Volume 27
Principles of Performance Testing of Laundry Detergents 1
THOMAS H. VAUGHN and H . . SUTER, Research and Development Division,
Wyandotte Chemicals Corporatior,:~ Wyandotte, Michigan
Introduction
H E use of laboratory performance tests for the
T evaluation of detergents for washing textiles has
grown to a considerable magnitude in t e r m s of
effort expended and in technical and commercial im-
portance. Several factors have contributed to this
growth, one of which is the multiplicity of detergent
materials which have become available in recent years.
Since there is no single material of clear cut superi-
ority which satisfies all requirements, even within a
limited field such as that being discussed here, com-
pounding is almost universally practiced either at
the point of use, by intermediate agencies, or by the
m a n u f a c t u r e r of the basic m a t e r i a l s . I m p o r t a n t syn-
ergistic effects are known (3, 8), and systematic and
precise evaluations are required in order that maxi-
mum advantage may be taken of this phenomenon.
Most organic detergents do not consist of single mo-
lecular species; r a t h e r they consist of groups of re-
lated compounds, the performance characteristics of
which may be affected by variations in raw materials
or in the conditions of processing. These effects are
not measurable with any degree of reliability b y the
usual chemical or physical determinations, and ac-
cordingly performance tests must be used for ade-
quate production control. F u r t h e r , it has been found
that detergents within a given type or class may
v a r y markedly in susceptibility to improvement with
synergistic agents. I n turn, different grades of syn-
ergistic agents may v a r y in their effect on a given
detergent. Obviously for compounding such materials
production control b y means of performance tests is
a prime requisite. Needless to say, performance tests
are invaluable in guiding experimental syntheses of
new detergents, where practically infinite variation in
composition is possible.
Until recent years the use of laboratory perform-
ance tests for detergents was largely intra-organiza-
tional. Now because of interchange of materials and
intermediates and because of the technical aspects of
the sale of detergents, laboratory methods are fre-
quently and importantly involved in inter-organiza-
tional n e g o t i a t i o n s . F o r such purposes the current
status of industry-wide practice is quite unsatisfac-
tory, not only because of lack of technical progress
in the development and improvement of the testing
methods but also because of lack of agreement as to
their scope, objectives, and applicability to a given
problem. Artificially soiled fabrics always have been
and still are a subject of controversy. The validity of
some types with respect to correlation with practice
1 Presented at the fall meeting of the American Oil Chemists' Society,
Chicago, Oct. 311Nov. 2, 1949.
JULY, 1950 No.
has been seriously questioned. There is little agree-
ment as to methods of carrying out the washing oper-
ation on the artificially soiled fabric or on methods
of measurement of the results. There is no uniformity
in the mode of expression of results and, perhaps the
least excusable of all, no standard reference deter-
gents have been established for industry-wide use.
In comparison with the progress which has been
made in t h e development and standardization of per-
formance tests in other fields, this presents a rather
sorry picture. Extenuating c i r c u m s t a n c e s are not
lacking, considering t h e complexity of the effects
which are involved and the lack of fundamental in-
formation on some of the most pertinent phenomena
concerned. It is believed however that the general
situation is worse than it needs to be. This paper is
offered with the hope that it may be a small contri-
bution to the resolution of some of the questions con-
cerned. It is not a review of principles of detergency
nor of published methods for its measurement. It is
merely an exposition of the underlying philosophy
of the methods currently in use in our laboratories
and in some instances in the laboratories of other
organizations. The details of our procedures have
been published (8) without explanation of their de-
velopment or a statement of reasons for choice of the
conditions specified, and this paper is intended to
supply some of the previously omitted background.
Scope
Like any laboratory performance test, detergency
tests are used for screening, for guidance in labo-
r a t o r y development programs, and for control pur-
poses. It is idle to criticize laboratory methods on
the score that they are inconclusive, that the ulti-
mate tests must be made in full scale equipment and
under practical use conditions. F o r the purposes for
which laboratory methods are properly used, full
scale trials are usually cumbersome and prohibitively
costly in time and materials. L a b o r a t o r y performance
tests are useful in increasing the probability of suc-
cess in full scale trials and in minimizing the number
of such triaIs which are necessary to yield optimum
practical results. In performing these functions, such
tests are useful only to the extent to which they ful-
fill the following requirements:
a) The test should be reproducible either on an ab-
solute or a relative basis.
b) The test should yield an adequate spread of
numerical results so as to cover the entire per-
formance range, with sufficient precision to show
the smallest differences which are significant in
practice.
249
250 TIlE JOURNAL OF THE AMERICAN OIL CHEMISTS' SOCIETY, JULY, 1950
c) The test should be capable of correlation with
practice in the specific field of use for which it
is intended.
I t is generally realized, and it has been f r e q u e n t l y
stated in the literature that cleaning operations are
so diverse with respect to the nature of the surfaces
to be cleaned, the nature of the soil to be removed,
as well as other limitations and characteristics of the
system in question, t h a t a n y p e r f o r m a n c e test for de-
tergents can a p p l y only within limited fields. The
procedures u n d e r discussion here a p p l y to detergents
for use in the commercial laundering of cotton fab-
rics employing r o t a r y wash cylinders. They have ade-
quate range, precision, and sensitivity and have been
correlated with practice over a period of several years
in a highly satisfactory manner.
Simulation of Use Conditions
I n performance testing it is generally considered
desirable to simulate use conditions as closely as pos-
sible. Actually, close simulation is neither practicable
nor necessary in this instance. Physical l i m i t a t i o n s
of the l a b o r a t o r y scale of operation do not permit a
close a p p r o a c h to the washing conditions which pre-
vail in commercial laundering. Close correlation with
field results has been achieved however with such at-
t e m p t e d sinmlation being disregarded in favor of
more i m p o r t a n t factors.
The mechanical action which is exerted on the de-
tergent solution-soiled fabric system b y commercial
washing cylinders is not obtained when such cylin-
ders are scaled down to sizes suitable for washing
small artificially soiled swatches. I n the f o r m e r case
the fabrics are partially lifted f r o m the solution b y
the ribbed inner circumference of the cylinder and
fall back into the solution with a rolling motion,
thereby receiving scrubbing action f r o m the cylinder
wall and cleats, as well as between the fabric surfaces
themselves, while detergent solution is forced through
the fabrics. When scaled down to small diameters the
scrubbing action is almost entirely lost. F u r t h e r , the
ratio of detergent solution to soiled fabric in com-
mercial laundering is f a r lower than ratios which are
convenient for l a b o r a t o r y purposes. A typical load-
ing ratio in a commercial washwheel is of the order
of 0.5 gallon per pound of fabrics. A t t e m p t i n g to
reproduce this in the l a b o r a t o r y washing device such
as the L a u n d e r - O m e t e r would result in almost com-
plete lack of mechanical action, as well as require
inordinately large amounts of artificially soiled test
fabric. A typical L a u n d e r - O m e t e r loading ratio is
two 2.5-in. x 3.5-in. swatches per 100 ml. of detergent
solution, which is equivalent to a p p r o x i m a t e l y 6.3
gallons per p o u n d of fabric. I n the L a u n d e r - O m c t c r
the nature of the mechanical action is quite different
f r o m that occurring in Commercial wash cylinders, be-
ing exerted almost entirely b y balls contained within
jars (1).
The m a t t e r of detergent c o n c e n t r a t i o n s presents
another difficulty insofar as simulation of practice
is concerned. I n commercial washwheels where low
ratios of detergent solution to soiled fabrics are the
rule, a considerable fraction of the detergent is con-
sumed in dispersing the soil and b y adsorption on
the fabrics. P a r t i c u l a r l y in the ease of soap, if large
excesses over this amount are added, foaming becomes
excessive and m a y actually p r e v e n t p r o p e r operation.
Thus in use the actual excess detergent concentration
remains within rather n a r r o w limits, which do not
necessarily comprise the o p t i m m n range for compari-
son of d e t e r g e n t s in the laboratory. I n a s m u c h as
practical detergent solution-soiled fabric ratios can-
not be conveniently duplicated in the laboratory, and
more importantly, such small concentrations cannot
be maintained at a constant level during testing due
to variations in the consumption of various deter-
gents, a t t e m p t i n g t o c a r r y out l a b o r a t o r y tests at
actual working c o n c e n t r a t i o n s would be needlessly
restricting. Because of these considerations, in the
development of the methods u n d e r discussion, pri-
m a r y emphasis has been placed on controlling the
factors affecting the p r o p e r t y to be measured r a t h e r
t h a n a t t e m p t i n g to simulate field conditions. Since
the L a u n d e r - O m e t e r provides a convenient means of
carrying out a washing process under controlled con-
ditions of temperature, time, and agitation, it is em-
ployed in both the soil removal and the whiteness
retention tests.
Published criticism of the methods employing use
of L a u n d e r - O m e t e r has not been lacking (2, 4). The
shortcomings which have been pointed out however
are concerned mainly with failure of different multi-
