39 35 62 45 1 29 57 22 16 5 24 18 5 20 24 18 S 26 5 31 6 3 37 5 43 5 30 37 S
0 5% 63 58 39 60 5 43 45 14 S 37 4 62 49 34 5 41 48 52 24 5 63 23 55 S 37 30 34 S 27 5 24 5 26 27 S 30 22 9 S 45 37 14 5 12
We ighted Average Rank
50 ppm 63 63 51 33 32 49 13 28 36 47 44 29 42 50 37 5 40 53 34 .8 61 27 20 46 .8 26 27 43 45 2, 39 25 31 37 5
135 pp... 63 51 33 48 31 43 24 26 23 54 5 52 42 30 36 63 34 32 47 54 5 60 16 20 33 15 19 22 27 38 12 41 .5 28 18
300 ppm 63 37 5 47 6 27 45 17 10 56 56 48 5 23 2(3 63 55 36 44 62 53 1 4 12 2 14 9 21 40 IS 34 30 29 32 5
Weighted
Overall
Rank 63 61 44 41 29 47 18 28 30 52 49 38 33 45 50 5 43 .8 39 33 59 13 19 42 14 24 25 37 46 20 36 27 31 S 31 S
-------
Table 7 cont
t IL L 2L. .JL JL ,.LL ,.JL ..i_ .sL .IL s Q L 12s s QL s1L dL ia. I lL lfl. ut a a. ia. , l2 , ui_ Zi. ia ia. ui..
SC ppm Water Haz es
01% 16 ,2 S eS 35 85 1 53 55 23516 23536 m l 59 s 51 60 Ic i i 5513550 18 44 Li 55 6 5
5 2% 20 sO 1 ? 5 1 ± 5 4 6 2 a4 3 47 5 1 7 21 11 5 52 5 52 5 8 .7 5 4 5 1 s S 13 5 2. 30 46 30 8 5 .1 5 10
7, s% .8 23 5 I S 51 18 16 5 12 1 57 .2 2 6 6 3 4 _2 50 33 5 30 21 49 .4 15 8 .0 31 6 42 .37 5 s s 15 9 5
3 5% 5 . 4 1 40 .2 5 Si 5 31 35 5 10 22 35 5 14 - 6 .39 3 51 5 27 12 5 2 s 35 5 55 .4 Se 25 5 29 29 48 5 29 24
125 ppm Water tardress
1% 52 40 5 38 45 .0 5 33 39 34 3 1 4 3 58 47 5 32 .0 21 5 50 60 53 62 51 - 5 5 39 54 5 57 51 53 5 5 1
2% 22 35 555105 45105i2 t ISmOS 9 1.53 1±53 59 ,csss7..c5053 ,3265.e18 2
c 3% 10 73 2 56 44 6 5 4 12 .6 57 2 5 e 22 5 12 51 5 30 5 4 5 .8 54 5 24 6 18 16 37 10 5 V 1, 8 5
0 5% 9 7 5 2 50 5 34 14 9 15 7 .6 6 42 , 3 5 5 20 29 5 38 44 17 , 5 41 .2 5 2o 13 37 1 33 6 27 5 22 24 s :7
300 ppm #ater tardnese
C 1% .6 5 20 5 3 5 31 2 1 5 i3 is 28 5 78 5 36 5 39 5 41 26 5 -o 5 35 11 5 51 5 48 5 efl 55 5 3. , 48 5 .3 5 .3 5 c i 46 65 5 c 5 29 5 45
0 2% 36 5 49 34 36 5 27 5 38 5 5. 32 6 5 59 59 5 57 42 5 40 5 :i 5 34 5 5 0 5 29 51 3-. 2 . 5 30 5 27 5 46 5 30 5 56 12 5
3 3% 35 -3 5 26 5 50 40 5 10 9 14 51 48 63 .5 13 11 5 48 2 55 5 52 43 5 .5 Il 5 4 .2 24 48 33 53 5 3 8
0 1% 32 sO 6 50 41 17 2 6 13 5 S9 60 5 13 9 .9 5 21 55 5 1 53 5. 51 57 16 2 5 33 19 47 41 45 19 1 5
0 deighted Average Rank
SOppm l4S 2 s 3 .0 30 : 58 56 2 11 19 . 0 i: C 14 55 52 59 13 12 s :2 41 57 35 145 8 6
.3Sppm2S .s .3 57 .4 8 10 14 53 60 13 6 11 I 3 .9 66 mA 59 51 21 4 1 s9 19 49 46 .0 5 2
200 ppm 32 5 39 19 43 38 24 26 16 25 7 58 50 31 18 2 57 8 61 54 59 5 4. 22 1 48 5 35 51 42 59 5 11 :3
etgnted
Overall
3ank 16 22 1 58 35 6 9 1 56 57 5 .2 17 7 35 43 50160 5562 23 ,0326 s4 54 .0 21 8 4
-------
anle P
135T..IIED PERFS3RZ4AIICE RANKIUC OF 31 24. tk 1 .e ,cro .
EM?!, Cloth
1c, of
syitn 1rs 4 t l ! a. - 1 i- sc i_ .. SL £ .a .. .L.. 1_. - l .a. _cL .&. _ L _29_. - -a. ..a .a _ 2_
50 ppn Water Hardness
01% 9 t9 58 2 5 4 I I i3 43 5 2o6 5 565. .2 110 - i i .5...95. 29 17 50 21613 15 12
02% 59 g 365 3 4518552 to 8 5 .2 15 - 8 54 16 19. 551, 3. 55 7 .3 11 255c35c0 9
o 3% S9 57 18 0 . 5 10 5 15 35 11 25 S 4 5 0 5 56 - 13 5 5 3 12 5 29 17 51 .5 12 7 S 16 23 27 5 35 5 38 5
C 5% 19 58 12 5 52 11 8 , 18 44 20 22 5 39 5 57 ½ I. 3 9 c - :4 14 5 9 25 12 5 7 9 23 5 39 5 .3 35 5
135 ppm date , , ardress
0 5% 59 59 18 2 12 Il 1 26 2o , tO 9 9 .1 2 . 12 22 42 . s to 22 2 37 - , 5 29 33 17 29 5 .3 3
02% .9 59 57 753 4 20 2i 135 1.,5512511511-.i 3 32 17 90 to ts 5 5 435i25 4 1
23% 9 59 4252255 2 20 135.75 75 7514 13 59 . S45 1j45 s Irs, 9 5S2525 .863 054 41 .9
3 5% 59 59 .3 5 53 7 2 15 5 10 47 1 it .4 5 13 5 - 21 5 .7 - 15 18 5 6 . - .9 - S S I a .0 31 12 3 , 5 1 48 29 5
300 ppm Water Hardness
01% 59 59 52514 5 195: .0 .6 27 1 -22552 -.71.952° 171 9 ,,3.532 59 10532 2512 2 4
02% 59 59 58 14 1 6510 i7 11 6 19 25 46 -.27 0,1,,50:4:53,,757 .44 65 5 2 205
03% 29 59 15512 1 5 16 315395 5 6 .5 tS 57 __39 3 5 5: 7 50 .8 4 / 36 11 o 4 9 31 215
0 5% 19 19 .1 40 1 16 15 5 25 5 32 5 . 5 i4 3 .9 5 57 - - 2i.u,./4 5 .33 5 10 1 4. .3915:5 1159517 14
a
o Weighted Average Rank
lOppe 99 .9 44 5 1 s10 14 39 . 4 15 - .2 58 -55 15-.0 19 . 10 32 5 51.8 40 26 24
s3Sppm 59 59 55 165 25 1 6 27 .2 4 31 7 a 53 -.9 2 41 24 - 4. - : .0 22 6 9 25 fl 14 13
300 ppm 19 59 55 19 1 8 5 :8 s 3 1. 11 21 51 - - 7 14 .1 10 4 . 35 35 43 37 10 iS 7 16 _2
%esgited
Overall
Rrk 59 19 c9 a 1 I 7 .9 40 3 14 11 8 58 - 55 5 47 .7 - 39 .7 .5 46 35 12 33 20 13 2 cc 22
-------
Fai.1e 8 Icon p
_ Q J - fl 72 73 5 fl 21. _t. Q1. 1L. A lL AQI. I l L flL UI 1 -L. L ii _ U9 Ut 111. L2Q. i lL Ut. 421. UL I lL 1L i lL
SO ppm Water hardness
0 3% 39 5 25 32 44 11 53 37 5 55 41 19 30 16 265 51 29 5 45 5 37 5 .3 5 28 1 .6 i I I o 68 .3 S $ 35 24 34 73
C 2% 33 29 31 49 2 57 51 58 53 6 29 45 5 25 5 44 20 5 48 .i 7 i 5 4 - 5 42 27 29 50 23 22 40 0 5 41 52
C 31. 2. 0 5 58 5 i 5 5 s 15 43 5 6 34 51 14 46 32 - .8 12 47 2 5 27 5 -.3 5 9 jO I 2. 5 SI 36 5 21 5 36 S 40 33 53
C 5. 23 5 10 59 41 54 .9 55 29 S 53 46 51 16.5 .8 -.2 33 5 3 2 I 41 7 ls 5 14 5 35 1 32 6 8 33 5 21 50
125 ppm ater
0 f. Q (5 5 56 14 5 2 C 36 5 35 5 5 16 [ 4 17 5 48 5 1/ 5 42 20 IS 5 24 54 15 5 53 24 30 55 51 34 4 50 40 19
I 2% .3 24 5 6 .9 5 2 27 5 47 53 .,5 1 14 21 5 24 5 34 .3 56 5 37 29 30 5 15 5 55 II 35 5 49 5 35 5 26 18 30 5 .6 49 5
1 35. 33 26 5 13 5 38 1 22 5 j7 75 5 -.1 5 6 IC. 15 5 . S Sb 33 5 7 5 33 5 18 5 17 t o .1 5 tl 5 51 5 41 10 22 5 2.. 5 49 53
