Full text of DOI:10.1177/004051750007000908

801
of Mohair
J. 54462-4,46 (1986).
Wortmann,
and
Cashmere with
and
Textile Res.
18.
Wool,
and
F.-J.,
Wortmann,
tron
Sheep’s
Wortmann, G.,
Elec-
Wool/
"Scanning
of
as
a
Tool
for the
Microscopy
Fiber
Analysis
16.
17.
zu
den
F.-J.,
Ams, W.,
Untersuchungen
Blends,"
Comett-Eurotex.
Guimares.
Speciality
Portugal,
textilrelevanter
Tierhaare,
Cuticulaschuppenkantenhöhen
1991.
in
"Proc. Int.
Wool Text.
Techn.
no.
2,
Cttee.,"
Org.
rep.
19.
A
New
to
Hair
Zielinski, M.,
Surface
Approach
Topogra-
1988.
France,
F.-J.,
Avignon,
Fourier Transform
and
Fractal
J. Soc.
Cos-
phy :
met. Chem.
Analysis,
and
Wortmann,
Wool and
Textile
Cuticle Scale
of
Phan,
K.-H.,
Fibers and
Heights
173-189
40,
(1989).
Their
Due to
Specialty
Changes
Textile
Res. J.
139-144
received March
1, 1999:
June
1999.
15,
69,
Processing,
(1999).
Manuscript
accepted
Color
of
on
6
Films
with
Concentration
Change
Dyes
Disperse
Nylon
Dye
TAKASHI NAKAMURA
AND
TAKAO
SHIBUSAWA
and
Chemical
Gunma
Faculty of
Engineering,
Department ofBiological
376-8151,
Engineering,
University,
Kiryu
Japan
ABSTRACT
of
on
6
film are
with
Spectral
changes
disperse dyes
nylon
investigated
decreasing dye
concentration
(Cf).The
wavelengths
visible
maxima
The
most
azo
(
&lambdxa; of
shift
absorption
decreasing
disperse dyes
dyes
to
with
shift is
for
with
longer
significant
dipole
Cf.
structures
caused
the
intramolecular
transfer. The
is
by
charge
spectral
change
analyzed
in
detail for CI
3
and
in
terms of
5,
McRae’s
Disperse
factor
Orange
The
practical
disperse dyes,
and
a
values for
these on film
in the
of low
equation
analysis.
m
la
a
mbd
x
a;
dyes
McRae’s
range
are much
than
those
estimated
and shift to
longer
wavelengths
by
The
Cf
equation
results of
shorter
with
the factor
wavelengths
increasing temperature.
of
analysis
indicate that
described as
at
the visible
films with
can
be
absorption
spectra
dyed
decreasing
Cf
the sum of
two
distinct
than
as
I
and II.
SpeciesI has
spectra,
designated
species
[species
II.
The ratio of
increases
&
la
a
mbd
x
a;
longer
wavelengths
species
II]
I]/[species
with
a
red shift
ofmla
a
mbdxa; with
nylon
This result is
consistent
decreasing
causing
decreasing
Cf,
Cf.
with the
sorbed
behavior of
these
6
film from
water,
where
the
are
sorption
the
dyes by
dyes
as two distinct
taken
taken
the
by
polymer
species:
L—species—dye
P—species—dye
up by
up by
polymer
the
and
mechanism,
through
Langmuir sorption
Nemst-type
For
both
the
relations
the
concentrations
between Cfand
of
I
dyes,
similar to the relations
partitioning.
species
and II
are
and the
concentrations of the
to L- and
between
L- and
very
We
Cf
estimate that
I
and II
in this
P-species.
species
study
correspond
P-species
in
studies,
sorption
respectively.