component soils to yield concordant results in testing
series of detergents and failure of some soils to cor-
relate with practice. I n the opinion of the authors,
these findings are concerned to a greater degree with
the soils and with the reflectance method for meas-
urement of the results t h a n with the L a u n d e r - O m e t e r
itself. Our experience has not revealed any serious
shortcoming of the L a u n d e r - O m e t e r as a l a b o r a t o r y
instrument.
The chemical nature of soils encountered in ac-
tual l a u n d e r i n g is complex and subject to wide vari-
ation. As a practical m a t t e r no close simulation can
be accomplished and therefore, r a t h e r t h a n use a
multi-component soiling m i x t u r e as a gesture in this
direction, we have sought to nmke the soil as simple
as possible. Simplicity of soil is of considerable im-
portance also f r o m the point of view of lessening
the amount of attention which must be given to the
rigorous control o f the characteristics of each com-
ponent entering into the soiling mixture. Our goal
has been to develop a s t a n d a r d soil r a t h e r t h a n a
typical soiI. The soiling b a t h is intended merely to
deposit carbon on the f a b r i c and to do this in a
controlled and reproducible manner.
Recently, Utermohlen et al.. (6) have published
work which supports this view. They have shown
t h a t the removal of oily m a t t e r and p i g m e n t s f r o m
cotton are separate phenomena and have pointed out
the desirability of simplification of test methods in
the direction which we have taken.
I n actual washing operations the removal of the
last traces of soil is more difficult t h a n the removal
of the bulk of the soil. I n end use p e r f o r m a n c e dif-
ferences between detergents fall within this range in
m a n y cases. I f it is a t t e m p t e d to design l a b o r a t o r y
methods so that swatches washed with high p e r f o r m -
ance detergents fall within this range of cleanliness,
serious disadvantages result. F o r i m p o r t a n t reasons
which will be set forth in detail in later p a r t s of
this paper, we have a c c o r d i n g l y elected to ignore
completely this phase of simulation of practice along
with the others.
 T I t E JOURNAL OF THE AMERICAN O I L C H E M I S T S ' SOCIETY, J U L Y , 1 9 5 0
Separation of the Factors of Detergency
As has been stated in previous publications from
this laboratory (8, 9), we consider it desirable to
conduct separate determinations to measure the soil
removal and whiteness retention properties of deter-
gent systems. Such separation is of no great concern
to the ultimate consumer of finished detergents, who
can evaluate products by means of full scale washing
trials and judge the results in terms of his own stand-
ards. The technical reason for failure, if it occurs, is
usually of little concern to him. This is not true in
the case of the manufacturer or in the case of the ex-
perimental investigator. It is highly advantageous in
the case of experimental syntheses of detergents, the
control of synthetic detergent production, or in the
blending of materials t o fulfill specific requirements,
to be able to separate these effects. Some materials
are effective in soil removal but ineffective in prevent-
ing redeposition, and with other materials the reverse
is true. Accordingly, blending cannot be done intelli-
gently by simple observation of gross effects. This is
particularly true when synergism is involved in the
system.
It has long been recognized that the d e t e r g e n c y
process comprises a reversible equilibrium of the fol-
lowing type :
Substrate 9 Soil + Detergent Solution ~-~
Substrate + Detergent Solution 9 Soil
The mechanism and factors affecting this process have
been discussed in previous publications from this lab-
oratory (9) and more recently by Schwartz and Perry
(5). Removal of soil is represented by the forward
reaction and redeposition by the reverse. The rates
c h a r a c t e r i s t i c of the two opposing tendencies are
dependent on numerous factors, some of which are
interrelated. Among these factors, of course, is the
composition of the detergent solution. In devising our
tests, attempts have been made to hold all factors
other than bath composition constant and to select
conditions in each case which will t e n d to minimize
the opposing tendency. In the simplest view the tests
may be regarded as methods for study of sorption of
carbon on cotton in aqueous systems. If this point
of view is taken, the tests might be considered to be
in a borderline position between performance tests
and characterization tests, the results being distin-
guished from those of the usual characterization tests
on detergents in that they are capable of correlation
with actual washing performance.
Soil Removal Test
Since previous publication of our procedures (8)
several improvements have been made. For this rea-
son and for the sake of convenience in the discussion
which follows, the current procedures are presented
in detail.
Apparatus and Materials.
1. Indian Head muslin, bleached, unfinished. Count 58 x 47.
Weight per sq. yd., 4.7 oz.
Manufactured by Nashua Manufacturing Company, 40
Worth street, New York 13, N. Y.
2. Shell Virgo Oil 38-1)', Code 3263. (Soluble Oil).
Manufactured by Shell Oil Company, 154 ]3agley street,
Detroit 26, Mich.
3. Colloidal Black Dispersion No. 10, approx. 25% carbon.
Manufactured by Binney and Smith Company, 41 E.
42nd street, New York, N. Y.
251
[NOTE: M a n u f a c t u r e of this dispersion has been dlscon
tinued. To the p r e s e n t it has been used exclusively iu
this l a b o r a t o r y and because of stocks on h a n d will be
used f o r some time in the future. A q u a Blak ]3 (ap-
prox. 35% c a r b o n ) , also a p r o d u c t of Binney and Smith
is applicable although it m a y necessitate slight altera-
tion in the soiling procedure in order to meet tenacity
specifications. ]
4. Tumbler, tluebsch, 36" diameter.
5. W a s h w h e e l - - M o n e l , 24" x 34".
6. Raven 11 (Carbon black used in m a n u f a c t u r e of Colloidal
Black Dispersion No. 10).
M a n u f a c t u r e d by ]3inney and Smith Company, 41 E.
42nd street, N e w York, N. Y.
7. L a u n d e r Ometer Type 12QEF.
M a n u f a c t u r e d by Atlas Electric Devices Company, 361
W. Superior street, Chicago, Ill.
[NOTE: The stainless steel bails and pint j a r s used in con-
j u n c t i o n with this device m a y also be obtained f r o m
Atlas.]
8. L u m e t r o n Colorimcter Model 402 E.
M a n u f a c t u r e d by Photovolt Corporation, 95 Madison
avenue, New York 16, N. Y.
Preparation of Standard Water Bound Carbon Soil Cloth.
Bleached, unfinished I n d i a n I I e a d muslin is used w i t h o u t pro-
treatment. :Prior to soiling it is stored in the roll for at least
7 days under conditions of 65% relative h u m i d i t y at 70~
Thirty-five panels m e a s u r i n g 10.5 in. x 36 in., or equivalent
total area, are cut f r o m the roll of conditioned cloth. Two of
the panels are weighed and identified with m a r k i n g pins pre-
p a r a t o r y to the moisture determinations which will be described,
Thirty-seven and three-tenths liters of softened w a t e r ~ having
less t h a n one grain as CaCOa per gallon is placed in the monel
washwheel and 441.2 g r a m s of Shell Virgo 38 P are added. The
wheel is r u n f o r 5 rain. in order to mix the ingredients, a f t e r
which 306.3 g r a m s of Colloidal Black Dispersion No. 10 are
added and mixing is continued for a n o t h e r 5 minutes. D u r i n g
this operation the t e m p e r a t u r e is nmintained at a p p r o x i m a t e l y
90~ The cloth panels are added piece by piece to the soiling
mixture, and the wheel is r o t a t e d at 42 r.p.m, f o r 30 minutes,
s t o p p i n g at 10-minute intervals to u n t a n g l e the cloth. The speed
of the wheel is then reduced to 15 r.p.m, and the carbon sus-
pension is drained, with the wheel running, d u r i n g a 30-minute
period. The soiled panels are removed and passed one by one
t h r o u g h a m a n u a l l y driven r u b b e r roll wringer, the tension of
which is a d j u s t e d so t h a t the moisture retention is 120 ~ 5%
b~sed on the weight of the dry fabric. The b a t c h is then placed
in the t u m b l e r which is operated f o r t5 m i n u t e s at room tem-
perature. One of the marked panels is removed and quickly
weighed while continuing t u m b l i n g the remainder of the batch.
T u m b l i n g is continued until the m o i s t u r e content is between
75% and 85% as determined on the second panel. The rate of
decrease in moisture content is a p p r o x i m a t e l y 1% per minute.
The total t u m b l i n g time is usually 20 to 25 minutes. The mois-
ture test panels are r e t u r n e d to the t u m b l e r immediately a f t e r
weighing. When t u m b l i n g is completed, the panels are removed
and allowed to dry by h a n g i n g edgewise a t room conditions
for 48 hours. On completion of drying, the cloth is cut into
test swatches m e a s u r i n g 2.5 in. ~.~ ~ 2 in. by 3.5 in. + 1~2 ~n.,
using a power-driven guillotine p a p e r cutter. They are stored
at 65% relative h u m i d i t y and 70~ p r i o r to use.
On completion of each batch of soiled cloth it is necessary
to determine its conformance with loading and tenacity speci-
fications. This is done by means of the soil removal procedure,
using two reference detergents. A s t a n d a r d sample of Kreelon
4D e is used at 2.5 g r a m s per liter in distilled w a t e r and the
test is conducted at 140~ The carbon concentration in the
wash liquor m u s t be between 9.0 and 12.0 milligrams per liter.
I n a second test s t a n d a r d Kreelon 4D at 2.5 g r a m s per liter
t o g e t h e r with s t a n d a r d Carbose z at 0.25 g. per liter is used. The
ratio of carbon concentrations in the w a s h liquors betweerL the
1Water prior to sof~e~ning has the following composition (analysis
furnished by Water Department, City of Wyandotte):
To~al solids ............................................................. 140.4 ppm.
C~eium hardness as CaCOa................................... 83.8 ppm.
:~It~gnesium hardness as CaCOc.............................. 30.9 ppm.
Alkalinity as CaCOa............................................... 78.0 ppm.
Sodium and potassium as Na ................................. 5.6 ppm.
Silica ...................................................................... 2.4 ppm.
Sulfate as SO~........................................................ 20.6 ppm.