O 51. 71 24 5 11 33 1 38 5 53 . 6 (7 36 5 34 5 13.5 47 5 39 b 4 5 51 29 5 31 5 36 3 52 45 fl 5 50 55 15 26 5 41 26 5 47
300 ppm Water #ardness
0 1% 3 7 10 5 18 a s 58 26 .6 8 5 iS 21 24 5 30 41 6 54 51 57 13 -.5 5 47 a .9 5 54 49 5 -.8 -.S 5 56 34 5 44
a 0 3% 13 s 11 20 5 4 56 38 50 15 U 29 .1 27 5 42 1 2 48 12 57 3. 5 35 .4 5 54 9 .7 52 65 36 5 26 40 49 53
3 p% 26 5 17 10 28 5 2 54 5 41 45 5 19 19 37 52 25 34 5 19 4-. 7 54 5 23 5 15 i4 I 3306530 5 56 l B 5 23 5 33 14 5 58
0 5% 18 29 1 6 5 35 2 Si 27 [ S 5 11 28 5 50 55 5 49 5 30 n3 38 6 5 47 5 .3 S I 9 5 45 21 2 42 5 36 2 5 23 37 53 49
Wesg5.ted verage Rank
50 p n 34 27 25 53 6 55 45 57 46 s7 31 33 21 52 7 .9 22 13 19 2 29 8 .13 10 51 10 11 -.1 28 36 12
133 pps 19 39 4 11 11 38 36 50 .8 2 5 15 24 16 5 44 39 14 5 .. 28 37 13 57 . 3 0 56 53 21 .3 40 46 45
.30 ?p 43 iS , 25 2 58 31 .Q 9 38 32 46 23 5 40 22 50 20 ? 26 13 5 29 53 34 .9 54 2 38 27 48 .7 56
Wenqnted
Over all
tank 29 24 16 51 3 56 43 57 41 10 30 34 21 50 36 52 18 28 23 9 28 53 27 15 54 42 15 32 31 39 44
-------
Table 9
DtFAILED PERIURnAICE BA8X1I OF 112A OV8I4ULATIONS
Coehined Cloths
No Of
Sa1 ples Brand A llAN 0 A E L C CCH 1 21 F 0 J IC B N N 0 24 iL .J&_ .AL ..IL ii. .Ji. . 4 1. .JQ_ i L. .iL ii. .iL
SO ppn Water Hardness
O 1% 59 59 58 2 3 16 4 S 13 44 8 10 5 37 5 7 56 53 6 19 57 6 36 2B 43 51 34 5 39 45 5 30 23 33 34 5
O 2% 39 59 48 5 3 1 42 21 27 5 37 37 27.3 13.5 - 24 33 5 - 58 49 5 55 5 10 44 29 54 46 5 49 5 11 16 5 25 5 13 5 22 5 33
O 3% 59 59 43 20 5 9 28 5 2 37 5 30 39 46 4 52 5 57 56 12 5 46 23 41 23 51 41 46 7 5 26 17 15 21 26
O 5% 59 59 38 53 25 5 25 5 2 5 46.5 34 5 30 5 36 4 54 SB 48 5 5 46 5 20 5 - 33 11 39 30 6 20 5 6 5 20 5 10 16 32 15
235 ppe Water Hardness
O 1% 59 59 47 1 3 9 5 2 B 36 5 12 16.3 29 5 6 49 22 5 22 5 44 3 - 28 13.5 15 22 31 45 24 56 38 5 29 5 18
0 2% 59 59 56 29 3 7 5 16 15 32 41 5 39 20 5 14 SB - 55 73 5 50 7 5 - 53 34 12 26 3 46 47 18 34 20 5 48 5 10
0 3% 39 59 30 52 4 6 5 23 42 33 48 57 29 3 40 SB 16 44 5 51 54 - 49 23 6 5 9 19 27 11 5 46 13 5 79.5 23
0 5% 59 SB 50 57 30 9 5 17 53 5 31 49 53 14 5 37 5 69 66 47 5 40 41 47 5 23 5 B 14 5 19 20 11 14 5 5 21 5 9 5
300 ppe Water Hardness
0 1% 59 56 6 40 10 5 3 16 S 2 33 36 S 20 21 5 18 14 50 38 39 46 5 . 31 14 24 23 27 5 16 5 35 5 19 7 5 1 6
0 2% 39 59 39.5 21 1 3 17 3 14 42 11 9 24 5 11 38 30 7 3 40 5 24 . 21 7 5 17 S 27 5 21 27 5 36 5 6 4 5 27 5 24
0 3% 59 59 42 41 1 7 19 19 13 5 13.5 21 38 5 23 57 49 5 26 5 53 17 39.1 49 S 51 43 5 45 11 9 5 a 5 12 38 26 S
0 5% 69 59 52 56 2 29 5 6 5 33 5 13 27 44 16 5 36 5 58 - 54 45 47 5 47 5 - 60 6 33 5 23 40 36 5 12 5 12 6 15 20 8 5 5
Weighted Average Bank
SOppa. 39 59 53 9 1 28 2 26 44 20 21 19 24 58 57 23 36 6 42 29 30 49 41 22 35 25 15 31 32
136 pp .0 19 59 55 32 3 2 7 27 37 40 43 21 19 5 58 - 49 35 51 22 5 - 47 21 5 14 31 42 11 4 18 36 9
300ppe. 59 39 47 323 1 8 3522326312 lB 20 16 58 32 30 54 15 - 37 22529 35 34 11 22 7 4 14 9
Weighted
Overall
BanS 59 59 54 11 1 16 5 3 24 38 21 29 19 20 58 57 28 56 7 - 46 22 43 45 37 26 33 27 10 32 26
-------
rdt.1, n tort
S L. .JL L. JL .2L .21. _IL .21. S. 5 121. AQs. 191. LU_ £11 I lL ,Jt. sO. lit Ut £11. -2L i lL UL UL Us. I lL IlL 21.
50 ppm Water H.,rnness
o in 25 15 17 .7 34 41 22 9 21 37 S .5 S 5 18 31 ° 55 aS a 50 52 11 5 12 9 11 5 48 27 o 1 . 23 10 5
2 211 lb 5 O 7 37 3 55 43 5 53 31 5 20 35 9 4 30 S , 5 ii S. S 52 3 5 39 I 14 5 9 13 5 .6 S 25 5 39 .3 5 22 40 5
O 3% _5 I5 58l0.2 5 54 5 11 23 1 32 5 5 i i 5 7 5 36 26 .6 19 5 .9 52 , 54 l1 54 5 35 34 31 32 5 19 5
o S n 17 Ii 1 56 25 a 57 .6 5 15 13 50 .2 .0 8 .5. a S s 5 13 23 2 5 34 5 51 25 5 9 52 8 5 28 5 i7 42 20 5 .2
135 ppm aater Hardness
fl 1% 33 25 16 S 57 al 5 41 5 C 36 S 35 19 1 .3 32 15 5 3. 7 26 36 54 50 59 53 16 5 9 5 11 15 52 19265. 13 5 4
o 2% 31 29 2 57 5 5 29 37 :3 5 1 43 5 sO 14 13 ,n 23 5 53 52 53 19 .4 26 5 10 49 5 39 .1 5 34 .5 23 5 1 8
0 3% 9 13 S 2 15 3 5 11 5 16 55 13 5 38 17 1 20 5 i i 79 35 S 36 5 , 2 47 42 18 9 .4 5 29 5 20 S 25 5 25 1 35 29 5
0 5% 7 25 2 5 44 1 26 a 4 3 5 28 5 32 .2 14 5 5 33 5 23 5 46 12 aS 5 11 39 .4 53 S 36 16 44 2 S 21 5 28 5 33 5 2 ° 5 35
300 ppm Water 9erdnass
a 0 1% 4 3 9 27 5 14 38 25 32 30 5 21 5 26 29 5 29 5 35 5 12 53 53 59 50 47 S 50 5. .1 43 55 45 47 5 56 5 35 1 .2
(A) 0 2% 16 37 5 31 39 5 57 47 52 23 33 5 42 52 31 5 44 5 2 .4 5 54 4s 19 5 35 52 ab 31 5 13 5 54 55 39 30 48 5 36 5 2
0 3% 32 S sO 9 49 2 34 5 19 33 4 5 59 5 55 58 32 5 16 23 2s 5 15 26 5 46 5 30 34 5 36 5 9 5 3 Se 54 .6 5 30 52 a .3 5
0 5% 22 24 5 3 50 5 1 40 9 5 39 4 53 57 40 10 lB S 31 24 3 22 lb 1 33 5 aS 5 27 55 14 6 5 47 5 21 .2 5 33 5 47 5 42 5 29 5
We Ighted Average Rank
50 ppm 16 ±3 4 55 10 51 27 54 17 36 40 12 1 .7 11 37 45 52 33 3 38 39 9 S 46 40 34 43 14 18
135 ppm 19 5 10 3 57 9 it 24 34 26 !0 46 33 4 28 12 1 33 54 56 52 5 50 46 I l 6 52 5 38 39 29 45 22 5
300 ppm 13 17 3 38 2 53 25 31 5 5 39 5 49 50 5 26 5 31 10 42 28 43 47 36 45 55 24 _9 57 50 5 41 39 5 56 32 S
We ighted
Overa ll
Rank 13 17 2 35 6 49 23 52 16 34 50 145 5 425 8536 395S5 43 12 .7 68 95 51 44 35 39530 18 31
-------
Table 10
SWO4ARY OF PCRFOR24MCE RANKING OF COMPOUND 11 281 FORMULATIONS
No of
samples Brand ANAI I C A 1. C CC K 2 11 F 0 3 K B N N o 20 ._LL. AL 2L _2L At. it.
