Journal of the Air Pollution Control Association

ISSN: 0002-2470 (Print) (Online) Journal homepage: https://www.tandfonline.com/loi/uawm16

Effect of Air Pollutants on Dyed Fabrics

Victor S. Salvin

To cite this article: Victor S. Salvin (1963) Effect of Air Pollutants on Dyed Fabrics, Journal of the
Air Pollution Control Association, 13:9, 416-455, DOI: 10.1080/00022470.1963.10468200

To link to this article: https://doi.org/10.1080/00022470.1963.10468200

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EFFECT of AIR POLLUTANTS on DYED FABRICS *
I he effect of atmospheric con-
taminants upon dyed fabrics has been
an object of concern to the American
Association of Textile Chemists and
Colorists since 1938. The AATCC
Committee on Colorfastncss of Textiles
to Atmospheric Contaminants (RA 33)
lias actively pursued this problem. The
scope of this research committee is one
which relates quite directly to the
activities of the Air Pollution Control
Association.
"To study the factors which cause
color change on atmospheric exposure
other than photochemical influences and
to establish test methods which would
correlate the fading test with service
performance. At present, the atmos-
pheric contaminants under study include
oxides of nitrogen, ozone, sulfur dioxide,
and the products of hydrocarbon com-
bustion."
Both the AATCC and the Air Pollu-
tion Control Association are interested
in the effects of atmospheric contami-
nants on fabric damage and on destruc-
tion of dyes7 in colored fabrics. There
have not been sufficient examples of
fabric damage by contaminants re-
ported to warrant serious concern. In
the course of dyehouse processing, the
range of fabrics, both synthetic and
natural, are exposed to the action of
dilute mineral acids, diazotizing acids
containing oxides of nitrogen, reducing
agents containing sulfur dioxide, and
bleaching conditions involving chlorine
and peroxide. Fabrics or fibers which
do not withstand these normal dyehouse
processing conditions are not successful
and are withdrawn. The presence of
residual quantities of mineral acid in the
fabric after finishing is always guarded
against, and especially in the case of the
cellulosics where some damage has been
noted under unusual exposure to indus-
trial acid gases.1
It is in the destruction of dyes that
the effect of atmospheric contaminants
is economically important. The extent
of fading damage has been reported
statistically by Johnson2 and also by
LaBarthe,3 who show that the fading of
dyes due to atmospheric contaminants
* Presented at the 56th Annual Meeting
of APCA, Sheraton-Cadillac Hotel, June
9-13, 1963, Detroit, Michigan.
416
VICTOR S. SALVIN, Celanese Fibers Company, Charlotte, North Carolina
can comprise a significant percentage of
the complaints which come to the atten-
tion of department stores and dry-
cleaners. It is the objective of the
AATCC to develop information which
will insure the production of fabrics
which are satisfactory to the consumer
because they withstand atmospheric
contaminants. This is attained by the
establishment of test methods which will
predict both good and bad service per-
formance and the selection and recom-
mendation of dyes and finishing proc-
esses which will give dyed fabrics that
do not show objectionable change where
exposed to atmospheric contaminants.
The.cost to the textile industry is in the
need for testing and in the use of more
expensive dyes and additional finishing
processes which are required to give
this consumer protection.
This paper summarizes five areas of
activity of the AATCC research com-
mittees :
(i) The study of the effect of oxides
of nitrogen on fading of dyes and the
development of a laboratory test pro-
cedure which correlates with service
performance.
{2) The study of the effects of ozone
and related oxidants on fading of dyes
and development of test procedures.
(3) The contribution of atmospheric
contaminants to fading of dyes by light
as a related activity of the AATCC
Committee on Colorfastness to Light
(R 50).
(4) The service exposures of a range
of dyes on various fibers in the air pollu-
tion atmospheres of Los Angeles and
Chicago as compared to the exposure
results in rural areas of Phoenix, Arizona
and Sarasota, Florida.
(5) A co-operative study with the
Division of Air Pollution of the Depart-
ment of Health, Education and Welfare,
on effect of irradiated auto exhaust gases
on dyes.
Table I—Typical Concentration of Atmospheric Contaminants, ppm
Maximum Ra?ige
Rural
Oxides of nitrogen 0.01
Sulfur dioxide 0.03
Carbon monoxide — 23.00
Ozone 0.06-0.11
Aldehydes — 0.3
Sources of Atmospheric
Contaminants
The analysis of the effect of atmos-
pheric contaminants on dyes must
include:
(a) The isolation of the chemicals
responsible for change.
(b) The demonstration that the
chemicals present can give reac-
tion with the dye which result in
the destruction of dye.
(c) The proof of means by which the
chemical comes in contact in
sufficient quantity with the dye
under exposure conditions.
The following materials are shown in
Table I as present in pollution areas.
Ozonides and peroxides of hydrocarbons
and per acyl nitrites have also been re-
ported.4
Sulfur Dioxide—-Coal contains up to
4% sulfur and its combustion emits
sulfur dioxide. Thus in New York, the
yearly emission of sulfur dioxide has
been estimated at 1.5 million tons per
year. In Los Angeles, coal is not used.