The shades of some
polymeric
on
the
CI
found that the
substances;
disperse dyes
depend
sorbed,
on
cluding polymeric
shifts to
they
with
Àmax
of
substrates on which
are
they
e.g.,
longer wavelengths
increasing polarity
3
shows
the solvent:
Disperse
Orange
yellowish
orange
secondary
and CI
acetate and
cellulose
brick red
on
[2],
polyamide
Violet
I
shows red-violet on
cellu-
Disperse
secondary
lose
and
blue-violet on
acetate
66
[21 ].
nylon
the
Irick and
Pacifici
in
visible
[5]
change
studied
maxima
of
with
solvents
in-
[I]
absorption
(Åmax)
dyes
Downloaded from trj.sagepub.com at UNIV OF MICHIGAN on January 5, 2015

802
Tr-electron
releasing
have
a
andelectron
and
where
Xand Ydenoteelectron
[I]
[II]
conjugated
and
system,
Dyes
withdrawing
substitu-
with both electron
concluded that
substituents,
withdrawing
They
donating
respectively.
of the molecule. Such molecules
ends
and
ents at
McRae’s
the modified
1,
[8],
prediction
opposite
contribution
have a
Equation
equation
structure
caused
of
of
in
[III]
dipole
transfer
changes
large
intramolecular
relationships permit
empirical
with solvents:
(cr) [5]:
charge
by
Åmax
where Av is the difference in
for
and
absorption frequency
to
of the cr band shifts
The
longer wavelengths
Åmax
+
in
and in the
solution
B)
gas
( ALo
Åmax
( vs)
(
v~);
with
of the solvents
[ 13].
polyamide
increasing polarity
Disperse dyes
which are
C
are
of solvent
constants,
independent
prop-
to
fabrics to
are often
applied
nDis the refractive index ofthe solvent measured
erties ;
of their excellent
to
because
ability
produce pale -shades
and
D
is the
con-
at the sodium
static dielectric
D-line;
effects
in color with
cover barm
Therefore,
[
1
].
changes
stant of the solvent. In
side
the
term on the
first
1,
Equation
will be
to both theoretical and
us information
decreasing
interesting
Cf
the
of the
contribution
right-hand
expresses
disper-
The
practical dyers.
spectral change gives
sion interaction of the
with the
and the last
solvent,
interactions.
dye
about
in the local
around the
in the
changes
polarity
dye
phenomenon
term
the
expresses
dipole-dipole
with
The
same
( 19].
polymer
decreasing
Cf
we
have
the
of
that
found, however,
Recently,
azo
J1m$X
also
basic data for
provides
computer color-matchingjobs.
the of
deriva-
4-aminoazobenzene
(4’-nitro,
6
dyes
nylon
decreasing dye
disperse
In this
we
study,
clarify
spectral
disperse
change
the nature of
on
film
to
shifts
tives) [II]
longer wavelengths
on
6
with
Then we
dyes
the
nylon
analyze
Cf.
with
in the
concentration
substrate,
(Cf)
for CI
3 and 5
shift
(abbre-
various
spectral
Disperse Orange
shown in
1. Wehave observed the
as
Figure
appreciable
6’-positions,
viated as
3
and
in detail
5)
Orange
through
shift for
with
chlorine
low
2’- and
at
atoms
dyes
since both
are
azo
with
methods,
dyes
(Orange
practical
or with
dyes
in
a
particularly
very
range.
Cf
structures
red
5).
3)
decreasing
simple
appreciable
in
shifts
with
Åmax
in
6
nylon
(Orange
Cf
Experimental
The
in
were identical to those used
and the solvents were
dyes
[ 15-18],
grade.
previous
studies
meric
spectrophoto-
drawn,
prepared
6
film was
Nylon
biaxially
Unitika Ltd. The film was treated in waterat 95°C for
by
25 hours before use.
The
film was
measurements
the same methodas that used
dyedusing
in
of
isotherms
and
17,
[ 15,
18]
sorption
the
concentration
of
in the
in the
in
profiles
[16],
dyes
dye
polymer
diffusion
studies
where
concentration
(Cf)
the
film
from saturation
zero.
ranged
approximately
mg)
(4-10 mL)
Cfto
The
in
the dried
film
was extracted with
at 80-90°C
(10-20
dye
aqueous
25%
solution
pyridine
1.