0 1% concentration
on l iST Cloth at
SO ppm 53 49 44 19 5 26 39 2 5 10 5 40 31 5 35 5 46 16 25 14 17 5 37 31 5 50 22 10 5 3 27 47 48 24 28 5 5 5 2 5
135 ppm 53 28 6 5 12 3 19 5 32 3 39 1 14 15 49 5 9 1 23 5 26 3m 35 16 43 4 2 1 23 5 21 5 32 26 36 37
300 ppm 13 31 5 18 18 15 5 20 5 36 S 6 S 2 28 5 11 5 46 23 5 4 44 47 IL 5 43 40 5 48 3 6 5 5 9 28 S 23 5 33 3 33 5 40 5
on ENWA Cloth at
50 ppm 41 47 46 3 4 23 23 9 3 13 9 5 2 27 43 1 5 11 3 45 29 28 36 39 30 34
135 ppm 47 47 46 39 7 19 27 44 24 19 14 42 34 10 30 25 3 22 24 35 5 iO 41 29 6
300 ppm 47 47 45 17 5 11 25 5 37 42 34 3 25 5 15 44 24 17 5 - 39 21 13 20 27 36 32 40 29
on Corilitned Cloth at
SO ppm 47 47 43 5 2 5 4 24 9 5 1 18 5 9 5 5 29 S 44 7 11 5 18 5 45 34 32 29 5 16 9 22 73
135 ppm 47 47 41 5 6 13 23 41 25 5 9 9 43 16 32 16 35 5 - 19 5 3] 38 39 5 30 5 11
300 ppm 47 46 40 15 I I S 23 5 16 37 18 5 25 .5 11 5 42 22 6 3 - 39 27 29 - 13 5 25 5 30 5 28 38 32 5
P Weighted Ranking
on liST Cloth at
SOppm 53 53 51 28 38 47 2 25 32 44 37 16 30 41 24 22 50 26 52 35 tO 5 33 46 43 20 29 9 8
115 ppm 53 51 28 42 26 41 17 5 22 43 46 45 44 19 29 25 20 32 30 38 5 40 11 30 9 33 23 5 23 5 52 5 15 31
300 ppm 53 43 5 13 46 5 34 27 37 12 7 50 39 5 49 30 18 5 4] 5 46 5 27 35 23 38 6 2 3 21 22 20 15 8 17
on EWA Cloth at
50 ppm 47 47 40 3 1 16 35 4 12 6 2 23 26 11 - 5 10 39 31 27 4] 44 29 24
131 ppn 47 47 45 6 1 12 30 31 11 8 5 33 27 19 - - 9 32 29 20 25 42 43 28 10
300 ppm 47 47 45 5 1 15 5 17 36 31 13 5 4 44 12 22 29 19 13 - 24 28 18 37 43 2
on Combined Cloth at
50 ppm 47 47 46 1 2 19 21 4 13 10 3 20 43 16 6 27 45 - 39 33 37 42 25 15
135 ppm 47 47 46 6 2 13 25 36 10 21 5 40 23 26 - 9 35 14 - 19 33 43 41 17 12
300 ppm 47 47 42 S 2 16 5 21 36 14 34 5 4 44 13 18 - 30 12 19 3 22 29 38 37 34 5 IS
Waiglited Overall Rank on
nET cloth 13 53 40 5 32 33 45 5 24 31 48 41 40 27 5 34 27 5 26 46 5 29 50 5 37 7 5 3 21 34 36 20 22 9 12
EMPAC 1oth 47 47 49 3 1 16 34 11 12 6 2 25 33 13 8 17 36 27 28 42 43 31 22
Combined C loths 47 47 46 7 1 18 29 11 12 13 3 27 39 37 9 25 45 33 32 41 42 22 15
-------
Table 10 (cont.)
L L QL 22 2L S S S S S S S S S 122 AQL IQL !QL QL AQL 12L 112
0 1% Concentration
on .J5T cloth at
50 ppm 8 15 22 4 38 43 31.5 12 8 42 45 41 31 5 34 22 8 28.5 35.5 19.5 17.5 50 5.5 13 52 53
135 ppm 51 45 48 46 5 46.5 44 29 5 29.5 12.5 41 32 21.5 18 38 39.5 8 41.5 10.5 10 5 19.5 49 5 34 17 52 5 52 5
300 ppm 31.5 20 5 14 11 23.5 30 18 11.5 23.5 1 27 36.5 26 36.5 42 8.5 45 33.5 36.5 39 52 49 50 5 50.5 53
on EMPA Cloth at
50 ppm 20 5 38 25 14 16 26 17.5 42 40 12 7.5 6 1 36 36 23 32.5 32.5 31 41 20.5 15 44 19 17 5
135 ppm 8 5 19 11 13 15.5 43 38 39 32.5 5 4 2 1 8.5 15.5 3 25.5 23 45 32 11.5 35 5 37 31 ±9
300ppm 15 13 2 8 7 23 19 9.522 6 4 5 3 15 9.5 1 28 32 30 34.538 41 46 43 32
on Combined Cloth at
50 ppm 13 27 20 6 21 25.5 16.5 41 36.5 16 5 15 11.5 2.5 34 28 14 31 34 25 5 42 5 39 5 8 42.5 38 39.5
135 ppm 30.5 28 19 5 23 28 45 5 36 5 36.5 16 12 7 3.5 2 14 18 1 28 9 44 21 23 35 34 42 39 5
300 ppm 17 13 5 3 6 8 23 5 16 9.5 20.5 2 5 9.5 4 18.5 20.5 1 34.5 32.5 30.5 34.5 44 43 47 45 41
Weighted Ranking
a on UST Cloth at
01 50 ppm 14 21 34 3 18 33 17 7 4 42 39 45 27 23 11.5 1 15 19 13 11 5 49 6 16 40 48
135 ppm 34 37 35.5 27 12 5 50 17.5 8 3 47.5 47.5 35.5 38.5 21 14 1 16 4 2 6 49 7 5 52 53
300 ppm 39 5 29 25 22 14 41.5 16 4.5 4 5 31 41.5 48 36 24 18 5 1 33 10 11 9 52 45 27 53 51
or EMPA Cloth at
50 ppm 33 37 32 14 15 23 13 46 45 19 9 7 8 28 26 18 30 34 38 42 20 25 41 22 17
135 ppm 26 34 22 21 17 35.5 16 44 37 13 7 3 2 24 14 4 38 39 46 41 15 40 35 5 18 23
30C .ppm 26 25 8 7 10 21 6 14 32 11 9 3 18 34 33 2 35 39 40 41 30 42 46 20 23
on Combined Cloth at
S0ppm 28 33 34 5 12 22 9 44 38 23 14 11 7 26 18 8 24 29 30 40 36 17 41 32 35
135 ppm 38 42 29 5 18 8 45 Il 39 15 22 14 4 3 24 7 1 29 5 20 37 31 27 28 16 32 44
300 ppm 27 25.5 10 7.5 7.5 31 3 6 11 19 5 16.5 9 23 28 25.5 1 39 24 32 33 46 40 45 41 43
Wo ighted Overall Rank on
USTC In1h 19 23 33 6 16 38 17 4 2 43 42 44 30 25 13 1 18 14 10 Il 505 7.515 9 52
EMPA Cloth 30 37 26 14 15 24 9 46 39 18 7 4 5 29 23 10 35 38 41 44 20 32 40 21 19
CombinedClotha 29 36 31 7 10 26 6 44 30 21 14 8 5 23 16 4 24 28 34 38 37 20 40 35 42
-------
table 11
SUIO4ARY OF PERFORX4AXICE R..NXI.G OF COMPOUI4O 212 FORI4UI.ntIO.iS
i so of
Samples Brand 555814 0 A j_ j,_ _η_ _η H I 41 ! 0 .3 C 0 I 55 0 28 29 30 31 42 i3 44 ..5 .6 47 48
57 54 50 42 21 43 5 14 5 41 10 5 52 36 17 22 45 5 48 39 28 37 45 5 50 i 4 5 2 27 39 .0 S 7 5 9 26 5 5
57 37 21 31 18 5 27 5 34 24 5 7 24 5 10 5 7 27 5 16 5 35 40 23 26 33 36 4 5 3 7 i 32 39 1. 5 9 20 15 4 5
57 41 37 35 24 29 5 27 5 39 5 5 32 5 31 5 5 22 5 29 5 42 34 19 5 27 5 32 5 37 l2 1 4 17 8 21 25 5 18 2 2 10 5 2
56 56 54 1 8 27 11 17 9 10 4 14555 2 42 45 14522 43 26 21 25 3 31 36 20 5 24 27
56 56 52 1 5 17 13 5 13 6 7 4 11 34 3 24 5 24 5 11 27 5 41 27 5 22 30 5 2 40 42 26 15 11 5 16 9
56 55 51 5 5 18 5 9 5 9 5 37 2 5 16 14 7 26 2 5 22 23 S 5 5 31 39 26 12 5 29 1 3., 42 23 5 52 5 4 20 11
56 56 55 1 9527 11 205 6 18 9513 54 5 43 15 20525 .9517 12 19 2 31 38 14 3 4 22 155
56 535 40 4 7 21 23 31 55145 25 9532 2530 33 17 29 37 22 14525 1 35 38 24 11 12 55 95
56 35 43 22 5 24 22 5 20 5 36 5 3 28 25 5 4 5 25 5 18 30 29 17 32 36 5 15 6 5 20 5 I S 33 35 16 6 5 1 5 4 5 12 5
Weighted Ranking on
UST Cloth in
50 ppm 57
135 ppm 57
300 ppm 52
EMPA Cloth in
50 pp.i 56
135 PP.. 56
300 pp. 56
Combined Cloth in
50 ppm 56
135 ppm 56
300 ppm 56
Weighted Overall Ranking on
l IST Cloth 57 57 45 48 27 50 5 11 44 13 56 34 22 32 50 5 52 41 40 39 47 49 4 7 6 2 18 31 14 17 28 38 3
EIWA Cloth 56 56 41 1 4 25 12 14 9 5 3 10 52 2 28 5 33 5 18 16 39 33 5 22 5 32 U 30 5 35 26 5 5 6 5 22 5 28 5
CombsnedCloths 56 56 45 1 7 34 13 19 4 18 55 9 55 2 35 36 - 23 27547 20 14 25 3 22 73 21 5510 29 16
O 1% Coecentrat ion
on LIST Cloth in
50 ppm
135 ppm
300 ppm
on EI4PA Cloth in
50 ppm
135 ppm
300 ppm
on Combined Cloths In
50 ppm
135 ppm
300 pm.