Heating is done mainly with oil. The
gases from internal combustion engines
are low in sulfur dioxide. A difference
in atmospheres exist between Los
Angeles and Chicago. The atmosphere
in the coal burning cities is a reducing
atmosphere due to excess of SO2 whereas
the atmosphere in Los Angeles is an
oxidizing atmosphere due primarily to
oxides of nitrogen and ozone.5
Oxides of Nitrogen—Although some
oxides of nitrogen are derived from
natural sources such as electrical storms,
the main source of oxides of nitrogen is
from combustion gases. Automobile
exhaust gases can give up to 500 ppm
of oxides of nitrogen (nitric oxide and
nitrogen dioxide). Space heating using
oil yields combustion gases containing
15 to 50 ppm of oxides of nitrogen. The
Los Angeles Chicago
0.26 0.22
0.05 0.25
—
0.21 0.005
—
Journal of the Air Pollution Control Association
 NHCH3
NHCH3
Fig. 1. Oxides of nitrogen vulnerable dyes.
concentration of oxides of nitrogen will
vary with location and with season.
Maxima of 2 ppm have been reported,
for example, in Los Angeles.
Ozone—-Ozone is present in both rural
and urban atmospheres. In the strato-
sphere, the content is 6 to 8 ppm. At
the ground level, concentrations up to
0.5 ppm have been reported.6 These
concentrations of ozone are present in
areas where no pollution exists such as
the Mojave desert. In Los Angeles the
presence of oxides of nitrogen and
organic oxidants acts as catalyst to con-
vert oxygen to ozone by photochemical
action. This accounts for the high
ozone concentration of Los Angeles.
However, in cases where much sulfur
dioxide is present and where oxides of
nitrogen are low, the kinetics favor a low
ozone content in the urban atmospheres.
In the average rural atmosphere, the
ozone content ranges between 0.01 and
0.06 ppm.
Photochemistry of Ozone Formation
Of the range of atmospheric con-
taminants, not all products absorb
ultraviolet radiation. Sulfur dioxide,
nitrogen dioxide, and aldehydes are
ultraviolet absorbers with nitrogen
dioxide being particularly activated.
Carbon monoxide, nitric oxide, and hy-
drocarbons are nonabsorbers.
The activated molecules react with
molecular oxygen to produce atomic
oxygen. The interaction of sulfur diox-
ide with oxygen is irreversible whereas
the reaction of activated nitrogen diox-
ide is not. A low concentration of NO2
can produce large amounts of atomic
oxygen to form ozone.7
SO2 + ho = SO**
SO2* + O2 = SO4
SO4 + O2 = SO3 + O3
H2O + SO3 - H2SO4
NO2 + hv = NO + O
O + O2 = O3
NO + O2 - NO3
NO, + O2 - NO2 + O3
NO.
NHC 6 H 5
Fig. 2. Oxides of nitrogen resistant dyes.
September 1963 / Volume 13, No. 9
A complex interaction is noted where
quantities of SO2 are introduced into the
system NO2-hydrocarbons which result
in disappearance of the SO2.
Aldehydes—Oxidants—In the combus- Blue 3 whence the typical reddening
tion of gasoline, 4 to 5% is evolved from
internal combustion engines as hydro-
carbons including olefins. Under the
influence of light and in the presence of
oxides of nitrogen, aldehydes are formed.
These may further, in the presence of
ozone, give peroxides possibly through
9
mechanism of free radicals.
The net result of the interaction of
oxides of nitrogen with olefin hydrocar-
bons according to Haagen-Smit8 is to
form aldehydes, peroxides, and to in-
crease the concentration of ozone or
organic oxidant.
RCHO + hv = R—CHO*
RCHO* + O2 = RCO3H
RCO3H + O2 = R—COOH + O3
Fading of Dyes by Oxides of
Nitrogen
It was in 1937 that Rowe and Cham-
10
berlain first demonstrated that the
relatively minute quantities of oxides of
nitrogen in the atmosphere (less than 1
ppm) suffice to produce the reddening
that had been observed on cellulose
acetate fibers dyed with blue disperse
dyes. This wasfirstnoted in the storage
of dyed fabrics in rooms heated by gas
whence this type of fading has been
termed gas fading. The active agent
has been shown to be nitrogen dioxide.
The dyestuff which fades is an anthra-
quinone dye—1 methyl ammo, 4
methyl amino anthraquinone. In simi-
lar fashion, the violet dye 1 amino,
4 amino anthraquinone fades. The
chemical reactions are those of nitrosa-
tion, diazotization, and oxidation.
11
Couper has isolated and identified the
degradation products resulting from the
action of oxides of nitrogen on one to
four dimethyl amino anthraquinone on
acetate. The typical reddening can be
obtained by exposure of the dyed fabric
NO 2 0
NHC 6 H 4 -CH 2 -CH 2 OH between nitrogen dioxide and amino
to NO2 gas from a cylinder or it can be
duplicated by treatment of the fabric in
solutions of nitrous acid. The structure
of vulnerable disperse dyes is shown in
Fig. 1.