Chlorides as CI....................................................... 21.0 ppm.
p n .......................................................................... 7.4 ppm.
2 Manufactured by Wyandotte Chemicals Corporation, Wyandotte,
Michigan.
252 T H ~ JOURNAL OF THE AMERICAN OIL CHEMISTS' SOCIETY, JULY, 1950
first and second test must lie between the limits of 1.74 and
1.84. Any batches failing to conform to these specifications
are discarded.
Procedure for Carbon Soil Removal Evaluation. The pro-
cedure is applicable to synthetic detergents or soaps, with or
without builders and promoters. It is not recommended for
testing soap systems in very hard water, where initial turbidi-
ties of solution raay contribute a major portion of the total
turbidity. The procedure consists of washing the test swatches
in a Launder-Ometer and measuring the light transmittancy
of the detergent solution by means of a photometer. A correc-
tion is made for the initial turbidity of the detergent solution.
Results are expressed on a relative basis; standard reference
detergents are measured concurrently. In these laboratories a
selected and homogenized stock of Kreelon 4D (having an
arbitrarily assigned value of 100) is ordinarily used as the
reference detergent.
One liter of the detergent solution to be tested is prepared
and 100 milliliters of this solution is transferred by means of
a pipette to each of 10 one-pint Launder-Ometer jars. The
jars are placed in a constant temperature bath and allowed to
stand until thermal equilibrium is reached. Ordinarily a tol-
erance of -~ 2~ is allowed. Fifteen 18-8 stainless steel balls
of ~/~" diameter are placed in each jar along with two swatches
of standard soiled cloth in the case of nine of the jars. To the
tenth jar two swatches of unsoiled, bleached, unfinished Indian
Head muslin are added. The contents of this jar is used to
determine the turbidity of the detergent solution. Immediately
following the addition of the swatches, the jars are sealed and
placed in the Launder-Ometer. The Launder-Ometer is operated
for a 10-minute period at 42 ~.~ 2 r.p.m. The jars are removed
and again placed in the constant temperature bath. The con-
tents of each of the nine jars containing soiled swatches is
poured through a Buchner funnel without filter paper into a
large beaker, which is also contained in the constant tempera-
ture bath. This removes the steel balls and soiled swatches.
The composite suspension thus obtained is mixed thoroughly,
and a specimen is placed in a 20~mm. photometer cell. (In
order to minimize temperature effects the cell is kept in a
beaker of distilled water in the constant temperature bath
prior to use.) The cell is placed in the Lumetron colorime-
ter and the transmittancy determined in reference to distilled
water contained in a similar cell. The multiplier filter which
is supplied with this instrument is used if necessary in order
to balance the instrument. It is left in place in balancing
against distilled water. White light is used in these measure-
ments. The light transmittaney of the solution from the jar
containing the unsoiled swatches is measured similarly, and
the transmittancy readings are converted to carbon concen-
trations by reference to a calibration curve or table. The cali-
bration data is obtained by making measurements on a series
of dilutions of a dispersion of 1 g. of carbon black (Raven 11)
in one liter of distilled water containing 0.5 g. of Triton NE.
The calibration should cover the range from 0 to 30 mg. of
carbon per liter. It will be noted that the light transmittancy
follows the Beer-Lambert law through part of this range, with
deviation at higher concentrations due to light scattering. The
net concentration of carbon in the detergent solution is cal-
culated by deducting the carbon concentration equivalent to
the turbidity of the detergent from that of the soiled suspen-
sion. This net carbon concentration is divided by a similar
value obtained by use of the standard reference detergent
determined concurrently on the same stock of standard soil.
The carbon soil removal value is reported in terms of percent-
age of the reference material. (~ote: I f the detergent being
tested contains soap, gelation may interfere with the light
transmittancy measurements due to cooling during measuring.
In this case the suspension and unsoiled solution are diluted
with isopropanol to twice their initial volumes. A separate
calibration curve prepared by the use of 50% isopropanol is
used.)
D i s c u s s i o n . F o r s e v e r a l y e a r s i n this l a b o r a t o r y soil
r e m o v a l tests w e r e m a d e a c c o r d i n g to a c o n v e n t i o n a l
m e t h o d w h i c h has b e e n u s e d in m a n y l a b o r a t o r i e s .
T h e soil co n s i s t e d of N o r i t C, l u b r i c a t i n g oil, a n d h y -
d r o g e n a t e d c o t t o n seed oil a p p l i e d to t h e f a b r i c f r o m
a m e d i u m of S t o d d a r d solvent. A f t e r th e w a s h i n g
process t h e l i g h t r e f l e c t a n c e of th e swatches was meas-
u r e d as w e l l as t h e t u r b i d i t y of t h e d e t e r g e n t solu-
tions. C o m p a r i s o n s of d e t e r g e n t s c o u l d be m a d e b y
m e a n s of p a r a l l e l m e a s u r e m e n t s , u s i n g th e same b a t c h
of soiled cloth. W i t h d i f f e r e n t b a t c h e s of soiled cloth,
d i s c r e p a n c i e s a p p e a r e d w h i c h l ed us to i n v e s t i g a t e
some of t h e v a r i a b l e s i n v o l v e d in its p r e p a r a t i o n , in-
e l u d i n g c o m p o s i t i o n a n d c o n c e n t r a t i o n of the s oi l i ng
b a t h , t i m e of i m m e r s i o n , m o i s t u r e c o n t e n t of t he cloth,
m a n n e r of c a r r y i n g out t h e so i l i n g o p e r a t i o n , a n d ag-
i n g of the soiled f a b r i c . I t was f o u n d t h a t t he mois-
t u r e c o n t e n t of t h e cl o t h at t h e t i m e of i m m e r s i o n
h a d a p r o n o u n c e d effect on t h e t e n a c i t y of t h i s t y p e
of soil. F o r e x a m p l e , soiled cl o t h p r e p a r e d f r o m cloth
p r e c o n d i t i o n e d at 2 0 % r e l a t i v e h u m i d i t y was consid-
erably more tenacious and somewhat more uniform
t h a n w h e n t h e cloth w a s p r e c o n d i t i o n e d a t 65% rela-
tive humidity, with other conditions constant. The
use of c o m p l e t e l y d e h y d r a t e d cloth s e e m e d i n d i c a t e d ,
a f a c t w h i c h w o u l d i n v o l v e some o b v i o u s difficulties.
I t was also f o u n d t h a t t h e r a t i o of m i n e r a l oil a n d
h y d r o g e n a t e d v e g e t a b l e oil to c a r b o n also affected t he
response to b u i l t soaps in c o m p a r i s o n w i t h soap alone.
I n v e r s i o n of r e s u l t s o c c u r r e d if t h e r a t i o s w e r e v a r i e d
o v e r a c o n s i d e r a b l e r a n g e . I t was p o s t u l a t e d t h a t
these f a c t o r s w e r e i n t e r r e l a t e d . T h e m e c h a n i s m of
the soiling process m i g h t be v i s u a l i z e d as i n v o l v i n g
a p h ase b o u n d a r y b e t w e e n t h e w a t e r i m m i s c i b l e sol-
v e n t a n d a l i q u i d film of w a t e r a d s o r b e d on t he
f a b r i c . T h i s c o u l d c o n s t i t u t e a b a r r i e r to t he a d s o r p -
t i o n of oily m a t e r i a l on t h e f a b r i c , e s p e c i a l l y d u r i n g
t h e e a r l y stages of the soiling o p e r a t i o n . T h e r e f o r e
v a r i a t i o n i n m o i s t u r e c o n t e n t of t h e c l o t h m i g h t be
e x p e c t e d to m a k e f o r e r r a t i c b e h a v i o r b y a f f e c t i n g t he
b o n d i n g of t h e p i g m e n t to t h e f a b r i c .
S t u d i e s of t h e effect of soiling t i m e i n d i c a t e d t h a t
t e n a c i t y i n c r e a s e d w i t h so i l i n g t i m e b e y o n d t he p e r i o d
w h e n the cloth was i n c r e a s i n g its t o t a l load, suggest-
i n g t h a t as e q u i l i b r i u m is a p p r o a c h e d , finer p a r t i c l e s
of c a r b o n w e r e d i s p l a c i n g co ar ser ones f r o m the cloth.
N o r i t C was t h e r e f o r e c o n s i d e r e d to h a v e too b r o a d a
r a n g e of p a r t i c l e sizes f r o m t h e s t a n d p o i n t of soiling
as well as r e g u l a r i t y of o p t i c a l response in m e a s u r i n g
soil r e m o v a l .
A l t h o u g h t h e d e g r e e of i n i t i a l soiling c o u l d be r e a d -
i l y c o n t r o l l e d b y selection of soiling b a t h c o n c e n t r a -
t i o n a n d so i l i n g time, choice of c o n d i t i o n s p r e s e n t e d
some u n c e r t a i n t i e s . A w a t e r w a s h b a c k w a s u s e d to
r e m o v e s u p e r f i c i a l soil a n d to b r i n g r ef l ec t a nc e val-
ues w i t h i n a s u i t a b l e r a n g e f o r m e a s u r e m e n t . I t was
f o u n d to be r a t h e r difficult to r e p r o d u c e t h e soil l o a d
r e m a i n i n g a f t e r t h e w a t e r w a s h back, a n d in t he e v e n t
of d i s t i n c t differences at t h i s stage i n c o n s i s t e n t r e s u l t s
w e r e s o m e t i m e s o b t a i n e d i n t h e c o m p a r i s o n of d e t e r -
gents. T h i s was p a r t i c u l a r l y t r u e i f final reflectances
a p p r o a c h e d t h e i n i t i a l r e f l e c t a n c e s of t he u n s o i l e d
cloth, in w h i c h case it b e c a m e a p p a r e n t t h a t r e d e p o -
sition effects w e r e c o n t r i b u t i n g s i g n i f i c a n t l y to t he
gross effect, t h u s r e d u c i n g t h e specific n a t u r e of t h e
test.
I n g e n e r a l , t h e p r e c i s i o n l e f t a g r e a t deal to be
desired, p a r t i c u l a r l y in t h e case of t h e r e f l e c t a n c e
m e t h o d w h e r e sm al l differences in i n s t r u m e n t a l r e a d -
ings w e r e i n v o l v e d in single w a s h tests. T h e t u r b i d -
it y m e t h o d y i e l d e d m o r e c o n c o r d a n t results, w i t h
b e t t e r s p r e a d of values.
T h e r ef l ect an ce m e t h o d is s u b j e c t to some i n h e r e n t
weaknesses. Th e p r e c i s e r e l a t i o n s h i p b e t w e e n soil con-
t e n t a n d rei~ectivity is still a s u b j e c t of some u n c e r :
t a i n t y a l t h o u g h it has b e e n f a i r l y w e l l e s t a b l i s h e d
o v e r a l i m i t e d 1oortion of t h e w o r k i n g scale f o r some
soils (7, 9). U t e r m o b l e n h as r e p o r t e d a l o g a r i t h m i c
r e l a t i o n in t h e case of a n i r o n oxide soil. T h e K u -
 T~IF. JOURNAL OF THE AMEalCAN 0m CHEMISTS' SOCIETY, JULY, 1950 253