FIGtJRE
films:
of CI
in
5
6
Absorption
two or three
spectra
times. There
no
Disperse Orange
nylon
spectrum.
were
concentrations of the
a
dotted line is
the
of each
passing through
Åmax
extracts
The amountof
in the extract
by evaporation.
dye
was estimated
(10-25 mL)
colorimetrically.
Visible
ofthe
in solvents
and
or
absorption spectra
dyes
on the film
were measured on
a
Hitachi
U-3300
U-2000A
at
in
room
the
spectrophotometer
For
temperature
usual
ofthe
film
measurements
at
way.
spectral
dyed
1 x
various
was
each film
2.5
(
cm)
temperatures,
specimen
sandwiched
betweentwobrass blocks
cmwide
( 1.25
Downloaded from trj.sagepub.com at UNIV OF MICHIGAN on January 5, 2015

803
x
0.6 cm
X
5.0 cm
thick
with
narrow slits at
their
and
decrease in
high)
solvents
for
molecules
E~
polar
contribution of
[ 13)
Eg
centers. The
two
blocks
combined
formed
a
structure the
with
structure
caused
an
dipole
a large
by
same
size as
a
normal
cuvette.
Theblocks
the
with
intramolecular
quartz
such as
3
and
transfer,
5.
charge
Orange
sandwiched
thermostatted at
utes. After
were
in the cell
holder and
about 20 min-
film was
But
of
the
specimen
excited state
in
placed
temperature
of the
solvents
de-
dif-
E,
polar
polar
This reduces
a
desired
the
for
creases to
ference
a
much
extent.
the
greater
that,
between
and
a
spectrum
U-2000A
dyed
red-shifted
E~:
increasing
pronounced
of
Eg
measured on
a
Hitachi
would
result in
the
spectrophotometer.
solvents.
with decreas-
contribu-
~1&dquo;,~
polarity
red
shift of
The
had
61m
thickness
about
0.0027
the
(1
enough
appearance
cm)
by
Therefore,
significant
Àmax
to
avoid
the
of
a
sinusoidal
curve caused
is
a
characteristic
structure
of
a
with
a
ing
dye
large
C f
’
the
interference of
incident
into the film
over the
value of
tion of
light
Thus,
dipole
visible
[ill]..
measured
the
measured
The
wavelength
Àmax
[7].
of
a
anthra-
absorption
spectrum
Disperse
typical
for
each
on the film
was
accurate.
CI
dye
Violet
1
quinone
disperse dye,
(1,4-diami-
in
solvents is
characterized
a
noanthraquinone),
polar
by
double head
peak
1
at
shorter and
2
at
(peak
Results and
peak
Discussion
longer
The
relative
oftwo
at
each
wavelengths).
strength
peaks
SPECTRAL CHANGE
FILM
OF
DISPERSE
DYES ON
NYLON
6
on the
Àmax,
IntensitYpeül!ntensitYPe8k1 ,
depends
polar-
WITH
DECREASING
of the
solvent
The ratio
increases
with
Cf
the
as
ity
[20].
increased
dielectric constant
of
on
the
(D)
same
solvents,
The results of
the
measurements are
summarized in Ta-
shown
in Table II.
For
the
1.040
Table II.
6
this
film,
dye
nylon
ble
and
indicate that
a red
in
shift
the
I,
of azo
An.
dyes
ratio
as
increases from
shown in
to
1.094 with
decreasing
with
C f,
the
Cfis
for
with an
electron
decreasing
appreciable
dyes
This
fact also
indicates that
at
the
substituent,
withdrawing
N02group,
X-position.
character
ofthe
mediumaround the
with
dye
changes
For
1-3
C f.
there is
a
red
shift with
(X
H),
dyes
only
slight
while for
an
red
shift
1.