The absorption of gaseous nitrogen
dioxide has been demonstrated for ace-
tate, nylon, cellulosics, polyesters, and
wool by Salvin, Paist, and Myles.12
Where the rate of reaction with the fiber
is low, the oxides of nitrogen are avail-
able for reaction with the dye. This is
shown by transfer of absorbed oxides of
nitrogen by dry contact or wet diffusion
to an acetate fabric dyed with Disperse
occurs. In the case of cellulosics, the
absorbed oxides of nitrogen are not
released.
The test procedure for determining
whether a dye is resistant to oxides of
nitrogen is to place the fabric dyed with
it in a chamber containing a gas burner
and expose the fabric to combustion
gases which contain 20 ppm of nitrogen
oxides. A control fabric dyed with 1%
Disperse Blue 3 is faded simultaneously
to a degree of reddening equivalent to
that of six months exposure in a semi-
industrial area. Details13 of the equip-
ment and procedure are given in the
AATCC Yearbook (Test 23—1957).
There are numerous service tests
which demonstrate that these vulnerable
dyes, sensitive to oxides of nitrogen, will
give fading complaints in the industrial
atmospheres where high oxides of nitro-
gen concentration have been established
in air pollution studies. This is shown
in the color slide which shows an acetate
fabric, dyed with Disperse Blue 3,
exposed to three months in the rural
atmospheres, of Sarasota, Florida and
of Phoenix, Arizona, as compared with
the pollution atmospheres of Los
Angeles and of industrial Chicago. The
test fabric has gone toward the typical
red showing oxides of nitrogen fading in
the pollution atmospheres while it has
essentially not reddened in the sunlight
exposure stations in Florida and Ari-
zona.
This tendency to fading on acetate
and on other fibers has necessitated
either (a) the synthesis of new dyes
which will be resistant to oxides of
nitrogen fading, or (b) the addition of
inhibitors which will protect the dyed
fabric against change. The inhibitors
used are either those which will main-
tain an alkaline condition on the fiber
under which reaction with NO2 does not
take place or the codyeing of a product
such as diphenyl ethylene diamine
which acts to preferentially react with
the oxides of nitrogen.
The diazotization of the primary
amine group, nitrosation of a secondary
amine group, and oxidation of amine
groups are mechanisms for the reaction
anthraquinone blue dyes. The point of
417
 Table II—Effect of Exposure Location
Spectrophotomeiric ShadeChanges—Ozone and NO2 Standards
Grey ozone fading standard dyed with:
1.25% Disperse Blue 27
0.35% Disperse Red 35
0.25% Disperse Yellow 37
Gas fading standard dyed with:
1.0% Disperse Blue 3
attack is the reactive ammo group.
This led to the concept of finding blue
dyes which do not contain a free amino
or alkyl amino group. The dye 1
hydroxy, 4 phenyl amino anthra-
quinone is fast to oxides of nitrogen
but is purple. The dye 1 to 5
dihydroxy 4 to 8 dianilino anthra-
quinone is a blue fast to gas fading but
lias limited affinity. The objective of a
blue dye with useful dyeing properties
was finally achieved in the synthesis
of the structure 1 to 5 dihydroxy
8 nitro 4 anilido anthraquinone.14
Other analogs of the dye were made and
Disperse Blue 27 (1 to 8 dihydroxy
5 nitro 4 hj^droxy ethyl anilido an-
thraquinone15) was commercially offered.
(Fig. 2.)
Fadings of Dyes by Ozone
Unexpected Fading of Fabrics Dyed
with Disperse Blue 27—A comprehensive
test was carried out by an acetate fiber
producer to determine whether Disperse
Blue 27 would perform as well in service
as it did in the accelerated oxides of
nitrogen test. Draperies made with
acetate fabrics dyed with Disperse Blue
27 as blue component to a variety of
mode shades were hung in a number of
homes, some of which were in areas
noted for prevalence of gas fading
(Pittsburgh, Pennsylvania) and others
were in localities where gas fading would
be at a minimum (Ames, Iowa).
By the end of six months, color
changes were noted which became even
more pronounced in the 12 months' ex-
posure samples. The changes occurred
in areas where the presence of oxides of
nitrogen was at a low level, such as
Ames, Iowa. In Pittsburgh, Pennsyl-
vania, where high concentration of
oxides of nitrogen was present, the
fabrics were less faded than in rural
areas. This anomalous behavior sug-
gested that some other agent than oxides
of nitrogen was responsible. Evidence
supporting fading as due to ozone was
offered by Salvin and Walker.16 The
various chemical constituents of the
atmosphere were reviewed in order to
determine which of them could produce
the extensive reaction necessary to con-
vert the blue dyes to light yellow or
colorless compounds. The reaction
could be either oxidative or reductive in
nature. The evidence pointed to oxida-
418
L A B
Original 37. 6 -1.3 -4.0
Phoenix 40. 9 +0.6 + 1.0
Los Angeles 45. 2 + 1.9 +3.4
Chicago 38. 6
+0.6 +0.5
Sarasota 41. 3 +0.8 + 1.6
Original 49. 4 +3.6 -46.2
Phoenix 51. 4 +2.2 -38.2
Los Angeles 52. 6 + 15.4 -18.7
Chicago 48. 7 +8.5 -28.5
Sarasota 51. 8 +2.3 -40.8
tion. If reduction were taking place,
the nitro group in Disperse Blue 27
would be reduced to an amino group as
an intermediate step. The reduced
compound is not resistant to gas fading
and reddens upon exposure to oxides of
nitrogen. This reddening was not ob-
served in the industrial atmosphere of
Pittsburgh, whose atmosphere has a
significant oxide of nitrogen content.