belka-Munk equation is used by some workers. Per- large changes in soil content at high loadings, which
haps the most serious objection to the use of the amounts to poor sensitivity. The situation is reversed
reflectance method is the disproportion between quan- at the other end of the scale. This is illustrated b y
tities of carbon which are redeposited and their effect F i g u r e 1, taken from work previously published b y
on reflectance, which may arise from the physical
state of the redeposited soil and its distribution over
the most accessible and therefore most visible por-
tions of the fabric. When testing detergents having
good soil removal and poor whiteness retention prop-
erties with lightly soiled cloth, we have experienced
O. 1 % SOAP
decreases in refectance values while actually remov-
ing soil as evidenced b y the accumulation of carbon + 0.000% M.S.
in the wash liquor. At best, reflectance measurements 8
o0.050" " "
are based on a secondary effect rather than a direct
l! II
measurement of the desired quantity, presuming of
course that the objective of the test is to determine
the actual quantity of soil removed. _g
These considerations, in the judgment Of the au-
thors, pointed to the adoption of an essentially single " 4
component soil to be applied from aqueous medium
and to the use of the t u r b i d i t y method in measure-
ment of results. These steps were taken in 1943, and
since that time the procedures here reported have
been under development and in use in our labora-
tories. It is recognized of course that other workers
have advanced the type of procedure which we aban- O A
doned to a better degree of t'eliability than existed 20 4O ~) 80
then, while our efforts have been devoted to working REFLECTIu
out procedures embodying the departures mentioned. F I G . 2. R e l a t i o n between soil content and light reflectance
In some recent instances close agreement has been ex- of artificially soiled cloth, as determined by multiple wash tests
using soap and modified soda.
perienced in cooperative testing, the other laboratory
using the reflectance method, with refined technique.
A n u m b e r of advantages accrue from the use of an this l a b o r a t o r y (9). The same conclusion can be
aqueous soiling m e d i u m . It probably represents a drawn from the work of Utermohlen (7). Freedom
closer approach to natural soiling conditions than the from these restrictions permits the use of rather heav-
use of organic solvents although that is not consid- ily loaded fabrics, which is a distinct advantage in
ered to be an important factor. Certainly it is sec- minimizing redeposition. The rate of deposition is a
ondary to the eonsiderations of reproducibility and function of the soil concentration in the solution and
appropriate tenacity and range of response to deter- on the fabric. F o r a given concentration in solution
gents known to have varying degrees of effectiveness. it is naturally at a maximum for perfectly clean
The effeet of moisture content of the cloth on the cloth.
soiling process is drastically reduced b u t not entirely The characteristics of soiled cloth prepared accord-
eliminated: A minor effect of tenacity remains, and ing to the procedure given above are shown in Table
for this reason the cloth is preconditioned at 65% I. In these multiple wash tests the detergent solu-
relative humidity at 70~ in our eurrent proeedure. tions were replaced after each 10-minute washing
Completely dehydrated cloth is not necessary or de- period. The degree of loading and general tenacity
sirable as the possibility of disproportionation of soil- characteristics can be judged from the reflectance
ing i n g r e d i e n t s , that is pigment, fats, and oils, is vahles which are quite low and do not change mate-
eompletely eliminated b y the simple soil system used. rially in a single 10-minute washing period. They
A very important benefit of the use of water ap- cover but little of the useful working scale of the
plied soil coupled with t u r b i d i t y m e a s u r e m e n t s is reflectometer through the series of washes.
the freedom of choice of soiling levels which is per- On the other hand, the transmittancy of the deter-
mitted. In the reflectance method one is restricted gent solutions encompasses the entire working range
b y very small changes in reflectivity with relatively of the Lumetron colorimeter. This provides sensitiv-