4-12,
decreasing
occurs,
dyes
appreciable
typified
acting
Cf,
SPECTRAL CHANGE
FILM WITH
OF
ORANGE
3
AND
5
ON
NYLON
6
for
as
in
10-12,
particularly
dyes
Figure
DECREASING
C f
These
have
dyes
two
chlorine
atoms
as
electron
at 2’
and 6’
and have
a
The
color
ofthese
withdrawing
have
groups
positions
one intense
large
changes
visible
dyes
only
wecan
contribution of
structure.
band in
the
with
dipole
assess
color
therefore,
value of
the
region;
The
uv/visible
arises
from the
reHect-
from
the
absorption
in the
visible
spectrum
molecular
change
region.
Àmax
C f
electronic transition
between
we
orbitals,
shift in
detail
Hence,
for
analyze
spectral
the
chemical
structure ofthe
The
these two
ing
of
compound.
position
energies
dyes.
showsthe
is
related to the
difference
between the
2
relation
between
A,,.
and
of
the
Figure
on
Àmax
Cf
(25%
at the
state
and the exited
state
Both
the film
and in
ground
the extract
(E~).
dyes
(Eg)
aqueous
pyri=
TABLE I.
in
maximum of
with
concentration in
Change
6.
absorption
disperse dyes
dye
nylon
* Measured for absorbance
below 2.5.
Downloaded from trj.sagepub.com at UNIV OF MICHIGAN on January 5, 2015

804
of
ratio
solvent.
solvent and
constant of
between dielectric
II. Relation
TABLE
I
in
the
Violet
I and
2 ofCI
at
absorbance
Disperse
peak
peak
*
at 25°C unless followed
for the
Dielectric constant
by
pure liquid
b
Measured at room tem-
I KHz from
in
another
[8].
at
temperature
parentheses
extrapolated
c
Values
log(frequency)
perature.
the
in
and D
between
linear relation
log(frequency)
experimental
ofthe
between
andthe
FicuttE 3. Relation
( Absll )
density
optical
3
Cf
unit thickness at
reference 2.
5
for Orange
Orange
and
(0)
film
(A).
dyed
per
A&dquo;&dquo;x
as the concentration
of
are liable to associate
5
with
shift in
of
The red
(Cs)
dyes
dye
dine).
Orange
decreasing
Orange
Åmax
the
dissolved
increases
In this
in water
of
than that
low
very
is much more
case,
has
3,
[4].
dye
appreciable
range
C f
a
at
a
in water as
a
monomer
the other
On
in the
of
longer
usually
Åmax
particularly
Cp
than
(e)
absorptivity
and
a
molar
are almost constant
in the extracts
the
values
hand,
higher
associated in water
wavelength
those of the
Åmax
This results in
a
in
that the shift
of
forboth
[4].
dye
the
regardless
indicating
dyes,
Cf
Cf,
e
ofthe
with
decrease in
with
shown in
1
and 2 cannot be attrib-
apparent
dye
increasing C,.
E
Figures
Åmax
uted
the values of for both
as shown in
to
However,
3,
Figure
during dyeing.
dye decomposition
are constant over the whole
of
C f examined,
range
dyes
in the
occurs
no
of the
film.
indicating
aggregation
dyes
OF
SOLVENT EFFECT ON ABSORPTION SPECTRA
AND
ORANGE
3
5
of
wave
Table III shows the values
number)
(in
Åmax
in various solvents and the
of
3
and
5
measured
ofthose
an
Orange
physical
solvents. The values
constants
D)
(nD,
in D. Wehave
of
decrease with
increase
vobs at kna,,
+
of
and
C
in
analysis
multiple regression
estimated the values
constants
B,
ALo
vg,
1
ofthe
means
by
Equation
in
Then we have calculated the values
shown
Table IV.
at
ofthe
using Equation
that the differ-
absorption frequency (veale)
Åmax
1.
ofthe
calculations indicate
The results
arises
from
the
ence in Avwith solvents
mainly
dipole
interactions
expressed by
2.