Ozone was suspected as the oxidizing
agent. Fading was observed on fabric
areas not exposed to sunlight.
(1) It is present in significant
quantity in both rural and industrial
areas. Although it is present only in
concentration of 0.01 to 0.06 ppm in
areas of dye failure, this could be suffi-
cient to cause change. Ozone in this
concentration causes visible cracks in
stretched rubber band within 24 hr.17
(2) The destruction of dyes could be
duplicated by reaction of ozone with
dyes in solvents.18
(3) The changes could be inhibited
by presence of antioxidants such as
tertiary butyl hydroquinone.
(4) The behavior in service could be
duplicated by exposing dyed fabrics to
ozone derived from ozone lamps.
(5) Dyes which show essentially no
change in the service tests also show no
change in the ozonizer tests. These
dyes generally show low reaction rates
when reacted in solution with ozone.
(6) Aromatic compounds such as
benzene and tetralin react with ozone
at the points of unsaturation to yield
unstable intermediate products (ozon-
ides) which split to form aldehydes,
ketones, and acids. Ozone will attack
the nitrogen substituent present as
amino or substituted amine on the
anthraquinone nucleus of the dye or the
aromatic amino group in azo dyes.
An AATCC test procedure using
ozone from lamps or a grid has been
developed. The procedure involves
exposure of dyed fabric to generated
ozone until a standard has faded to
control shade. The ozone lamps are
electric filament bulbs charged with
mercury droplet (Westinghouse or Gen-
eral Electric) whose output is 4 w on a
110 v line when wired in series with a
protective ballast. Ozone produced in
two bulbs is 0.0034 milliequivalcnts per
minute.
The fading rate of dyes by ozone
correlates with the position of the dye in
the fiber. Thus disperse blues on ace-
tate, triacetate and polyester fibers fade
at a higher rate if the dye is in the outer
layers of the fiber. If dyeing is carried
out under conditions which give penetra-
tion of the dye to the core of the fiber,
the dye is not destroyed to the same
extent. The chemical reaction would
depend on (a) the diffusion of ozone
within the fiber, and (6) the absorption
of ozone on the surface. In the case of
surface absorption of ozone, high
humidities could give a water film which
would raise the absorption rate while
increasing the surface concentration.
At higher humidity, fiber is in a more
receptive condition due to swelling.
The extent of ozone fading is related
to locality as shown in the service trials
reported in detail later. Since it is the
blue component dye which tends to be
most vulnerable to oxidative effects,
tertiary shades on cellulose triacetate
were dyed with a stable yellow, stable
red, but reactive blue and exposed in
four areas which are characterized as
(a) sunlight station of Phoenix, Arizona,
dry, nonpollution; (6) sunlight station
of Sarasota, Florida, moist, nonpollu-
tion; (c) the smog area of Los Angeles,
a high ozone, low sulfur dioxide area;
and (d) industrial area of Chicago, very
low ozone with greater sulfur dioxide.
Exposure for a three month period gave
changes in all areas. The rural areas of
Florida and Arizona showed appreciable
change. Chicago showed least change.
However, Los Angeles where ozone con-
tent is significantly higher, showed most
pronounced change.
The ozone standard, losing blue,
gives clear cut visual changes. The gas
fading standard shows combination of
oxides of nitrogen and ozone change in
the air pollution areas, i.e., a reddening
and lightening whereas in Florida and
Arizona only lightening occurs. Spec-
trophotometric data from the Gardner
Automatic Color Difference meter con-
firms the visual observations.
Atmospheric Contaminants and
Daylight Lightfastness Testing
The study of the fading of dyes due to
oxides of nitrogen and to ozone was
initially limited to the acetate and poly-
ester fabrics. It was in the critical
examination of variables affecting day-
light testing of dyes that the effect of
atmospheric contaminants on other
fibers including cotton, viscose, nylon,
and wool became increasingly apparent.
In 1957, the AATCC Committee on
Colorfastness to Light presented a re-
port on its three-year investigation on
the variables encountered in natural
light fading.19 The conclusions were:
(1) The sun-hour method or any
natural light method in which exposures
are calculated or expressed on the basis
Journal of the Air Pollution Control Association
 Table III—Analysis of Fading Results at Three "Stations on 38 Samples
(Covers Exposure Each Month for 12 Months)"-
Greatest
Chicago
Phoenix
Sarasota
Chicago and Sarasota equal
Chicago and Phoenix equal
Phoenix and Sarasota equal
All three equal
Transfer from Column A (all 3 equal)
Transfer from Column B (all 3 equal)
No appreciable change
a
Only seven months at Chicago (August, September, October 1957 and April, May?