a
57 50 44 29 485 9 46 16 56 31 22534 55 52 40 42 43 47 51 5 8 6 3 20 33 12 18 28 37 33
56 35 55 23 50 33 43 38 53 44 27 20 24 45 33 43 21 54 29 2 5 9 3 13 22 28 30 46 47 10
50 26 5 49 20 37 5 35 42 31 5 51 S 23 14 30 39 5 51 5 43 11 5 25 28 39 5 24 21 15 6 13 lb S 26 5 5 9 16 5 4
56 39 2 7 30 12 13 10 8 3 11 55 1 27 36 19 36 41 33 20 29 9 24 31 26 6 5 23 34
56 45 1 3 16 23 25 5 7 4 6 495 S 29 24 21 20 39 32 22 38 9 35 37 27 34 12 18 19
56 50 1 3 12 16 38 13 6 5 8 33 2 29 S 26 18 22 34 32 28 37 14 5 35 5 41 31 7 20 10 5
56 45 1 9 38 5 15 7522 7530 55 2 34 39 24 25 51 23 12 2053 20533 19 6 11 32 18
56 48 5 3 6 27 27 23 5 4 Id I I 4 1± 1 1 39 25 23 5 29 5 41 i4 11 34 5 32 35 27 14 U. 29 5 16
56 41 11 5 23 5 23 5 40 9 5 19 12 e 38 9 5 35 26 5 21 22 36 30 25 31 13 28 5 32 26 5 3 4 15 5 8
-------
o 1% Concentration
Gn UST Cloth in
50 ppu 34 50 16 12 5 33 1 18 5 18 5 53 3 2 55 16 ii 5 24 20 13 36 57 35 43 1 2. 39 30 5 5 12 5 24 29
135 ppm 13 5 10.5 22 12 18.5 2 13 5 29.5 45 .8 38 42 1.7 29 5 .1 49 51 44 52 55 .6 53 54 50 43 56 47
300 ppm 15 8 8 2 S .4 30 5 lo 25 5 57 55 15 .4 22 19 5 r c 5 50 40 56 53 50 74 2 43 29 47 50
on DW :lnth in
50 ppm 32.5 32.5 3 2i. 29 fl 53 .7 40 13 i S 39 u iS ;9 5 .1 I 51 4b 4 8 .9 5 30 34 52 35
135 ppm 8 23 32 21 18 19 30 5 55 48 28 20 20 3: 14 15 fl 44 .5 47 50 51 53 46 39 37 49 45
300 ppm 16 16 21 8 38 5 26 29 So 49 .4 31 3 i3 30 40 45 49 3 54 52 50 53 47 41 44 38
on Combined Cloths in
50 ppm 36 39 33 24 28 8 15 5 65 53 40 26 29 5 34 3 5 .7 .1 5 29 5 2 49 5 41 5 49 5 45 23 32 49 5 36
135 ppm 9 5 20 28 s8 16 8 26 .4 .5.5 41 27 3- 56 1° 36 43 47 Si 549 51 50 55 48 .2 39 52 45 5
300 ppm 12.5 9 10.5 3 12 5 14 s8 5 53 54 49 39 5 39 :; 38 .5 s _; 5 34 So 51 50 52 ..7 5 42 44 .1 45 5
Weighted Ranking on
UST Cloth in
22 5 39 10 7 25 2 33 27 45 39 53 5 14 15 17 32 35 48 5 30 41 21 36 26 4 11 19 24
6 11 7 4 18 5 3 8 16 11 49 51 52 17 18 14 41 39 57 33 41 25 41 36 37 12 26 18 5
19 7 9 2.5 9 1 2 5 22 57 5.. 55 56 31 18 32 48 44 5 53 44.5 41 36 37.5 46 47 34 33 29
32 28 35 18 22 25 23 50 44 38 1. 15 .0 43 8 47 17 53 49 46 52 51 45 37 54 42
10.5 31 33 26 28 8 13 41 46 36 15 17 34 10 5 44 43 42 30 49 5 51 55 47 54 40 48 53 52
21 25 29.5 10.5 19 9 14.5 54 43 40 23 24 35 5 37 42 45 52 5 27 55 44 52 5 46 47 39 48 49 51
31 30 27 13 1 16 1 46 49 .2 26 29 36 4 40 48 4. 28 54 53 43 52 47 37 35 50 41
8 31 22 12 20 2 9 36 43 44 17 21 3 19 37 45.5 45.5 38 51 52 5 54 50 55 42 40 52.5 47
17 18 20 3 14 2 6.5 49 54 46 34 33 37 15 5 39 48 53 28 5 55 45 51 44 51 42 5 47 51 42.5
50 ppm
135 ppm
300 ppm
P2WA Cloth in
50 ppm
135 ppm
300 ppm
Combined Cloth in
50 ppm
135 ppm
300 ppm
Weighted 0#erall Ranking on
USTC loth 16 30 8 5 21 1 10 25 46 43 54 55 15 20 19 36 37 53 33 42 26 35 29 9 12 23 24
E!QA Cloth 27 30 5 36 18 24 20 18 49.5 44 38 i3 15 37 8 43 47 45 21 54 49 5 48 51 53 42 40 55 45
Combined Cloths 24 30.5 26 11 17 32 15 43 49 42 27.5 30 5 37 8 40 8 46 32 54 53 44 52 50 39 38 51 41
i Lie I I nit I
_ L L. fl V at t Ss At 50_ 91 °) 9 C . (3.. 125 I. ) I I i ; ii Ii i . 13L 1_3j
1
-------
t iat only with compound 212 did the use of carbonate appear
to 1 ve any beneficial effect.
The discontinuance of the use of NTA completely eliminated
this compound from consideration as a component in any of
our formulations during the present project even though
earlier experiments (formulations F, J, K and 0) had
indicated that NTA could significantly enhance the
performance of all three of our surfectants. Formulations
.T and 0 were among the top ranking formulations with
compounds ll2A arid 212. Word that the use of NTA was being
reconsidered came too late to resume testing of NTA under
this project. Although we continue to view the use of NTA
with some reservations, primarily because nitrogen content
can possibly be made available as a plant nutrient and
hence contribute to eutrophication, we would recommend that
further formulations of our candidate surfactarits con-
tainJng limited concentrations of NTA be bested for
deterqenl efficiency.
One of the difficulties in deriving any significant
behavior pattern for our candidaLe surfactanfs stems from
the fact that many of the formulations tested exhibited
larqe differences in their detergency on the two cloths.
Aithcugh the ENPA cloth appears to be much easier to clean,
the detergency values falling into the 40-50 RU range for
the 4r nd standard and 3545 RU for the MiAM I as compared
to the OST cloth where detergencies ranged from 10-20 RU
for both standards, the relative performance of our sur-
£nctants appea s to be less favorable on that cloth than on
the latter cloth. While generally most formulations which
ranked high on the UST cloth also rank high on EMPA, many
formulations, e.g., 112A78, 112AM, did show large
differences in their relative rank on the two cloths. This
was particularly true at the 0.1% concentration. Compound
212 was somewhat less susceptible to the differences in
the two cloths than either 112A or 112B1.
Some trends did, however, emerge. For example, the addition
of sodium citrate to formulations in most cases markedly
eLihanced the detergency on the EMPA cloth with both corn
pounds 112A and 212, although its contribution to the
riffectiveness of these formulations on UST cloth was
uegligible. Lowering the alkalinity of the formulations
by dc creasing the amount of silicate or sub t&tuting N
ηxade siIic te for the Star grade further er anced this
effect with these two surfactants. Addition of electr-
tispenially sodium chloride, further improved the
performance of many of these formulations. On the other
h-3, the se of citrate in formulations wi - urfactant
48
-------
112B1 appeared to have no significant effect on the
detergent efficiency. Surprisingly, the addition of
Tergitol 15S-9 had relatively little effect on improving
the performance of our surfactants. We had added the
nonionic surfactant in the hopes of achieving a synergistic
effect by improving the removal of nonpolar soil components
which the Tergitol should have been a somewhat better
solubilizer for. This did not seem to be the case.
Formulations ll2A73, 112B171, 112B198 and 21229 which
contain Tergitol are directly comparable to formulations
112A72, ll2Bl70, ll2Bl97 and 21268 respectively, which
do not contain the nonionic surfactant. In all of these
formulations, we dropped the use of cocodiethanolanude
(CDA) because we felt that this foam supressant was not
required with our surfactants. In fact, it turned out that
these formulations without the CDA were significantly
superior to formulation A to which they are also directly
comparable. This effect is particularly noticeable on the
EMPA cloth.
One of the shortcomings of surfactant 212, its relatively
poor performance at the very low concentration level (0.1%)
was partially overcome by the use of N grade sodium
silicate. This grade of silicate differs from the Star
grade in the ratio of Si0 2 to Na20 and in the relative pH.
The Si0 2 /Na 2 O ratio for the N grade is 3.22 while that
for the Star is 2.5 and the pH is lower in solutions of
equivalent concentration for the N grade than that for
the Star. Both grades were supplied by the Philadelphia
Quartz Co. Although the overall performance of the
formulations, 21253 to 21255, using the N silicate was
not significantly better than that of similar formulations
using the Star silicate, their effectiveness at the 0.1%
detergent formulation in the wash water use level was
materially improved. Similar effects were also found for
surfactant 112A where formulations using the N silicate
were somewhat superior to those with the Star grade.
To further follow up the effect of silicate and of pH on
the performance of surfactant 212, formulations 212-56
and 212-57 were tested. These formulations completely
eliminated the silicate and, in addition, formulation
21256 was titrated with citric acid to a pH of 7. The
silicate free pH of formulation 21257 was slightly over 9.