A
in
0
3
FIGURE
with
3 in
Change
J1&dquo;&dquo;x
decreasing
Orange
C.:
=
5
in
in extract
6,
6..
nylon
(25%
nylon
Orange
Orange
Orange
in
5
extract
(25°6
pyridine), A
pyridine).
interaction
rather than the
dispersion
by
expressed
3
the
shows
of
versus the
Figure
density
plots
optical
C f
of
film
unitthickness ofthe film
Each
(Absll)
dyed
per
and
at Åmax for Orange
respectively.
3
plot shows
5,
a
line
meets the
4
shows
of
the
straight
origin.
decreasing dye
Figure
experimental absorption
1fie filled
plot
versus
Red shifts in
with
concentration
at
Åmax
symbols
symbols
frequency ( vobs)
Årnax
vc.1c.
have
been observed for some
in
where
the
solvents and
open
the
denote
values in
water,
dyes
vrnax
I
Downloaded from trj.sagepub.com at UNIV OF MICHIGAN on January 5, 2015

805
TABLE III.
constants of
solvents used
and
Physical
absorption
solvents.
maxima
of
3
and
5
in
the
Orange
Orange
FIGURE 4.
Plots
of
versus
=
for Orange
3
and
5:
O
3
=
in
Veale
0
Voo,.
Orange
3
in
5
in
6,
6, ·
Orange
nylon
Orange
Orange
nylon
Orange
A
5
in
solvents.
solvents,
a
Refractive index
another
at the
in
D-line of
sodium at
25°C
unless
followed
constant
in
b
Dielectric
another
by
temperature
[ 14].
parentheses
for the
at
25°C unless
followed
pure liquid
in
terms of
by
temperature
or the
local
interpreted
hydrogen
bonding
in the
presence
polarity
C
d
Measured
at room
parentheses [ 14].
Values
temperature.
of
but
rather to
water,
changes
taken from
reference
3.
around
the
Such effects
on
cannot be ex-
dyes.
macroscopic
Àmax
such as
+
TABLE IV.
C
determined
equation.
B,
the
modified
or
D
of
AL~
plained
by
vx,
by
properties
nD
McRae’s
---
I
polymer.
FACTOR
ANALYSIS OF
SPECTRAL
CHANGES IN
ORANGE
3
AND
5 ON
NYLON
6
FILM
[6]
The
6
is not
a
substrate,
a
film,
polymer
solid but
nylon
homoge-
neous
one in which
there
are
heterogeneous
denote
distributed
in
6
film. The
filled
line
are
various
with
different
orders of
chain
Vrnax
nylon
a
symbols
(dotted
regions
segment
theoretical
fromthe
ordered
along
nuclei
line)
and
to
straight
alignment,
(crystalline
region)
with
standard deviations of
507
cm-’
for
3
the
disordered
domain
Orange
magnitudes
completely
of dye
(amorphous
region).
219cm-’
for Orange
The
5,
of
The
a
with
6
a
contribution of
respectively.
large
dipole
the
deviations
from the
theoretical
line
are of the same
structure
in
shifts to
a
as
[III]
nylon
longer wavelength
order as those
obtained
Iric and
by
Pacifici
the
interaction
of the
with
[5].
the
energies
dye
polymer
Points
1
and
2
denote
values
Vrnax
in
dioxane. The two
become
The
higher.
deviate
to
from
attributable to
interaction
points
on
appreciably
the
in
the
space
longer
wavelengths
energies
depend
the
the
theoretical
these deviations
are
line;
in
which the
is
such
the
as in the
sorbed.
surface of
polymer
dye
that
forms
between the
or
on the
hydrogen
bonding
proton-
amorphous
portions
regions
[ 11,
sorbed
crystalline
of
the
and
atoms
in
or both
We
donating group
have found that
dye
nonionic
two
proton-acceptor
1 S].
the solvent.
shifts in
of
some
solvents often
azo
are
6
from
water
Frequency
dyes
by nylon
mechanisms, i.e.,
through
include the
contribution
which
is
different
hydrogen bonding,
sorption
Nemst-type
parti-
not taken
in
McRae’s
and
mechanisms
equation.