TABLE I
Effect of Multiple W a s h i n g of W a s B o u n d C a r b o n Soiled Cloth
D e t e r g e n t c o n c e n t r a t i o n , 2.5 g. p e r liter distilled w a t e r . T e m p e r a t u r e , 1 4 0 ~

Distilled w a t e r Kreelon 4D L-1386"

Transmit- C a r b o n con- Transmit- C a r b o n con- Transmit- C a r b o n con-
W a s h i n g time, m i n . Reflectance, tancy, ~ of centration, Reflectance, taney, % of c e n t r a t i o n , / Reflectance, tancy, % of centration,
% of M g O distilled mg. per % of M g O distilled rag. p e r L %ofMgO distilled mg. per
water liter water liter I water liter
0 ........................................... 11.7 11.2 11.2
5 ........................................... 15.8 45.8 24.8 9.7 13.1 14.3
10 ........................................... 17.2 32.5 7.8 12.5 18.2 11.8 14.6 32.0(1~) t 21.3
20 ........ ~.................................. 18.3 23.4 10.1 13.1 13.5 14.1 15.7 17.o(M) 25.9
30 ........................................... 19.4 19.5 11.5 13.2 12.0 15.0 16.0 . 12.5 ( M ) 28.1
40 ........................................... 19.9 15.0 12.5 13.9 10.5 15.8 17.4 9.9 ( M ) 29.8
*A l a b o r a t o r y refer@nce d e t e r g e n t c o n t a i n i n g K r e e l o n 4D, Carbose, a n d modified soda.
t ( M ) i n d i c a t e s r e a d i n g s t a k e n w i t h o u t m u l t i p l i e r filter i n L u m e t r o n Colorimeter.
254 T H E JOURNAL OF THE AMERICAN OIL CHEMISTS' SOCIETY, JULY, 1 9 5 0