These two formulations performed surprisingly well being
only slightly less effective than their silicate containing
counterparts 21253 and 212-22. Total elimination of
silicate also had only a relatively minor negative effect
on formulations with surfactant ll2A particularly in the
-------
fully built formulation 112A119 and 112A120. The series
112A75 to ll2A77 further illustrates this trend. It
should be of interest to further investigate this matter
arid possibly achieve formulations having relatively low pH.
Sodium gluconate also tended to enhance the detergency of
formulations using 11Th and 212 and combinations of
gluconate and acetate were particularly effective. While
the acetate arid gluconate combinations were very effective
with 11Th on the UST cloth with relatively little effect
on the EMPA cloth (112A80 and 112A-112), addition of
electrolytes improved their efficiency on the EMPA without
impairing the effectiveness on the UST cloth (112Al22 to
125) . Addition of citrate to these formulations markedly
improved the detergency on the ENPA cloth but appeared to
c3iminish their effectiveness on the UST cloth (ll2A-lll,
.112All8 to 121) . Surfactant 212 behaved in similar
fashion and nearly all of the formulations (212-94 to 96 and
:212-128, 130, 131, 134 and 138) ranked among the top ten
.n the combined cloth rankings.
Seqiene, a proprietary sequestering formulation, the
anionic surfactant Gantrez, and Weston, a polyelectrolyte
product, were riot tested sufficiently to establish any
definite trends but appeared to have very little effect on
the formulations in which they were investigated.
Surfactant 210, the C 10 homolog of compound 212, was also
tested and found to be somewhat less effective than the C 12
compound. Although there appeared to be a tendency for
the 210 compound to clean slightly better at the 0.5% formu-
lation in the wash water level, these formulations performed
consistently worse at the 0.1% and 0.2% use levels than did
the corresponding formulations using the C 12 homolog. The
performances of these two homologs are compared in the five
formulations (formulations 21053 to 57) presented in
Figures 4446.
The C 10 homolog of surfactant 11231, llOBl was also investi-
gated. Because of the limited amount of this compound
available, t was decided that an abbreviated test method
should be used in order to be able to test a larger number
of formulations. This approach was preferred since a larger
number of formulations would help to establish a definite
.rend while little could be concluded from the full testing
of only one or two formulations. The 11OB1 formulations
ere therefore evaluated only at two concentrations, 0.1%
and 0.3% at each of two water hardness levels, 135 and
300 ppm.
50
-------
The results of this series of tests with the 11OB1 compound
are presented and compared to those obtained with the 112B1
homolog in Figures 47-49. It will be noted that with all
five formulations tested the C 10 compound outperformed the
C 12 homolog at the higher detergent concentration, while
the latter did better at the lower concentrations indicating
that the C 10 detergent efficiency is more affected by
concentration factors than its larger homolog. This effect
is particularly obvious with the EMPA cloth but less
consistent in the 1.1ST cloth.
A number of selected formulations using surfactants 112A
and 212 were also tested on the dacron/cotton wash-andwear
fabrics. Both of these compounds performed well on both the
permapress finished cloth as well as the cloth without this
finish. Most of the formulations with 212 easily out-
performed the two reference standards while those with
ll2A, although not quite as consistently effective
did well at the lower concentrations in the higher hardness
water. Both types of cloth, as supplied by Testfabrics,
come with only half their width soiled leaving a white flag
which permits the simultaneous testing for redeposition.
We washed these cloths, therefore, with the flags attached
to determine whiteness retention. In none of the formu-
lations tested did we find any significant loss of white-
ness. The detergency data for the dacron/cotton cloths are
presented in Figures 5055 and the whiteness retention
values are given in Tables 1213.
The consistent failure of surfactant 112B1 to perform as
well as the other two compounds clearly eliminated it from
consideration in our final recormtendations, although we
believe that it has sufficient promise to warrant further
investigation.
Although some of the formulations using surfactant 212
appear to be superior to any of the 112A formulations, we
have some reservations about recommending these at this
time. It was our practice to use the 212 in the form of
a slurry as obtained in a single step extraction from the
reactaori mixture. This slurry usually contained about 30%
active surfactant, the balance being a 1:1 mixture of
isopropanol and water. A recent test using dried surfactant
212 yielded detergency results approximately 15% lower than
those obtained with the identical formulation using the
slurry. This may indicate that some detergency effects
were contributed by the isopropanol. Since, in a finished,
spray-dried detergent product these effects would also be
absent, we hesitate to choose this surfactant without
further investigation into this problem. We strongly
51
-------
T73Lc [ 2
fl1ITFWF35 Rpr?NTION 3 b
Dacron, .otton (6 ,/35) Fac ric SiUt nd 141t1Out Perm pres FLnlsh
112A Fcrr.d tiots
50 ppm 135 ppm 300 opm
H 07
. 3 -22
72 06
75 1
77 1. 4
78 3 3
80 17
104 -08
117 08
118 -2 3
121 -19
01
08
-0 3
01
01
07
2 1
07
12
-0 4
-1 4
0.8
-c
-0 3
04
04
-0 7
10
OS
04
01
04
-0
-0 2
07
Os
1 1.
- 73
10
04
05
10
0 o (3
-0 7 0 5
0 8 -O 8
16 2:
-1 0 -0 1
-1 a -c 7
32 25
01 01
24 23
-1 -a:
-t 0 .1) 7
1 08 L 2
0 4 -0 9 -0 2
09 04 07
0.704 07
-I 9 0 £ -0 1
-o 3 -L 0 0 1
24 2( 1,
0 08 10
I I S I;
-I 0 C 0 3
0 9 0
125 3 1 0 6 0 3 1 2
Sample
0.1
Without
010203
05
UI
02
C3
05
0 . 0203 0.5
Witho .
01020 05
01
Wi _
0203 05
No.
02 0.3
05
0609
14
272930
26
06
10
12
10
25-09
06
07-05-050
05
06
05-0
14-0
07
-020403
36
04
06
03
06
22-03
09
17 73 18
20
29
23
21
20
1 -L 0
0 4
-4 3 -1.8 -1 1
-0 8
-0 4
-0 5
-0 9
-0 6
3 5 I 8
0 3
0 4 I 2 -0 7
-0 4
0 4
0 5
0 1
-0 4
20 22
IS
13 15 2.0
18
12
18
23
2.1
-1 7 1 5
0 9
0 2 -0 5 -0 1
0 4
0.2
0 4
0 6
0 7
1523
14
212.323
3.1
19
20
23
27
-3 5 -1 7
0 9
-2 8 -2 0 -1 5
-0 8
-0 1
0
-0 5
-0 2
4I- .
08
-) 08-0o - 6
030
0204
0 4
7 0
1 7
.3 7
.3 i 3 7 5
0 8
0 8
1 7
I 3
1 4
0 4
0.3
0 2
0.1
Brand
13
1117
7
15 7i
19
2-
(1
I
131.820
2_
Qt
10
15
19
20
19
20
25
HA14
-l 8
-1 0 -o 8
0 ,
-0 3 0 .
0
1
-.
-0
- 9
- 0 -0 C 4
1 7
-1 9
-3 0
-0 8
0 3
-1 0
0 4
0 7
0 5
bLf&rencc s
Lfl n -ef1 cti,it.,
ea It
..c.
rn r
I c.
tr rr I.,
t. .
after ashtng
07
30
10
03
08
08
18
1
1
1
1
11
29-1 -1-0
10
11
I Q
lΰ
06
08
1.9
09
09
13
71
13
08
Li
02
06
16
a
13
09
:0
1.3
09
09
3
02
Oi
10
7
10
05
radarc soiled c1o i . t.. - --chrc .i- . Zt. :r n ;c
-------
I j . 13
lcHIrFI ., 1FTEN11(.,
D .c icn/Co1ton (55-35) Faz..i Ic Wiil and ilithout Pr-rmapre5s Fir,ish°
212 Io:riul t ion.,
aDi frnces in reflectivity. negatlvc values mean losa in r ulectivit afr.er washing
50 oom
Sample _Without With -
Bo 01020305 01 020305
U i
w
30
-17-05-010
43
0
05
08
1.2
44
04
03
17
06
74
01
08
10
10
89
-10
02
05
09
130
-08
0.3
06
00
132
136
-0 4
-040
0 4
3
0 7
06
1 1
I I
Without With
01 720305 01020305
1 5 1 1 0 9 0 5
-0 3 -0 -0 i 0 4
-0 4 -0 5 -0 8 -0 6
-1.0-05-0 04
-1 9 -0 3 -0 6 -0
-l o -0 7 -0 8 -0 3
2 0 -l 4 -1.4 0 6
2 9 -1 1 -1 I 0 6
inn
tB 04 100.4 02
020 051703
0.0 12 11 08 02
0 5 0 - 0 8 1 0 -0 5
0.6 0 2 0 5 0 6 -0.4
0.8 0.5 0.8 1 0 -0
0 0509 10 -3
0 4 0.2 0.8 1 0 -1
Without With
01020305 0102030.5
Brand 0.3 0 8 0 8 1.4 -0.6 0 2 0 I 0 8
?JIAZI -1 8 -1 0 0 8 0 5 -0 3 0.6 0 7 5
0.103-05
Ii
12
11
09
06
05
02 .C
-05-0 .. 04
04
01-0
06
-02-0
-04
02
040201
07
06
13
1.1
03
06
06
0.3
-01-0106
04
05
06
12
0
04
03
07
-03-0 -01
09
09
11
08
-0
-04-0
-01
0 6 -0 4 -0 4
1 1
1 2
1.0
1 0
0 3
0 5
0
0
0
l i 0 9 -0
0 9
1 1
1 0
0 8
-0 2
-0 2
-0 6
-0.6
3
-1 1 -0 8 -0 3
1 0
1 1
0 8
1 0
-0 3
0 1
0 4
-0.4
01 05 08 13 0201 02 07
_3 5 o 5 -0.3 0 9 -1 0 -0.2 0 4 1 7
bStandard soiled cloth with attached white flag from Testfabrtcs. Inc
110.802 10 0403030.5
-1 9 -3 0 -0 B -0.3 -1 0 0 4 0 7 0 5
-------
recommend the further investigation of this surfactant,
however, since even at these lowered detergency levels
some of the formulations would still compare favorably
with formulations using 112A.