In
tioning
Langmuir sorption
[ 15-18].
isotherm of
in
line. Irick
4
deviate
from
the
ourearlier
of
the
Open symbols
a
Figure
nonionic
greatly
out
analysis
nylon
sorption
the
saturation
water,
theoretical
and Pacifici
in
that the
azo
6
from
[5]
value for
pointed
dye by
of
nonionic azo
shifted to
in
dual-mode
Årnax
increased with
dyes
polymers
longer
Langmuir sorption
sorption
Wealso
than
those
1.
the
the
the
of
6
wavelengths
found
that for
predicted by
Equation
They
[ 15).
crystallinity
nylon
ascribed this
to
the
of
water in
the
of
phenomenon
presence
shift of
microfibers,
sorption
disperse dyes
by
polyester
films.
the red
with de-
However,
shown in
contribution of
polymer
to the total
Årnax
4,
Langmuir sorption
dye
large
2
and
cannot
be
1,
was
for
creasing
the fiber with
a
Figures
Cf,
uptake
appreciably greater
Downloaded from trj.sagepub.com at UNIV OF MICHIGAN on January 5, 2015

806
that
These
size
[9].
(010)
findings suggest
crystallite
ofnonionic
in the dual-mode
is associated
sorption
sorption
Langmuir
obtained as
can be
of
of
The number
the number
independent species
base vectors
with the
the
crystalline
first
by
polymer
dyes
the
forming
independent
we assume
the factor
To calculate
analysis,
as an
phase.
of the matrix Z.
space
Weobtain an
the
of
ac-
in
exists
that the
assembly
polymer
dye
E
and an
matrix
eigenvector
[ 12]:
eigenvalue
Jacobi
for Z
visible
with different
distinct
several
spectra
species
method
the
matrix
Q
using
with the
of
the
to the interaction
dye
energies
cording
be ascribed
in the
in
with
can
shift
the
substrate.
Then
J1&dquo;,~
Cf
of each
in the
the
to
species
composition
change
with
polymer
Factor
13
matrix
E
is an
where
C f.
eigenvalues
eigenvec-
having
eigenvalue
elements
has been used to
overlapped
separate
analysis
is
a
and Q
at
corresponding
diagonal
each
and
the number of
individual
To
[6, 10].
species
get
spectra
spectrum
at columns. The
of how
tor matrix
eigen-
having eigenvectors
we have ana-
based on the
species,
each
the relative
weights
values are
important
6
film
of
3 and5 on
nylon
Orange
changes
lyzed spectral
data. If the num-
the
is for
factor
reconstructing
species
spectral
a
factor
means of
with
analysis.
by
are
is
then
n
active
of
Cf
ber
n,
large
eigenvalues
on
6 film with
are
of
nylon
changes
dyes
Spectral
When the
or small.
are
C f
and
other values
any
negligible
formed of ab-
wavelengths
which is
matrix
data
a
D,
expressed by
are
to the former
eigenvalues
by
corresponding
eigenvectors
extracted,
of 31
3,
intensities,
e.g.,
Orange
sorption
constructed
of the
lining them
matrix
is
matrix
Q’
The
newly
transpose
In the case of this
concentrations.
13
and
the
example,
and 13 columns. Each
dye
matrix
in
columns.
eigenvector
up
Q’
of 31 rows
D
consists
to
similar
rows and 13 columns
n
has
of
dimensions
each
film.
the
of
to
column
Onthe
dyed
corresponds
spectrum
matrix
first
of the
is the
C and
matrix
expression
composition
columns
has
a
where
other
R,
n
hand,
spectrum
the
1
31
Multiplying Dandthe
C
matrix C.
n
gives
transpose
for each
consist ofindividual
pure species,
spectra
rows and
same dimensions as
R
and is
which has the
of the
matrix,
by
n
columns. And a
dimensions of 31
composi-
R:
matrix
one
expression
spectral
rows
the concentration
tion matrix
distributions
where
the
C,
of
represent
at each
has
film,
dyed
pure species
of
R
and
Therelation
13 columns.
dimensions of n rows
of factors
n
can be selected as the smallest
The number
with
D
can be
C
and
by
expressed
error.
that
D
such
RCwithin
number,
After treatments
experimental
to
we
3-5,
Equations
two rows and 13
corresponding
of
C
obtained
a
matrix
matrix
composition
2
R
of
rows
the
columns and
columns
a
31
and
A
matrix
Z
is obtained
covariance
by multiplying
spectral
out the
to
D
1D and the
eigenvectors corresponding
by taking
original
transpose
FtauteE 5.