June, July 1958).
of time only cannot be a valid, re-
producible and repeatable test method.
(2) In natural light exposures, the
greatest contributing factor in the
amount of color change produced is the
total amount of radiation received.
Therefore, the Langley unit appears to
provide a satisfactory control for
evaluating lightfastness properties.
(5) The amount of color change
produced is also affected, but to a lesser
degree and not equally on all specimens
by variations in the following:
(a) Specimen temperature
(6) Moisture content
(c) Radiation intensity
(d) Spectral distribution
(e) Possibly other factors not yet
recognized or identified.
(4) The new AATCC Daylight Ex-
posure Method, employing exposure
under glass 24 hr a day against AATCC
Lightfastness Standards, while not as
reproducible as the AATCC Sunlight
Test under glass only between the hours
of 9:00 AM and 3:00 PM, will better
predict service performance.
A second report by C. H. A. Schmitt
of the Lightfastness Committee,20 "Day-
light Testing by the Langley Method"
summarized the effect of locality and of
time of the year on lightfastness results.
The localities were in sunlight ex-
posure stations in Phoenix, Arizona, and
Sarasota, Florida, and in a semi-
industrial area in urban Chicago. Each
specimen was exposed during the month
for the required number of Langleys as
recorded on the Eppley Pyrheliometer.
The objective was to detect variations
in the fading of a specimen from month
to month and from station to station.
Temperature and relative humidity
were recorded variables at constant
Langleys.
The conclusions of this work were that:
(1) The humid areas of Florida
showed statistically more change than
that of dry Phoenix.
(2) Certain direct dyes on cotton
September 1963 / Volume 13, No. 9
A B C D
Greatest Least Least
Color Shade Color Shade
Loss Change Loss Change
2 3 11 4
10 4 15 10
21 15 2 3
2 5 7 1
.—. 1 2 1 subsequent lightfastness tests (Fade-
2 —. — —.
1 2 — —
38 30 37 28
1 fading effects when noted are more
2 evident in fabrics left acid.
8 8
38 38 38
show abnormal behavior as did the acid
dyes for nylon as a function of location.
(3) An analysis of the temperature
and relative humidity conditions during
testing helped to explain partly the
fading on a number of dyes on cotton,
both direct and azoic. However, the
data also indicated that some of the
variations noted on direct dyes on cotton
were not influenced by excessive heat or
moisture.
(4) Testing methods should be studied
which would indicate when fading is due
to factors such as contaminants or
moisture and not daylight.
The variables of the effect of atmos-
pheric contaminants to light fastness
were examined. The anomalous fading
behavior of certain direct dyes for
cotton and rayon has been reported by
C. H. A. Schmitt.21 His observations
were based on dyeings exposed in frames
protected from sunlight in areas which
include Los Angeles, Chicago, Sarasota,
and Phoenix. Several dyes showed
fading equal to that of the samples
exposed to sunlight. He postulated
that moisture is only a contributing part
of this abnormal fading. When the
fabric becomes moist, various materials
in the atmosphere are more readily
absorbed. These contaminants react on
the dyestuff within the fiber. Cunliffe22
has discussed the effect of humidity as
has McLaren23 in reporting on exposures
of fabrics in Bombay, India, vs Man-
chester, England. Niederhauser24 has
exposed various dyed fabrics in France
in his correlation of Fadeometer testing
with sunlight exposure and has shown
variation in various localities, with the
mountain regions showing less change.
The approach used by the Lightfast-
ness Sub-Committee studying atmos-
pheric contaminants was the laboratory
testing of a range of dyes on nylon,
wool, and cellulosics using accelerated
test procedures.25 In particular, the
resistance to oxides of nitrogen and to
ozone was sought. In view of develop-
ment of acidity through oxidation of
sulfur dioxide, the effect of pH on rate
of change was included. The effect of
humidity was not included in the initial
work.
The oxides of nitrogen test showed
appreciable change on the direct dyes
for cotton, Direct Red 75 and Direct
Blue 76.
When the dyes are left acid, there is
appreciable reduction in lightfastness in
ometer). . .
The ozone fading tests showed slight
fading on Direct Blue 76. The ozone
The effect of humidity appears to be
an important factor in effect of ozone.
Thus Bogaty, Campbell, and Appel26
have shown that dry ozone has no effect
on cotton; whereas, moist ozone causes
significant degradation. In the case of
textured nylon dyed with Disperse
Blue 3, exposure to dry ozone gives no
color change; whereas, exposures at
higher humidity give destruction of the
blue dyes.
Service Exposure Trials in Urban
vs Rural Areas
The planning of extensive service
trials was justified by the following
considerations :
(a) The observation of the anomalous
fading to sunlight despite exposure to
same number of Langleys as shown in
the report by the AATCC Lightfastness
Committee RA 50.
(b) The accumulation of a number
of examples of fading on cotton, rayon,
nylon, and wool for which no explana-
tion could be found.
(c) The evidence that ozone fading
is a hitherto unrecognized factor in
destruction of dyes.
(d) The need for specific information
on dye destruction in areas of high
contaminant content.