ity and precision well in excess of that inherent in

the other steps of the procedure and obviates the
necessity for a n y elaborate s t a t i s t i c a l approach to
this phase of the test. The solutions from the nine
jars involved in the single test are easily and relia-
bly averaged b y merely mixing the solutions prior
to the transmittancy measurements.
The t r a n s m i t t a n c y measurements are reproducible
within 0.3% of the transmittancy of distilled water,
corresponding to a range of uncertainty of 0.045 mg.
of carbon per liter. The precision of this measure-
ment alone, for the average amounts of carbon re-
moved in single wash tests, is in the order of one part
in 400.
Excluding errors involved in handling swatches,
H u n t e r reflectometcr readings are r e p r o d u c i b l e to
0.1% on the magnesium oxide scale. Therefore to
reach purely instrumental precision of 1 p a r t in 400~
it would be necessary to wash the swatches through
a reflectance change of 40% of magnesium oxide.
Also it would be necessary to measure the reflectance
of each side of 18 swatches to equal the precision
of the t u r b i d i t y method.
B y proper choice of cell thickness in the light
transmittaney measurements, one is free to select any
degree of loading of the cloth which is desired. As
previously stated, we have chosen to use r a t h e r heav-
ily loaded cloth in order to minimize redeposition. An
additional advantage in providing a rather large res-
ervoir of carbon lies in the fact that during the wash-
ing procedure in the Launder-Ometer there is little
change in the soiled fabric with respect to tenacity
and total removable soil.
The data from Table I are shown graphically in
F i g u r e 2, in which the cumulative amounts of carbon
]~m. 3. Electron photomicrograph of Raven 11 (dry carbon
black).
that prolonging the test would only serve to broaden
the differences.
F o r the sake of rigor, it might be argued that
the soiled cloth should be subjected to a water wash
back prior to use in order to remove any superficial
carbon along with any soluble oil and d i s p e r s i n g
agent picked up from the soiling bath. Although this
can be done, we have not f o u n d it to be necessary for
ordinary purposes. The quantities of soluble oil and
dispersing agent present in the cloth are such that
their concentration in the detergent solution being
tested is less t h a n 0.20 g. per liter. Their effect on
the light transmittancy is small, and it is cancelled
out when the results are expressed in terms of the
reference detergent. The effect of the carbon which
is removed b y water alone is significant, however its
removal would only serve to change the slope of the
curves without altering their relative positions. Ex-
cept when working at extremely low concentrations,
where the traces of dispersing agent might interfere,
we have no evidence to indicate that the extra labor
of making a water wash back is warranted.
I t is believed that an important factor contributing
to the behavior of the soiled cloth is the fine particle
size and the range .of particle size distribution of the
carbon which is used. Figures 3, 4, and 5 are electron
micrographs of Raven 11, the d r y carbon, Aqua Blak
B, and Dispersion N u m b e r 10. In the dispersed forms

IIl il i I l lilt/
FIG. 2. Effect of multiple washing of water bound carbon
soiled cloth. Detergent concentration, 2.5 g. per liter in dis-
tilled water. Temperature, 140~

removed are plotted against the logarithms of the

time intervals. The ordinate is intersected at the
1-minute period in which case no datum points were
obtained because of manipulative uncertainties. The
regularity of response is clearly evident, and it is
apparent that multiple wash tests are unnecessary
with this technique. The differences between the de-
tergents are amply shown b y a single 10-minute wash
period. I t is evident that these differences are in the
nature of rate or intensity of soil removing action and ~IG. 4. Electron photomicrograph of Aqua Blak B.
 Tn.~ JOURNAL OF THE AMERICAN OIL CHEMISTS' SOCIETY, JULY, 1950 255

Whiteness Retention Test

Apparatus and Materials.
1. Hunter Multipurpose Reflectometer.
Manufactured by Henry A. Gardner Laboratory inc.,
Apparatus Division, 4723 Elm street, Bethesda, :Md.
2. Gyrosolver.
Manufactured by Fisher Scientific Company, Pitts-
burgh, Pa.
3. 1Prosperity Pony Press, Model 219-P0.
Manufactured by Prosperity Company inc., Syracuse,
N.Y.
4. Other materials and apparatus as listed under soil re-
moval test.
Procedure. Bleached, unfinished Indian Head muslin is cut
into swatches measuring 2.5 + 1A2" by 3.5 + 1~2". The light
reflectance of each side o f each swatch is measured by means
of a Hunter Multipurpose Refleetmneter, using a standard white
hacking having a reflectance value of 68.8% of magnesium ox-
ide behind the cloth. The green filter supplied with the instru-
ment is used. The reflectance of the front and back Of each
piece is averaged, and the swatches are classified in a multi-
Fro. 5. Electron photomicrograph of Colloidal Black Disper- compartment box marked off in 0.1% units. The swatches for
sion NO. 10. any single test are drawn from one compartment. A s t a n d a r d
soil suspension is prepared by diluting 28.55 grams of Aqua
Blak B to 1 liter with distilled water. A weighed quantity
there is no a p p r e c i a b l e a g g l o m e r a t i o n i n c o m p a r i s o n of the detergent to be tested is placed in a 1-1iter volumetric
w i t h the d r y form. The p a r t i c l e size "range is f r o m flask and dissolved in 200 or 300 ml. of distilled water. The
soil suspension is shaken vigorously, and 50 ml. are transferred
0.02 to 0.08 microns. to the flask containing the detergent solution by means of a
The e x t e n t to w h i c h r e d e p o s i t i o n has b e e n ex- pipette, after which the mixtm~ is diluted to one liter. One
c l u d e d f r o m the soil r e m o v a l test has been e s t i m a t e d hundred-ml, portions of the suspension are transferred to each
of 5 Launder-Ometer jars, 15 stainless steel bails are added,
b y m e a n s of e x p e r i m e n t s d e s i g n e d to reveal the maxi- and the jars are placed in the constant temperature bath and
n l u m possible r e d e p o s i t i o n effect. Soiled swatches heated to the test temperature. The jars are placed in the
were washed a c c o r d i n g to the r e g u l a r p r o c e d u r e a n d Launder-Ometer and rotated for 5 min. at 42 _~+ 2 r.p.m. The
t h e c a r b o n c o n c e n t r a t i o n s of the r e s u l t i n g s u s p e n - Launder-Ometer is stopped, and, without removing the jars
from the machine, the lids are opened and two pieces of cloth
sions m e a s u r e d . The s u s p e n s i o n s were r e t u r n e d to the added to the contents of each jar. Immediately prior to their
L a u n d e r - O m e t e r j a r s a n d two clean white swatches addition the swatches are soaked for one minute in distilled
a d d e d to each jar. A f t e r r u n n i n g i n the L a u n d e r - water. The covers are ~placed on the jars and the Launder-
O m e t e r for a n o t h e r 10 m i n u t e s , the c a r b o n concen- Ometer rotated for 30 minutes. The jars are removed from the
Launder-Ometer and the swatches transferred immediately to
t r a t i o n was a g a i n m e a s u r e d . The resu]ts are shown one of the flasks of the autmnatic rinsing device. This device
i n T a b l e I I . I t is seen t h a t the r e d e p o s i t i o n effect is consists of a gyratory shaker holding four 1-Iiter Erlenmeyer
flasks, each of which is equipped with outlets to the drain and
inlet connections to receive water from individual 3-liter dis-
T A B L E II tilled water reservoirs. Three liters of distilled water is passed
~ax~mum Possible l%edeposition During Soil l%emoval Test continuously through the flask containing the 10 swatches while
Detergent concentration, 2.5 g. per l i t e r i n shaking, the operation being completed in 5 minutes. The
distilled water. T e m p e r a t u r e , 1 4 0 ~ swatches are removed and placed flat on clean paper towels
~rhon COU- C a r b o n con- I
and allowed to drain, then are pressed until dry on a PrOs-
eentration eentration perity press at 328 ~ to 338~ The reflectance of each side of
Soiled
a f t e r wash- a f t e r wash- ] D i g fence, Percentage the 10 pieces of cloth is measured and the whiteness retention
Detergent i n g soiled i n g w h i t e I mt p e r of total value for the detergent under test calculated. This value is
cloth swatches, swatches, ~ 1 ~er effect
rag. p e r mg. per I equal to the ratio of the average reflectance after washing to
liter liter 1-- the original reflectance, multiplied by 100. Finally the results
346 L-I386 21.1 20.9
are expressed in terms of percentage of whiteness retention rela-
0.95
352 L-1386 17.3 17.1 .2 1.16 tive to a standard reference detergent determined concurrently.
348 Kreelon 4D 10.9 9.5 .4 12.8
346 K r e e l o n 4D 11,7 10.3 .4 12.0 D i s c u s s i o n . I n p r i n c i p l e the w h i t e n e s s r e t e n t i o n
352 Kreelon 4D 8.3 7.1 .2 14.4 test is less i n v o l v e d t h a n the soil r e m o v a l test. T h e
soil c o n c e n t r a t i o n i n the d e t e r g e n t s o l u t i o n is rela-
g r e a t e r i n the ease of K r e e l o n 4D t h a n i n the case of t i v e l y high, a p p r o x i m a t e l y 0.50 g. o f c a r b o n p e r liter.
the c o m p o u n d e d d e t e r g e n t (because of the p r e s e n c e T h i s p r o v i d e s a l a r g e r e s e r v o i r of soil, t h e r e b y m i n i -
of Carbose i n the l a t t e r ) which is i n a c c o r d a n c e w i t h m i z i n g a n y c h a n g e i n r a t e i n deposition d u r i n g t h e
expectations that interference would increase with course of the test w h i c h m i g h t o r i g i n a t e f r o m this
decrease i n whiteness r e t e n t i o n properties. Since the source. Since t h e r e is v e r y l i t t l e change i n the ear-
o p p o r t u n i t y f o r r e d e p o s i t i o n i n the tests s h o w n i n b o n c o n c e n t r a t i o n d u r i n g the test, it is n o t feasible to
T a b l e I I is g r e a t l y e x a g g e r a t e d b y the use of white d e t e r m i n e the q u a n t i t y deposited on the cloth b y pho-
swatches r a t h e r t h a n t h e h e a v i l y l o a d e d cloth which t o m e t r y of the dispersions, a n d t h e r e f o r e the r e s u l t s
is a c t u a l l y p r e s e n t d u r i n g the soil r e m o v a l test, it is are d e t e r m i n e d a n d expressed i n t e r m s of reflectance.
r e a s o n a b l e to assume t h a t r e d e p o s i t i o u does n o t occur The c a r b o n c o n c e n t r a t i o n a n d the d u r a t i o n of wash-
to a n y s i g n i f i c a n t e x t e n t i n this test. i n g are such t h a t the reflectance values lie b e t w e e n
The a b i l i t y of a d e t e r g e n t system to remove fats or 20% a n d 8 0 % reflectivity on the m a g n e s i u m oxide
oils f r o m f a b r i c is n o t m e a s u r e d b y this test. I t is scale, i n the case of poor a n d good d e t e r g e n t s w i t h
o u r b e l i e f t b a t where i n f o r m a t i o n on this p r o p e r t y respect to the whiteness r e t e n t i o n p r o p e r t y . The con-
is r e q u i r e d , it is best d e t e r m i n e d s e p a r a t e l y , exclud- d i t i o n s are i n t e n d e d to f a v o r d e p o s i t i o n w i t h the ex~
i n g p i g m e n t s , i n which case the r e s u l t s are r e a d i l y c l u s i o n of soil removal, b a s e d :on c o n s i d e r a t i o n of the
m e a s u r e d b y m e a n s of s o l v e n t e x t r a c t i o n procedures. e q u i l i b r i u m concerned. The soil c o n t e n t of the solu-
256 TtIE JOURNAL OF T H E AMERICAN OIL CHEMISTS' SOCIETY, JULY, 1950