~ =
of
of
on
―~―
--a--
of
3
6
film:
measured
specwm,
(A)
spectrum
Separation
absorption spectrum
Orange
nylon
spectrum
of
concentration
species
in the
concentration of
of
II.
I
and II with
I,
I,
(B)
species
species
Change
species
species
increasing
Cj:
=
of
II.
concentration
Downloaded from trj.sagepub.com at UNIV OF MICHIGAN on January 5, 2015

807
FIGURE
-8-
6.
of
of
(A)
spectrum
5 on
concentration
6
film:
I and II with
Separation
of
measured
increasing
absorption spectrum
--~ =
=
C¡: ~
of
Orange
nylon
of
speculum
concentration of
species
I,
-8-
II.
in the
(B)
species
species
Change
species
I.
Species
concentration of
II.
_
.
the
two
But
these matrices
had
some
5
with
this
largest
values,
as shown in
eigenvalues.
6. It
method,
Orange
suggests
Figure
so
we had to
rotate
the base
axes ofthe
that
negative
matrices R and
there are
distinct
in
sorption
regions
nylon
C. The
rotation
matrices T-’
and
T
6
and
the
bind
to substrates
film,
with
different
dyes
binding energy.
T-’T
I
is
the unit
(TT-’ -
had to be
levels
I,
of
matrix)
inserted between
R and
C
SPECTRAL
SHIFT BASED ON THE
DUAL-MODE
SORPTION
.
MODEL
When we
selected the rotation
matrices so as
to avoid
Wehave
found-that
the
of
3
and 5
sorption
follows
Orange
7
by
absorbances and
we
negative
concentrations,
negative
6
film from
water
nylon
( 18]:
Equation
R’
determined
An
and
of
but
not
C’,
uniquely.
the sets
of R’ and
C’
obtained for
example
3
is
shown
in
5.
The
of
3
Orange
Figure
spectra
Orange
on
6
film can be
well
described as
the
two
nylon
sum of
intrinsic
I
and
the fraction
of
where
on
and
are
the
spectra
II);
(species
concentration
the
species
C,
and in
equilibrium
and
dye
Cf
I
and II changes
with
C~.
We
obtained
a
similar
result for
solution,
polymer
C p
CL are
equilib-
FIGURE 7.
Relations
between
and
estimated from
the
isotherms for Orange
CL’
3
and
(A)
5
on
6
film from
Cp,
CL
sorption
Cf
(B)
Orange
nylon
=
water
at 60°C:
0
experimental
points,
Cp,
Cf, ---------
Downloaded from trj.sagepub.com at UNIV OF MICHIGAN on January 5, 2015

808
of
5
on
Cf
FIGURE 8.
Spectral change
Orange
with
film
6
temperature:
increasing
nylon
9.32
x
10-4
mol/kg.
with
film shifts to
6
a
decreas-
Nernst-
sorbed
concentration on
and
rium
wavelength
in solvents
longer
dyes
nylon
ing
longer
by
dye
polymer
Langmuir
also shifts
a
to
of the
with
The
respectively, S
Àmax
sorption,
type partitioning
Cf.
of the sol-
around
is
saturation value for the
is the
the
wavelength
vents. These
increasing polarity
sorption, KP
Langmuir
Langmuir
the local
facts
that
the
con-
is
and
coefficient,
polarity
suggest
KL
partition
with
in
6
film increases
the
stant.
decreasing
dye
nylon
studies
Cf.