Exposure was for a 90 day period
during October-December of 1961.
The areas were:
Phoenix, Arizona—Sunlight exposure
station, low humidity nonpollution.
Sarasota, Florida—Sunlight exposure
station, high humidity non-
pollution.
Chicago, Illinois—Industrial area,
pollution, NO-2 high sulfur dioxide,
low ozone.
Los Angeles, California—Smog area,
pollution, NO2 low sulfur dioxide,
high ozone.
The dyeings, as listed, were on a range
of fibers including wool, cotton, rayon,
nylon, Orion, acetate, and polyester.
Although not inclusive, dyes were
chosen which are in common use for
each fiber. Thus for cotton, the range
included directs, fiber reactives, vats,
and sulfurs. Medium depths of yellow,
419
 Table IV—Color Changes on Dyed Fabric—Exposed Without 'Sunlight air to the specimens. The test cabinets
in Pollution and Rural Areas were those supplied by Atlas Electric
Devices Company for daylight exposure
Los
Phoenix Angeles Chicago Sarasota tests. The 55 dyed samples were
mounted to give access to ambient air
Acetate currents on both front and backsides.
Disperse Red 35 4.5Y 4Y 4.5Y 4.5Y
Disperse Blue 27 3W 2W 2.5W 2W
As a measure of the general type of
Oxides of nitrogen fading control atmosphere, control standards as used
Disperse Blue 3 3.5 1.5R 2. OR 3.5 in exposure trials reported by Salvin
Ozone control-gre3r dyed with: and Walker16 were included. These are:
Disperse Blue 27 3.0 1.5 3.5 2.5 (1) The gas fading standard ribbon
Disperse Red 35
Disperse Yellow 37 dyed with 1% of Disperse Blue 3. In
Polyester an atmosphere rich in oxides of nitrogen,
Disperse Yellow 37 4.5 5 4 4.0 it will redden.
Disperse Blue 27 4.5 4 3.5 4.5 (2) The ozone of fading standard
Disperse Red 60 5 5 4 4.5 ribbon dyed to the tertiary grey shade
Wool with the Disperse Blue 27 which is
Acid Black 26A 5 4.5 3.5 4.5 resistant to oxides of nitrogen, but will
Acid Red 89 5 3.5 3.5 2.5Y change on ozone (oxidant) exposure.
Acid Violet 1 4.5 4 3 4
Acid Blue 92 4.5 4 2.5 4 After the exposure, the fabrics were
Acid Red 18 5 4 3.5 4.5 returned. Evaluation was according to
Cotton the International Grey Scale by a panel
Direct Dyes of four observers. Their evaluations
Direct Red 1 4 1.5 1.5 3 were checked by the Gardner Automatic
Congo Red B 4 2.5 2.5 2Y Color Difference Meter. The cases
Direct Red 10 4.5 3.5 3B 4
Direct Blue 76 4 2 grey 1R 3 where color changes were pronounced
Direct Blue 71 4 2.5R 2R 3R (rating of 3) were recognized by all
Direct Blue 86 4 1G 1G 2.5G observers. In the Chicago area, there
Vats was some dulling due to soiling. A
Vat Yellow 2 5 4 3G 5 light scouring on both original and
Vat Blue 29 3G 3G 2.5G 1.5G
Vat Blue 6 4 3.5R 3 4R exposed samples for several Chicago
Vat Red 10 5 4.5 3.5 5 samples was useful in several borderline
Fiber Reactives cases.
Reactive Yellow Y 5 5 4.5 4.5 Results are tabulated for visual
Reactive Red 11 5 5 4.5 5 changes. In the International Grey
Reactive Blue 9 4.5 4R 3.OR 4.5
Reactive Yellow 16 5 5 4 5 Scale, the color differences are on a
Reactive Yellow 13 5 5 4 5 geometric rather than an arithmetical
Reactive Red 23 5 5 4.5 5 scale. Thus five is unchanged, four is
Reactive Red 21 5 5 4 5 slight change, three is an appreciable
Reactive Blue 19 4.5 3 1R 4
Reactive Blue 21 4G 1.5G 1.5G 3G and definite change, two is a severe
Reactive Yellow 12 5 4.5 3.5 4.5 change, while one denotes very severe
Reactive Red 19 5 5 3.5B 4.5 change. Changes in hue are easier to
Reactive Red 20 5 4 4 4.5 recognize than changes in depth, and
Reactive Blue 17 4.5 3 lgrey 4
letters are used to denote reddening—R;
Cotton greening—G; yellowing—Y; weaker—
Sulfur Dyes W.