The final choice of the formulation which we are recommend-
ing for full-scale consumer use and ecological compatibility
testing (112A-121) depended on the consideration of several
factors. While not the best formulation tested, its
choice was a compromise based on its relatively good
performance at the low concentration and in the medium
hard water which is close to the water hardness most
commonly found in the U. S. Although it ranks rather low
on UST cloth (26 out of 63) a glance at the actual
detergency data shows that its performance is, in fact,
quite close to that of the best. This problem of low rank
values for relatively well performing formulations was
discussed earlier and is particularly critical here since
for some of the test conditions nearly half of the 112A
formulations yielded detergency data falling within a
range of only 5 RU. With such a narrow range, differences
in the actual performance of the individual formulations
are relatively insignificant but become blown up out of
proportion by being spread over a much larger range of
rank numbers. Thus, in spite of its low rank, formulation
ll2A-121 performs very well on UST cloth. This is further
borne out by the fact that ]n the combined cloth ranking
this formulation scored 51 out of a possible 59, indic. ing
that its overall performance was, in fact, good.
The composition of the formulation appears to be quite
innocuous in the sense that all, builders used are present
in relatively low concentrations and none of them are
likely to affect the ecology adversely. Although the pH
of this formulation (approx. 10) is somewhat higher than
we would like, it is commensurate with that of most common
phosphated brands. None of the components should pose any
hazard to safety. Finally, it is a 100% solids formu-
lation, thus requiring no further formulation effort.
Economical factors were not considered in the production
of any of our formulations, nor were these within the
intent of this program. Since none of the candidate
surfactants are currently being commercially manufactured
their eventual price will depend largely on the degree of
acceptance these surfactants command. This also applies
to the cost of some of the formulation constituents, like
sodium citrate, whose price will depend largely upon the
demand created for them.
54
-------
SECTION VII
ACKNOWLEDGMENT S
This project was carried out by the lIT Research Instit.ute
under Contract No. 1412937 for the U. S. EnvironrnenLal
Protection Agency.
The concept of using pot.eritially selfchelating sur
factants in phosphate free detergent formulations was
fostered by Dr. Warner M. Linfield, formerly Manager,
Organic Chemistry Research Section, IITRI. Adclitiona
formulation ideas were contributed by Mr. Helmut G. Reilich,
Associate Chemist.
IITRI personnel who directly participated in this project
include L. Hytry, F. Ribich, L. Ward, C. Wetter and
T. Yamauchi of the Organic Chemistry Research Section. fhe
fish Toxicity arid the Provisional Algael Assay Procedures
were carried out by Biometrics Laboratories, Enylewood
Cliffs, New York under the direction of Dr. Samuel Posner.
Special thanks are given to Dr. C. C. Harliu. Jr., Chief
of the Water Quality Control Research Prograi 1 i, Robert S.
Kerr Water Research Center, EPA, whose suggestions end
interest provided guidance in the evaluation of our work.
This project was designed, operated arid administered by
IITRI ; Dr. Warner M. Linfield was Project Director and
Mr. Helmut G. Reilich was Project Leader.
55
-------
SECTION VIII
REFERENCES
1. Development of Phosphate-Free Home Laundry Dete:g L1t.,
Water Pollution Control Research Series No. 16OBOIJVF
12/70, EPA, U. S. Government Printing Office,
Washington, D. C.
2. Osaka Shiritsu Daiqaku Kaseigakunu-Kiyo, 2, 29 (l u4)
CA, 63:13582b.
3. H. Schott, J. Am. Oil Chemists Soc., 45, 414 (l9 3).
4. R. C. Davis, Soap & Chem. Specialties, 39(8) , 47 (1963, ,
5. A. M. Schwartz and J. Berch, Soap & Chem. Speciai ties,
39(5), 78 (1963).
57
-------
SECTION IX
APPENDIX A
Additional data for detergency and ranking
Figures 813 - Detailed Detergency Performance Data for
Compound 112A Formulations on UST and
ENPA Cloth
Figures 14-19 - Detailed Detergency Performance Data for
Compound 112B1 Formulations on UST and
EMPA Cloth
Figures 20-25 - Detailed Detergency Performance Data for
Compound 212 Formulations on UST and
ENPA Cloth
Figures 26-31 - Performance of Compound 112A Formulations
at 0.1% Concentration in Wash Water
Figures 32-37 Performance of Compound ll2Bl Formulations
at 0.1% Concentration in Wash Water
Figures 38-43 - Performance of Compound 212 Formulations
at 0.1% Concentration in Wash Water
Figures 44-46 Comparison of Performance of Compound 212
and 210
Figures 47-49 - Comparison of Performance of Compounds
112B1 and 11OE1
Figures 50-52 - Performance of Compound ll2A Formulations
on Dacron/Cotton Fabrics
Figures 53-55 Performance of Compound 212 Formulations
on Dacron/Cotton Fabrics
59
-------
20
Figure 8
PERFORMANCE OF COMPOUND 112A FORMULATIONS
ON UST CLOTH
5 ) ppm Water Hardness - 0.1, 0.2, 0.3 and 0.5%
> .
U
1)
0
0
Formulation in Wash Water
-------
30
Figure 9
PERFORM? NCE OF COMPOUND 112A FORMULATIONS
ON UST CLOTH
135 ppii W i:er Hardness 0.1, 0.2, 0.3 arid 0.5%
20
>1
U
V
V
10
3
Formulation in Wash Water
-------
30
>1
U
C
I ,
Li
(A)
10
0
PERFORMANCE OF
FORMULAT ION
?igure .w
COMPOUND 112A
ON UST CLOTH
300 ppm Water Hardness 0.1, 0.2, 0.3 and 0.5/s
FDrmulation in Wash Water
-------
50
Pr RF0RMANCE OF COMPOUND 112A FORMULATIONS
Ot1 E 14PA CLOTH
50 p a Water Hardness 0.1, 0.2, 0.3 and 0.5%
Formulation in Wash water
40
U
a
a .
Ftgure 11
-------
sO
PERFORM1 NCE OF COMPOUND 11 2A FORMULAT IONS
ON EMPA CLOTH
135 ppm Water Hardness 0.1, 0.2, 0.3 and 0.5%
U i
40
>,
C)
c i )
30
20
10
Figure 12
Formulation in Wash Water
-------
50
Figure 13
PERFORMANCE OF COMPOUND 11. 2A FORMULAT IONS
ON EMPA CLOTH
300 pp n Water iardness 0.1, 0.2, 0.3 arid 0.5%
40
U
q)
Li
4 )
30
20
£0
U, U, F l U i a a
o .D 0 I-
For nu1ation in Wash Water
-------
20
I
2
4
>1
N(1J
10
4)
p- I.- - I-
I I W D O .OOOOO CO-
C tTlt 4 O- iO J u
Figure 14
P1 FORMANCE OF COMPOUND 112B1 FORMULATIONS
ON JST CLOTH
50 ppm Water Hardness - 0,1, 0.2, 0.3 and 0.5%
Formulation in J 3h Water
-------
L v
10
G)
GD
0
Figure 15
PERFORMANCE OF COMPOUND 112B1 FORMULATIONS
ON UST CLOTH
135 ppm Water Hardness 0.1, 0.2, 0.3 and 0.5%
Formu1atiO 1 in Wash Water
-------
30
Figure 16
PERFORMANCE OF COMPOUND 112B1 FORMULXPIONS
ON UST CLOTH
300 ppm Water Hardness - 0.1, 0.2, 0.3 and 0.5%
20
>1
U
c
w
14
0
0
10
0
1
I
r
P
I
it
L
t
Formulation in Wash Water
-------
PERFORMANCE OF COMPOUND 11 2B1 FORMUL T IONS
ON EMPA CLOTH
50 ppm Water Hardness 0.1, 0.2, 0.3 and 0.5%
C)
4)
30
4)
0
20
Figure 17
Forraulation in Wash Water
-------
50
PERFORMANCE OF COMPOUUD 112B1 F WLATIONS
Ot J MPA CLCT
135 ppm Water Hardness 0.1, 0.2, 0.3 a d 0.5%
>.