tion is high and nearly constant through the test, and TABLE IV

the system reaches equilibrium, within experimental Precision of the Whiteness Retention Test
Detergent concentration, 2.5 g. per liter in
error, during the 30-minute washing period. distilled water. Temperature, 140~
The rinsing procedure is intended to standardize P e r cent
this operation in the interest of precision. The steam Sample No. of Sample Arithmetical mean
operators population mean deviation
press m used in p r e p a r i n g the swatches for final re-
flectance measurements in order to avoid the effects Blended
Detergent No. 1 2 11 342 -4-4.8
which a n y sliding or r u b b i n g on the surface might
have on the observed reflectance. Blended
Detergent No. 2 2 19 212 ~5.3
We believe this procedure to be superior in prin- Average.................................................................................... 5.1%
ciple to tests in which white swatches are included
with soiled swatches in a detergent solution, in which
case the soil content of the solution rises continuously Interpretation of Values
d u r i n g the test period and is dependent on the soil The results of the soil removal and whiteness reten-
removal p r o p e r t y of the detergent being tested. tion tests should be interpreted with full realization
of the nature of the tests, that is, that they are essen-
Precision tially comparisons of the rates of soil removal and
The precision of the test methods described is not redeposition between detergents. Satisfactory levels
considered adequate for expression of the results in in both respects does not constitute final proof that
absolute terms. Therefore control determinations are the detergent will p e r f o r m satisfactorily in the field.
carried out regularly, and all results are expressed They are however reliable indications t h a t the deter-
relative to a s t a n d a r d reference detergent. This com- gent will be satisfactory with respect to these two
pensates for differences in lots of standard soil test properties and t h a t the p r o b a b i l i t y of overall suc-
fabrics as welI as other sources of systematic error. cessful p e r f o r m a n c e is extremely high. Results m a y
The precision of the soil removal test is shown in be used v e r y effectively in predicting field perform-
ance if they are used in comparison with values for
T A B L E III
materials for which clear cut field p e r f o r m a n c e pat-
Precision of the Carbon Soil Removal Test
Detergent concentration, 2.5 g. per liter in terns have been e s t a b l i s h e d . This is illustrated in
distiFed water. Temperature, 140~ F i g u r e 6 which shows typical ranges of values f o r '
Arithmeti-
No. of Sample cal meal1, Mean CARBON SOIL WHITENESS
Sample opera- popula- percentage deviation,
tors tion of Std. per cent REMOVAL RETENTION
Kreelon 4D
Experimental PROMOTED
malBIm
Non-ionic detergent 8 212 ~2.9 SYNTHETIC
K r e e l o n 4D
(Laboratory A) 29 99.5 •
Kreelon 4D 1 22 105 •
Blended detergent SOAP OR
~11 SOAP
No. 1 (Laboratory A) 3 19 143 • z~-- j PROMOTED
Blended detergent SYNTHETIC
No. 1 (Laberatory B) 1 22 150 --~t.6 BUILT SO&r
Blended detergent
No. 2 (Labo:atory A) 8 19 182 +6.7
Blended detergent
No. 2 (Laboratory B) 1 20 183 +2.7
BUILT SOAP +
Average........................................................................................ • Ioo~-- i KREELON 4D KREELON 4D