Sulfur Yellow 2 3.5R 3R 2.OR 2.5R
Sulfur Brown 37 5 4.5 4.5 4
Sulfur Green 2 3B 2.0B 2.0B 2B Color Changes in Service Tests
Sulfur Blue 8 4 3.5G 3G 4
Sulfur Black 1 4.5 4.5 4.5 4.5 (1) The changes in the gas fading
Nylon test ribbon and in the ozone fading
Acid Red 85 5 4.5 3 5 ribbon characterized the air pollution
Acid Orange 49 5 4.5 3 4.5 area of Los Angeles as containing ap-
Disperse Blue 3 5 4 3.5 3.0W
Disperse Red 55 5 4.5 4 3.5 preciable content of nitrogen oxides and
Disperse Red 1 5 4.5 3 4.5 ozone. The rural, nonindustrial areas
Alizarine Light Blue G 5 4.5 3.5 4.5 of Phoenix and Sarasota showed essen-
Orion tially no oxides of nitrogen but were
Basic Yellow 11 5 4.0 4 4.5 moderately high in ozone. Chicago was
Basic Red 14 5 5 4.5 4.5 fairly high in oxides of nitrogen and
Basic Blue 21 4.5 4.5 4 5.0
Disperse Yellow 3 4 5 4.5 4.5 quite low in ozone.
Disperse Red 59 5 5 4.5 4.5 (2) The fading of dyes is shown on a
Disperse Blue 3 5 5 4 4.5 range of fibers including cotton, rayon,
nylon, wool, and acetate. The changes
are most pronounced in air pollution
red, and blue were dyed with no after products of photochemical action on areas where the combined effect of
finish. hydrocarbons. The physical effects of oxides of nitrogen and ozone (oxidant)
The areas chosen were those where humidity in both the swelling of the are present. However, changes are also
the concentrations of atmospheric con- fibers and in increasing absorption were noted in nonpollution areas which could
taminants were reasonably well estab- considered. The exposure cabinents be due to ozone.
lished. These contaminants included used were those used for sunlight ex- The fading is noted on dyes of various
those discussed previously—oxides of posure trials. However, the top was structures including vats, directs, fiber
nitrogen, ozone, sulfur dioxide, and the blocked off. There was free access of reactives, acid, and disperse dyes.

420 Journal of the Air Pollution Control Association


Fig. 3. Average concentrations during days of eye irritation in downtown Los Angeles. Hydrocarbons, aldehydes, and ozone for 1953—54.
oxide and nitrogen dioxide for 1958. From data of the Los Angeles County Air Pollution Control District.
(3) Although the number of dyes
used represents only a small fraction of
the available dyes for each fiber, it is
demonstrated that dyes vary in their
vulnerability to chemical change by
atmospheric contaminants. Choice of
dyes is available to give shade ranges
which will retain their shade on atmos-
pheric exposure in both urban and rural
areas. The use of inhibitors which are
co-dyed or applied in finishing will
afford additional protection.
(4) The atmosphere of Chicago which
is richer in sulfur dioxide shows specific
examples of color destruction not ob-
served in Los Angeles. The direct cot-
ton dyes suffer more pronounced hue
change in Chicago.
Exposure to sulfur dioxide in the
AATCC stoving test shows acid wool
dyes and several direct cotton dyes as
showing shade change. However, the
possibility of higher acid content on the
fiber due to oxidation of sulfur dioxide to
sulfur trioxide must also be considered.
Certain direct dyes on cotton will show
color change with oxides of nitrogen
under more acid conditions. The effect
of low ozone in Chicago is to modify
changes.
(5) The color change of dye due to
atmospheric contaminants—oxides of
nitrogen, ozone, and possibly sulfur
dioxide—will give variable results in
lightfastness testing. This is the basis
for the proviso in the AATCC Daylight
September 1963 / Volume 13, No. 9
h 4. T H
Test Method that fabrics be exposed in
test cabinets away from sunlight to
determine whether change is partially
due to contaminants.
(6) The Florida area showed changes
on several dyes which are unaffected in
Phoenix, Arizona. The greater humid-
ity in the coast area is a factor. It is not
known whether the fibers are in a more
receptive condition because of water
swelling or whether ozone is more
concentrated in the water film.
The photochemistry of stability of
ozone in dry air versus moist air and the
presence of salt are under consideration.
Thus Yeatts and Taube28 have suggested
that the action of ozone on chloride ion
in water solution yields chlorine.
Effect of Irradiated Auto Exhaust
Gases on Dyed Fabrics
The Division of Air Pollution of the
U. S. Department of Health, Education
and Welfare has been examining the
biological effect of auto exhaust gases in
its laboratory at the Robert A. Taft
Engineering Center in Cincinnati, Ohio.
Because of interest in the economic
effect of air pollutants on materials,
experimental facilities were made avail-
able to the Committee on Atmospheric
Contaminants RA 33. With the assist-
ance of J. B. Upham, fabrics were
exposed to the diluted auto exhaust
gases.
These fabrics were duplicates of those
P.M.
Nitric
which had been exposed in Los Angeles,
Chicago, Phoenix, and Sarasota. .The
objective was to determine whether
exposure under controlled conditions
would confirm service exposure results
especially from Los Angeles.
The equipment used is described in
detail by R. G. Hinners.27 Basically,
the atmosphere is one which simulates
the Los Angeles atmosphere.
The exhaust gases from a six cylinder
144 cu in. engine are controlled for con-
centration, relative components, and
diurnal variation. The exhaust gases
after filtration are cooled and humidity
controlled. The air diluted gases are
then irradiated in large chambers with
ultraviolet radiation. The effluent gases
are continuously analyzed for NO and
NO2, carbon monoxide, hydrocarbons,
and ozone. Aldehydes, hydrocarbons,
and peroxy acylnitrites are analyzed by
wet methods.