U
C
a 3 )
I i
a)
3
20
10
Figure 18
ForrTu1 tion in Wash V -:te
-------
PERFORMANCE OF COMPOUND 11281 FORMULATIONS
ON EMPA CLOTH
30() p . 7z ter Hardness 0.1, 0.2, 0.3 and 0.5%
F. rrnu1atiori in Wash Water
C)
C
a)
1
Figure 19
-------
i igure u
PERFORMANCE OF COMPOUND 212 FORMULATIONS
ON UST CLOTH
50 ppm Water Hardness - 0.1, 0.2, 0.3 and 0.5%
Formulation in Wash Water
>1
o 10
V
41)
4 )
11)
w
-------
Figure 21
PERFORMANCE OF COMPOUND 212 FORMULATIONS
ON UST CLOTH
135 ppm Water Hardness - 0.1, 0.2, 0.3 and 0.5%
U
0
I - I
C)
10
0
Formulation in Wash Water
-------
Figure 22
PERFORMANCE OF COMPOUND 212 FORMULATIONS
ON UST CLOTH
300 ppm Water Hardness 0.1, 0.2, 0.3 and 0.5%
>1
C)
C
0 )
10
C - i l
Formulation in Wash Water
-------
so
P 4 RFORNANCE OF COMPOUND 212 FORMULATIONS
O I EMPA CLOTH
40
4
>,
U
30
20
10
Figure 23
50 ppm Water Hardness - 0.1, 0.2, 0.3 and 0.5%
Formulation in Wash W 3ter
-------
50
Pi RFORMANCE OF COMPOUND 212 FORMULATIONS
ON EMPA CLOTH
135 ppm Water Hardness - 0.1, 0.2, 0.3 and 0.5%
_40
U
U
U
U
30
20
1
Ftgure 24
Formulation in W3sh Water
-------
50
PERFORM? 1 NCE OF COMPOUND 212 FORMULATIONS
ON E 4PA CLOTH
300 ppm W:3ter Hardr ess - 0.1, 0.2, 0.3 and 0.5%
Formul& ion in Wash Water
40
C
w
30
20
Figure 25
-------
20
Fi ure 2
:oMPo L IJ 2A O .MULATi0N
D J LCY T H
5C ppm Wat 0.1%
Forinulatic,n in Wash Water
C -)
10
0
-------
PE FCR AN E OF C )MPOUND 112A FORMULATIONS
Or1 HT CLOTH
>1
L i
ci)
01
a)
GD
0
20
ic
0
Fioure 27
13. nj n Wdter Harth 1 e3 0.1%
Formulation lh Wash Water
-------
20
PERFORMANCE OF COMPOUND 112A FORMULATIONS
ON UST CLOTH
300 ppm Water Hardness - 0.1%
U
t j)
cr
0
Figure 28
Formulation in Wash Water
-------
50
Fi- ur 2 )
POR MANCE Oi COM UNi; 1121. D ULTku
D EMPA CLOTH
,0 ppm Watet - 0. t
Forrnu1atio ut Wa W3te
40
3o
20
Ni
()
-------
P RFORIv1ANCE OF COMPOUND 112A FORMULATIONS
ON EMPA CLOTH
135 ppm Water Hardness 0.1%
>1
U
U)
a)
a)
50
40
30
20
10
0
c,J
Figure 30
Formulation in Wash Water
-------
40
P PFORM i; . O COMPOUND 11Th ORMt t ATION
ON E 4PA CLOTH
v)) ppm i er H rdne3s 0.
U
U)
a)
C)
30
20
10
0
Figure 31
or: i io ri W J 1 i Wat
-------
PERF0 NC E
OF COMPOUIID 112B OR LATION
O L ST LOTH
Watr Hardness - 0.1%
aD
( 71
>1
a 10
c i )
0
Figure 32
5U pnru
Fr j t.1Cifl in W .}!
-------
PERFORMANCE O COMPO JND 112B1 FORMULATIONS
ON UST CLOTH
135 ppm Water Tardness - 0.1%
Formui ti.c in Wash Water
>,
c - i
10
1)
c i )
0 )
0
C)
Flaure 33
-------
PERFORMAi;CE cF COrIPOUNL 12ii FCI L T A ION.
ON UST CLOTH
300 pm Water H rdne s - 3.1%
20
10
0
F ui 34
Forrulatior ir Wasi Water
-------
so
40 - -
C
t 20--
2
cc
10
I u C C U C. LI 4
X
I --4.- -
L . tL
Ficure 35
PERFO RN J C E OF COMPOUND 11 2B1 FORMUL AT IONS
ON EMPA CLOTH
50 ppm Water Hardness - 0.1%
Formul2tlcn in Wasr Water
-------
PERFORMJ½NCE OF COMPOUND 112B1 FORMULATIONS
ON EMPA CLOTH
135 ppm Water Hardness - 0.1%
Formulation in Wash Water
U
1)
s - I
0
4 )
ό)
50
40
30
20
10
0
OD
Figure 36
-------
+0
PERFOk i NCE CO tP NL Ii 2B1
O 1 Ei°A CLOTH
FC PMCLAT TON
3 )1) .t r H rdne - 0.1%
3o
C)
a)
(. )
0
20
10
0
F ure 3 i
Forru] at cr1 a ri W h W
-------
P ERFORMANCE OF CONPOUND 11 2B1 FO RMIJL AT IONS
ON ST CLOTH
50 ppm Water Hardness - 0.1%
Formulation in Wash Water
>1
U
La
w
-U
U
Figure 38
-------
PERFORMANCE OF CONPOUND 212 FORMULATIONS
ON UST CLOTH
1 3 ppru Water H rdr es5 - 0.1%
>1
U
0
Ό0
0
Figure 39
Formulation in Wash W te
-------
a:
>1
0
C
Figure O
P 1 RFO Hi A C OF COVtPOUND
212 FORMULATIONS
ON UST CLOTH
300 ppm Water Hardness - O. %
Formulatioti in Wash Water
w
10
0
.1 U . a U I I U U
-------
PERFORMANCE OF COMPOUND 212 FORMULATION5
ON E A CLOTH
30 ppm Water Hard ss - 0.1%
4
( I,
C)
50
40
30
20
LO
0
Lcj.i:e 41
F rmu1ation ira Wash Water
-------
PERFORMANCE OF COMPOUND 212 FORMULATIONS
ON EMPA CLOTH
135 ppm Water Hardness - 0.1%
Formulation in Wash Water
40
30
U
C
3
I.i
4J
U i
20
10
0
Figure 42
-------
pERF0RM1 NCE OF COMPOUND 212 FORMUL1 TIONS
ON EMPA CLOTH
300 ppm Water Hardness - 0.1%
Formulation in Wash Water
>
C)
c i)
a)
-1 -I
40
30
20
10
0
Figure 43
-------
COMPARI SON OF COMPOUNDS 212 AND 210
50 ppm Hardness Water
1
C .)
I D
ID
ID
Figure 44
-------
COMPARISON OF CONP0U1 DS 212 AUD 210
Ό0
C)
G)
Figure 45
135 ppm Hardness Water
-------
COMPARISON OF COMPOUNDS 212 AND 210
0
C
q)
U)
U)
Figure 46
300 ppm Hardness Water
-------
40
>1
U
w
0 1 12B1
IIOBI
I35ppm
Figure 47
COMPARISON OF 112B1 AND 11OB1
i35ppm 0.1%
0.3%
300ppm
0.1% 0.3%
I-
0.1% 0.3%
- 300ppm
D.I%03%
30
I-
0
-J
C)
4
0
w
10
40
30
20
10
10
10
I
-
II -
0
C.)
:
-
p
._L___g
FormulatiOn A
Formulation C
100
-------
0 1 12B 1 IIOBI
COMPARISON OF 112B1 AND 11OBI
I35ppm 0. 1%
0.3%
300ppm
0.1% 0.3%
0
/
I . I
I II
0
I-
0
-J
C-)
4
a-
U i
1)
a)
l35ppm 0.1%
0.3% -
300ppm
j 0.I%0.3%
1
V
V
111 0
/
4
0/
%
40
30
20
10
10
40
30
20
10
10
-
ilIi L
- - -p.
0 I
0 -
,,
:i
Formulation F
Formul at
Figure 48
on I
101
-------
Formulation K
PC 0
30 0
-4
U
( .4
W r-4
20 -4
. 0
z
0
10
0
U
PC
0
l0 1
40
40
30
20
C
q )
10
1
102
-------
11Th FORMULATIONS ON DACRON/COTTON FABRIC
50 ppm Water Hardness
L I I WITHOUT PERM PRESS FINISH
5
WITH PERMAPRESS FINISH
>
(1
3)
(I)
I
Figure 50
103
-------
112A FORI4UI 1 ATIONS ON DACRON/COTTOi FABRIC
135 ppm W iter Hardness
0 WITHOUT
PERMAPRESS
FINISH
D WITH
PERMAPRESS
FINISH
U
1)
4. )
50
40
30
20
10
Figure 51
104
-------
112A FORMULATIONS ON DACRON/COTTON FABRIC
300 ppm Water Hardness
Eli WITHOUT
WITH PERMAPRESS
PERMIAPRESS FINISH
FINISH
x
U
Ό1)
01
a)
I)
Figure 52
105
-------
60
50
U
Q)
a)
4 )
40
212 FORMULATIONS ON D RON/COTTON FABRIC
O ppm Water Hardrie s
30
20
0 WITHOUT PERMAPRESS FINISH
D WITH PERMAPRESS FINISH
Figure 53
106
-------
50
>1
U
C
a)
c i )
4.)
c l i
40
30
20
212 FORMULATIONS ON DICRON/COTTON FABRIC
135 ppm Hardness Water
60
Figure 54
107
-------
50
>1
U
c i )
.1
ci)
c i )
40
30
212 FORMULATIONS ON DACRON/COTTON FABRIC
300 ppm Water Hardness
WITHOUT
PERMAPRESS
FINISH
PE RMAPRESS
FINISH
60
20
108
-------
APPENDIX B
Facsimile copy of report from Biometrics.
109
-------
Biometric
CLIENT: ItT Rese.3rch Institute
10 West 35th Street
Chicago, Illinois 60616
ATTENTION: Dr. William Linfield
ST iDY: TLm 96-hour determination static and
dynamic in Fat Head Minnows
TEST MATERIALS: Compound 112A
Compound 112B1
Compound 212
LAS (control)
EXPERIMENTAL
REFERENCE NUMBER: 49-98
DA1t ; June 8, 1971
/
- - -:- . A, , -
Samuel Posner
Director of Environmental Services Division
111
-------
METHOD
The tolerance limit median (TLm) perforrnedon this tudy is desκribed
by Mount and Brung 1,2 of theFederal Wat r Pol1utio& ontrol Aaa ini-
stration. Fingerling fathead minnows, 2 4 t grams, were ac cliirhted td
the laboratory water supply foi at least 96 hours prior to range finding
test. The fish were led a standard fish diet and then fasted for 24
hours prior to use. During the test procedure, the animals were fasted
so as to uninimiz the it gestion of test material via the food chain.
The tanks used were 30-gallon all-glass aquaria filled to apptoxiinalely
16 gallons ci pre-fittered water. Water temperature was maintained
between 19°C. anc 41°C. during thu entire test. DisscL ed oxygen (02)
analysis was pcrformed daily dui ing the dynamic phase.
PROCI DIiRE
Static Phaso
len to fifteen fin 6 erl trig fathead minnows per group were exposed to the
cc L compounds in 30-gal Ion all-glass aquhia. In the static test,
the tt,t material waa introduccd on I)ay 0, thoroughly mixed and then
th fish added. Observations were mace at 24hour dnd 48-hour intervals.