Table I I I . These data which were collected over a

period of several months were determined b y 7 oper-
ators, on 7 batches of soil and in 3 Launder-Ometers.
The determinations were made on a routine basis in
two separate laboratories which are under separate
supervision, one being a control l a b o r a t o r y and the
other a research laboratory. With the exception of
the e x p e r i m e n t a l non-ionic detergent, the samples
were carefully h o m o g e n i z e d materials which were "1" Z PARTS SOAPj I PART SODA ASH

specially p r e p a r e d for the purpose of obtaining sta- F r o . 6. P e r f o r m a n c e l e v e l s o f d e t e r g e n t s . M e a s u r e m e n t s m a d e

tistical data. The average mean deviation over a wide in d i s t i l l e d w a t e r a t 1 4 0 ~ a t t o t a l c o n c e n t r a t i o n s o f 2.5 g.
per liter.
range of levels is • 3.4%. Statisfaetory agreement
m a y be obtained between laboratories, the largest dif-
ference between the arithmetical means reported b y high titer tallow soap, built soap, and a synthetic de-
the two laboratories on the same material being 5 . 5 ~ . tergent composition containing sodium c a r b o x y m e t h y l
I t m a y be noted that the degree of precision ob- cellulose. The whiteness retention properties of built
tained b y a singIe operator is slightly better t h a n t h a t soaps are critically dependent on th e composition of
obtained among a group of operators. the builder and the ratio of builder to soap used. By
The precision of the whiteness retention tests is assuming average values for built soap as a criterion
shown in Table IV. The average mean deviation is of acceptable performance, acceptance levels are read-
_+ 5.1%. ily apparent. I t follows of course t h a t comparisons
 TIlE JOURNAL OF T I I E AMERICAN
made at single a r b i t r a r i l y chosen concentrations and
t e m p e r a t u r e s are not adequate for complete evalua-
tion of a given detergent, and such investigation in
the l a b o r a t o r y can be of great value in pointing the
way to obtaining optimum results in actual use.
I n our experience, for successful use in commercial
laundries; a detergent must have soil removal and
whiteness retention properties of the order of magni-
tude of built soap as first requirements. We have
also found that the higher the values, the more satis-
f a c t o r y the product is likely to be in actual service.
I n correlating l a b o r a t o r y tests with practice the
practical aspects of laundering have not been ne-
glected. Because of commercial relationships with
thousands of laundries and because of the use of
the test methods for production control of synthetic
detergents, sodium carboxymethyl cellulose, l a u n d r y
builders, and completely f o r m u l a t e d built and pro-
moted synthetic l a u n d r y detergents, as well as for
experimental purposes, a considerable f u n d of cor-
related information has been collected. I n m a n y cases
actual l a u n d r y performance has been determined b y
the use of test bundles carried through 20 or more
washes in a c c o r d a n c e with the generally accepted
practices in the trade, in addition to direct observa-
tion. Within the limits of their applicability the labo-
r a t o r y tests have not once failed, in the past several
years, accurately to reflect field performance.
The tests do not measure the tolerance of the de-
tergent solution to soil loading especially for oil or
greasy matter. This must be determined b y other
tests or b y actual field trials.
Summary
L a b o r a t o r y p e r f o r m a n c e tests for l a u n d r y deter-
gents can fill i m p o r t a n t needs in l a b o r a t o r y develop-
ment p r o g r a m s a n d in control testing, in which eases
full scale practical testing is inapplicable, I t has been
f o u n d to b e unnecessary and undesirable to a t t e m p t
close simulation of practice conditions. I n order to
be most useful to the experimental investigator or
the m a n u f a c t u r e r of detergents the soil removal and
whiteness retention properties should be measured b y
separate tests,
A. soil removal test has been devised in which the
soil, which consists essentially of carbon black, is
applied to the test fabric f r o m aqueous medium. Soil-
Report of the Smalley Foundation ,,Committee, 1949-50
FOLLOWING the eustom initiated a y e a r ago, the
reports of the five subcommittees of the Smalley
F o u n d a t i o n Committee are combined into one
report. I n doing this it appears desirable to discuss
the activities of the various subcommittees individu-
ally and briefly. I n most cases individual detailed re-
ports covering grades, methods of grading, etc., have
been mailed to the individual collaborators b y the
subcommittee chairmen. A b o u t 3,200 samples were
distributed b y this committee.
R . T. D0.VG~TIE J ~ . S.W. GLou
W . C. A U n T R . W . BATES, c h a i r m a n
A . S. RIOHAP~I)SON
OIL CHEMISTS' SOCIETY, JULY, 1950 257
ing f r o m aqueous medium has advantages with respect
to reproducibility in tenacity and in variation and
susceptibility to removal b y detergents having dif-
ferent degrees of effectiveness. The quantity of Soil
removed is measured directly b y means of light trans-
mission measurements on the soiled detergent solution.
This eliminates uncertainties and limitations inherent
in the reflectance method and permits the use of high
soil loads in the test cloth, which minimizes redeposi-
tion effects. Multiple wash tests are not required.
The whiteness retention p r o p e r t y is determined b y
agitating unsoiled swatches in the detergent solution
containing carbon black dispersion and measuring the
reflectance change of the swatches.
The results of both tests are expressed in relative
terms, reference detergents being used as controls.
The precision of the soil removal tests is approxi-
mately • 3.4% in terms of mean deviation and that
of the whiteness retention test a p p r o x i m a t e l y • 5.1%.
Both tests have been used over a period of several
years for research and control purposes and have been
successfully correlated with actual results in commer-
cial laundries.
Acknowledgment
A large n u m b e r of i n d i v i d u a l s in our l a u n d r y
research organization have made substantial contri-
butions to the development of the test procedures
described in this p a p e r and to the accumulation of
the large mass of l a b o r a t o r y and field data which
has made practical correlation possible. We are p a r -
ticu]arly indebted to Clifton E. Smith and Maurice
G. K r a m e r for their contributions. The electron pho-
tomicrographs are the work of L. E. Kucntzel of our
physics laboratories.
REFERENCES
1. Bacon, 0. C., a n d Smith, g. E., Ind. Eng. Chem. 40, 2361 (1948).
2. Crowe, a. B., Am. Dyestuff tgeptr. 32, 237, ( 1 9 4 3 ) .
3. H a r r i s , J. C., Soap a n d Sanit. Chemicals 19, 21 ( 1 9 4 3 ) .
4. Lambert, J. M., a n d Sanders, H. L., Abstracts of Pauers, Ameri-
can Chemical Society, Atlantic City Meeting, S~ptember, 1949.
5. Schwartz, A. M., a n d P e r r y , J. W., Surface Active Agents. In-
terseience Publishers, New York, 1949.
6. Utermohlen, W. P., Fischer, E. K., Ryan, M. E., a n d Campbell,
G. I-I.. Textile Resea.rch J. 19, 489 ( 1 9 4 9 ) .
7. Utermohlen, W. P., a n d Wallace, E. L., ibid. 17, 670 ( 1 9 4 7 ) .
8. V a u g h n , T. H., a n d Smith, C. E., J. Am. Oil Chem. Soc., g5, 44
(~948).
9. V a u g h n , T. It., Vitlone, A., a n d Bacon, L. R., Ind. E n g . Chem.
3S, 1011 ( 1 9 4 1 ) .
[Received December 6, 1 9 4 9 ]
REPORT OF THE SUBCOMMITTEE ON
OIL SEED MEAL
This y e a r 15 samples were distributed instead of
30. It was believed that this mm~ber of samples dis-
t r i b u t e d over the same period would be more desir-
able t h a n 30 samples. At the end of t h e period we
submitted a questionnaire to the collaborators asking
their comment on the n u m b e r of samples preferred.
The results are listed:
P e r c e n t r e t u r n i n g t h e q u e s t i o n n a i r e .......................... ~. 89
P e r c e n t p r e f e r r i n g 15 s a m p l e s ..................................... 91
P e r c e n t p r e f e r r i n g 30 s a m p l e s .......................... ........... 7