The pollutant concentrations vary
over a 24 hr period as found in Los
Angeles. These concentrations are
controlled by running the automobile
engine during stated periods during the
day and turning on the ultraviolet lights
for 12 hr. The temperature is kept at
80 to 85 °F. The humidity of the
irradiated dilute exhaust gases is low—
10 to 25%.
Figure 3 shows the average concentra-
tions of ozone nitrogen oxides and other
contaminants through the day in Los
421
Table V—Dye Changes in Irradiated Auto Exhaust Gases to Service Trials
in Pollution Areas
Oxides of nitrogen standard
Ozone standard
Disperse Blue 27—acetate
Direct Red I—rayon
Congo Red B—rayon
Direct Red 10—rayon
Direct Blue 76—cotton
Direct Blue 71—cotton
Direct Blue 86—cotton
Vat Blue 29—cotton
Vat Blue 6—cotton
Vat Red 10—cotton
Reactive Blue 9—cotton
Reactive Blue 19—cotton
Reactive Blue 21—cotton
Reactive Blue 17—cotton
Sulfur Yellow 2—cotton
Sulfur Green 2—cotton
Acid Red 85—Nylon
Benzyl Orange G—nylon
Disperse Blue 3—nylon
Disperse Red 1—nylon
Acid Red 89—wool
Angeles. The concentration of con-
taminants delivered from the irradiation
chambers is in the same ratio as in Los
Angeles but somewhat higher in con-
centration. Thus, at noon in the labora-
tory system, the NO2 is 1.2 ppm and
ozone is 1.0 ppm.
The irradiated exhaust gases are led
to an exposure chamber which receives
them at the rate of 1 cfm. The ex-
posure was for a period of 47 days.
Change was noticeable on some of the
samples at 26 days. The samples were
withdrawn when the oxides of nitrogen
fading standard and gas fading stand-
ards showed appreciable change equiva-
lent to one unit fading by AATCC
standards.
Table V compares the behavior of
dyes when exposed to irradiated auto
exhaust gases with actual service results.
The dyes listed arc those which have
shown significant change in Table IV in
any location.
Color Changes Due to Auto Exhaust
Gases
In general, those dyes which were
found to show significant changes in
Los Angeles exposure also showed same
tendency to fade and same type of hue
change when exposed to irradiated auto
exhaust gases. The exceptions were in
the direct dyes on cotton, i.e., Direct
Red I and Fiber Reactive Blue 19.'
The exposure for 47 days in the
laboratory exposure cabinet is perhaps
two-thirds as severe as the three month
service exposure in Los Angeles. The
oxides of nitrogen standard and the
ozone standard are a qualitative measure
of the severity of exposures. Direct
comparison of dye changes by Inter-
national Grey Scale rating should
consider that exposure is not of the same
422
The results of service exposure of a
range of dyes on diverse fibers in Los
Angeles, Chicago, Phoenix, and Sarasota
Auto can be correlated with the contaminants
Exhaust present. The results also check labora-
Gas Los
Chamber Angeles Chicago tory test methods used to predict
performance. Exposure in the air
3 1.5 2.0
pollution area of Los Angeles shows
3 1.5 3.5
3 2 2.5 fading on dyes vulnerable to oxides of
4 1.5 1.5 nitrogen and to ozone.
4 2.5 2.5 In Chicago, the presence of sulfur
3 3.5 3 dioxide which results in greater absorbed
3.5 2 1
3.5 2.5 2 acidity and the low ozone content gives
2 1 • 1 fading differences.
3 3 2.5 In Sarasota, Florida, only ozone
3.5 3.5 3
4 4-5 3.5 fading is noted. The high humidity is
4 4 3.0 responsible for greater changes than
4.5 3 1 those observed in dry Phoenix, Arizona.
3.5 1.5 1.5 Exposure to irradiated auto exhaust
3 3 1
3.5 3 2 gases under controlled conditions gives
3.5 2 2.0 fading results which are equivalent to
4 4.5 3 service exposures in Los Angeles.
4.5 4.5 3
4 4 3.5 Acknowledgments
4 4.5 3
4 3.5 3.5 In the preparation of this paper,
acknowledgment is made to the con-
tributions of the AATCC Lightfastness
degree. Committee RA 50 and especially to
The low humidity of the laboratory J. E. Norton and C. H. A. Schmitt, to
chamber could be responsible for the the Task Force of the AATCC Atmos-
slow rate of change of the direct dyes. pheric Contaminants Committee R 33,
In the accelerated oxides of nitrogen J. G. Stass, W. N. Pardey, J. M.
test (AATCC Test 23—1957), the Straley, C. A. Baker, V. D. Lyon, and
changes in the direct dyes are more to R. 0. McCaldin, and J. B. Upham of
pronounced at higher humidities and the Division of Air Pollution of the
greater absorption of acid gases. U. S. Department of Health, Education
and Welfare.
Summary
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ber 1949).
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September 1963 / Volume 13, No. 9 455