Because this static procedur is for range finding only, i i was not
nace sary to cacry the observatLonb beyond 48 hours.
Dynamic Phase
Aft eL completing the static range finding phase, two hundred fat} ead
minnows were acclimated as previously described. Six (6) 30-gallon,
all-gla s tanks, each with 10 fingerlings of approximatel, 5-8 grams
each were used. We were able to maintain a dissolved bxygen (02)
level of approximately 8-10 ppm. during the course of the dynamic tests.
02 was maintained daily using the modified Wlnkler technique 3 . The 02
value is extremely important so that we can determine the chemical
1. Mount, D. I., and Brung, W. A., A Simplified Dosing Apparatus for
Fish Toxicology Studies Water lies., Vol. I, pp. 21-29, 1967
2. Water Quality Criteria, FWPCA, April 1968, p.. 59
3. Standard Method -Water and Wasie Water Analysis , APHA, AWWA, 12th Ed.,
1 968
112
-------
oxygen demand (COD) of the test compound and control the 02 level if
necessary by adding pure oxygen. For example, if the COD of the test
material is high enough to reduce the 02 to a level of 4 ppm or less,
the fingerlings will die due to the lack of oxygen and not from the
direct absorption of the test material.
OBSERVATION
A. Static
Table I summarizes the static TLm 24 hour which were run preparatory
to the dynamic phases.
Table I
Compound TTAU 24 hour (ppm )
ll2A 1.8 1.9
11281 5.5
212 4.0
(1) LAS b.5
(2) LAS 6.6
The static TLm was read at 24 hours because the rapid degrading (bio-
degradation) of the material led us to believe that like active
material was left in solution after 24 hours.
(1) original shipment
(2) May 18th shipment
The LAS was run twice using different lots of fish and two different
shipments of LAS. (original shipment-2nd shipment May 18th). It
should be noted that the TLin 24 hour values are statistically the
same.
B. Dynamic
Using the static values the compounds were run on the dynamic system
previously described. Table II is a summary of the dynamic data.
113
-------
Table II
(ppm)
Compound TLM 96 hour (ppm) Dissolved Oxygen
112A 2.0 8.2-10.4
112B1 6.0 7.8-9.4
212 3.2 7.28.0
(1) LAS 12.0 7.28.4
(2) LAS 9.5 7.0-8.6
In most cases, other than compound 212, the dynamic TLm is greater than the
static value.
DISCUSSION AND CONCLUSION
All the compounds evaluated were readily soluble in water.
The static TLrn 24 hour values in most cases were less than the dynamic
values. This is most likely due to the biodegradability of the compounds
tested.
The water temperature during the dynamic test was maintained between
58-61°F. Dissolved oxygen values for all compounds ranged from
approximately 7.0-10.5 ppm.
114
-------
APPENDIX I
Provisioned Algae Assay Proct dures
Test organism: Selenastrum capricornutom
Source: Environmental Protection Agency - FWPCA Laboratory
Corvallis, Oregon
Procedure: PAAP described in Provisional Algae Assay Procedure
published in 1969 by the Joint Industry/Government
Task Force on Eutrophication
Procedure I, Bottle Test :
METHOD
PAAP procedure, 1969, Bottle Test
A. 125 ml. Erlenmeyer flasks were used as culture vessels.
B. Algae Cell counts were performed by a binocular micro-
scope and a Sedgewick Rafter counting cell.
C. Dry weights were done with an Ainsworth balance by
filtering and weighing after oven drying.
115
-------
PAAP TEST
Compound IIT-112A Concentrations
1.4, .14, .014 ppm
*Table 111
DATE ; 5/13 - 5/20/71
Compound
dilution
Results of Incubation - Cell Counts
5th day 7th day
No/mi Dry W t. Mo/ml Dry Wgt.
*
Control
Control
Control
Control
Ave.
l.4ppm
1.4ppm
1.4ppm
l.4pprn
Ave.
l4ppm
l4ppm
l4ppm
l4ppm
Ave.
O l4ppni
Ol4ppm
. Ol4ppm
.fll4ppm
Ave.
900,000
416,000
766,000
616,000
1,233,000
2,017,000
1,617 .000
1,533,000
1,000,000
1,683,000
1 ,617 ,000
1,300,000
1,417,000
1,000,000
1,702,000
1,233,000
3,000,000
1 ,033,000
3,111,000
2 ,450,000
4,717,000
5,367,000
5,767,000
5,633,000
, 33,OOO
4,933,000
4,850,000
5,817,000
3,1 . 3,000
5,0 3,00o
5,033,000
3,583,000
116
-------
Results of Incubation - Cell Counts
5th day 7th day
Compound No/mi Dry Wgt. No/mi Dry Wgt.
dilution _________ ________ ___________
Control 3,467,000
Control 1,983,000
Control 2,883,000
Control 3,350,000
Ave.
l.Sppm 5,150,000
1.8ppm 4,317,000
l.8ppm 4,033.000
l.8ppm 4,000,000
Ave.
PAAP TEST
Compound IIT-212 Concentrations 1.8, .18, .018 ppm
DATE:
678,000 .00625
911,000 .0125
589,000 .00632
589,000 .00632
.l8ppm
l8ppm
.l8ppm
.l8ppm
Ave.
. Ol8ppm
.018 ppm
Ol8ppm
O lSppm
Ave.
4,544,000
3,767,000
3,567,000
3,867,000
3,644,000
6,333,000
7,615,000
4,300,000
*See Table III
117
-------
PAAP TEST
Compound IIT-112B-l Concentrations 3.0. .3, .03 ppm
DATE : 5/4 - 5/11/71
Results of lncubatio - Cell Counts
5th day 7th day
No/mi Dry Wgt. No/mi Dry Wgt.
*
Compound
dilution
Control
Control
Control
Control
Ave.
3.Oppm
3. Oppm
3. Oppm
3. Oppm
Ave.
3ppm
3ppm
.3pprn
3ppm
Ave.
.O3ppm
.O3ppm
O3ppm
.O3ppm
Ave.
127,001
188,001
142,001
293,001
170,001
203,001
238,001
417,001
228,000
242,000
313,000
263,000
105,000
223,000
78,000
213,000
1,233,000
2,450,000
2,767,000
1,017,000
2,283,000
2,933,000
3,850,000
3,450,000
.83,000
3,533,000
3,483,000
4,633,000
950,000
2,833,000
2,150,000
1,517,000
*
f
*Table III
lip
-------
Compound
dilution
Control
Control
Control
Control
Ave.
Results of Incubation Cell Counts
5th day 7th day
No/mi Dry Wgt. No/mi Dry Wgt.
*Table Ill
(1) These two are possibly low because of failure to receive
proper inoculation - eliminate from calculations - use
3 replicates.
PAAP TEST
Compound lIT - LAS ConcentratIons 5, .5, .05 ppm
DATE : 4/14 - 4/21/71
1,520,000
1,550,000
1,870,000
1,670,000
116,000
2,110,000
2,240,000
1,750,000
1,500,000
2,180,000
1,460,000
1,960,000
1,060,000
3,000
2,130,000
1,760,000
(1) 5.Oppm
5. Oppm
5. Oppm
5.Oppm
Ave.
.Sppm
.Sppm
.5ppm
.5ppm
Ave.
.0 5ppm
(1) .O5pprn
.0 5ppm
.O5ppm
Ave.
3,440,000
2,230,000
3,980,000
2,810,000
670,000
4,570,000
5,160,000
3,380,000
7,640,000
5,110,000
2,520,000
3,650,000
14,520,000
6,000
4,700,000
3,630,000
1I
119
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TABLE III
Equivalent Dry Weight Chart For Selenastrum capricornutom
Concentration Equiv. Dry
of Cells/mi Wgt .
8 x i0 6 .1 mg/mi
4X 10 6 .05
2 X 106 .025
1 x 106 .0125
500,000 .00625
These weights are based upon weights obtained by filtering and weighing
after oven drying. These weights should not be considered as accurate
as the actual counts made by microscope and a Sedgcwick-Rafter counting
cell.
120
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___:!___j A . sIoiI vIafl iber I 2 cub, I Pu I c! C, roiip
05G SELECTED WATER RESOURCES ABSTRACTS
INPUT TRANSACTION FORM
Or flfli7 .itiofl
lIT Research Institute, Chicago, Illinois
Title
TECHNICAL EVALUATION OF PHOSPHATE-FREE HOME LAUNDRY DETERGENTS
j_9j Author(s)
H. C. Reilich
Pro;oi. t Dc : notiOn
16O8ODVF
Nol
Citation
_ j Descriptors (Storred Fin.t)
Detergents,* Algal Control,* Formulation,* Surfactants,*
Eutrophication, Linear Alkyl Sulfonates,Phosphates, Organic Compounds,
Water Pollution Control
lIont,(ioru (Starred First)
Phopshate-free detergents*
27 IAbSt r
Evaluation studies were carried out on a number of phosphate-free
home laundry detergent formulations based on three of the surf ctants
developed during the previous investigation sponsored by the Environ-
mental Protection Agency. All formulations were aimed at the devel-
opment of a lOO7 solids, powdered producc and contained 20% of tne
selected surfactant and 2/ carboxymethylcellulose. A combined
total of 123 formulations were evaluated using two different arti-
ficially soiled, cottoa test cloth3 and 20 o.f tnese Q r2 fucther
te5ted on daccoi ,cot t : a i-a id 73dC bci )O.h a I L - -
out permapress finish. The detergency data compared favorably
to that of a commercial phosphate containing brand and one the lOO7
fully built formulations is being recommended for full scate use
testing.
Abstruetor I I I st it ittlon
as 102 (REV JULY ( 9I SEND ro WA rEP RESOURCES SCIEUTIFIC INFORMATION CENTER
WRSIC U S OEPAR uCN F OF TII C INTERIOR
WASHINGTON 0 C 202 0
AUS GOVERNMENT PRINTING OFFICE 1972 484-4851Z15 (-3
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