of
of CI
the iso-
Detailed
3
to
we have
7,
changes
Disperse
spectral
According
Equation
separated
and
of
in terms
6 film
the factor
and
5
on
into
therms
Langmuir sorp-
Orange
nylon
Nernst-type partitioning
behavior of the
of
indi-
dyes
and for the
as two
tion. The
exists in the
distinct
sorption
spe-
analysis
dye
polymer
the
is
cate that the visual
mechanism
the
cies : that sorbed
(P-
dyes
absorption
by
by
partitioning
spectrum
sum of two distinct
the
as
and that
mechanism
the
the
e.g.,
spectra,
expressed
spectrum
Langmuir
amounts
species)
sorption
of
I with
at a
of
are
The
species
species
A,,.
Àmax
longer wavelength
usually
L-species
(L-species).
II with
at a shorter
that of
and
smaller than the
The ratio
increases
wavelength.
P-species.
C~/C~
of
in the
with
are the result
decreases
with
with
changes
rising temperature
Spectral changes
decreasing
Cf
Cfand
in the film. The
shifts
ratio of
II]
with
181.
[15,
I]/[species
Àmax
[species
in
The
7A
B
show
between
and
to shorter
decreases
shorter
and
the relation
for
I].
wavelengths
[species
Figures
at the
Cf
and
a
with
of the
shifts to
3
5,
wavelength
dye
Orange
~max
CP, CL
sorption equilibrium
increas-
the values of
and
x
also decreases with
We calculated
Cp
CL
increasing temperature. CL
respectively.
x
105
The relations between
and
1.06
103
from
4.08
ing temperature.
[species
dM3/kg,
KP
KL
Cf
x
are
similar to
very
between
the relation
from the
estimated
2.46
for
and
10-;
7A,
dm3/mol, S
I],
and
III
3 mol/kg
Figure
[species
Cf
experi-
x
2.15 x 10;
2.60
106
dm;/mol,
dm;/kg, KL
[L-species], [P-species]
Kp
x
I and II
10-4
for
7B
mental
S
6.90
isotherms,
sorption
[18].
suggesting species
Figure
mol/kg
to the L- and
The relations between
and the concentration of L-
P-species,
correspond
respectively.
Cf
7
and
shown in
seem to be
similar
Figure
very
P-species
to
concentrations of
and 6B.
the relations between
I and II shown in
and the
Cf
Literature Cited
The
5B
species
Figure
Figures
shift
8
shows the
of
5
on
spectral
Orange
Àmax
nylon
1.
of Nonionic
to Fi-
J.
R.,
Dyes
Man-Made
Aspland,
Application
and Their
film
to
a
6
with
The
shifts
rising temperature.
bers :
Nonionics
Fibers,
by
Sorption
4),
shorter
with
This
wavelength
increasing temperature.
Chem. Color.
36-40
(1992).
Textile
2
that
I
with
decreases
fact indicates
species
increasing
W.
and
J.
2.
3.
C.
Bamford,
The
H., Boulton, J.,
of
E.,
Ward,
S.,
Hanby,
as the concentration of
de-
Soc.
Disc.
temperature
creases with
L-species
Figures
analysis
(CL)
Synthetic
Farady
Dyeing
Polypeptides,
7A and
B
222-229
increasing
16,
(1954).
and
temperature.
E.
with
Hand-
the results of the factor
shown
H., Eds.,
J.,
Brandrup,
book,"
V-115.
Immergut,
"Polymer
1989,
NY,
pp.
agree
qual-
3rd
John
&
Sons,
ed.,
V-109,
in
5B and
if we consider the dif-
were measured.
Wiley
6B,
itatively
ferent
Figures
at which
temperatures
they
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5.
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J.
E.,
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Dyers
G.
on
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the Ultraviolet-Visible
Spectra
Dyes,
Absorption
(1972).
43921-3,97
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Shades of
6
with
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nylon
Cf
change
Textile Res. J.
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in the
of low
for
with
6.
the
Set of
E.
particularly
range
dyes
large
on
Malinowski,
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and
Key
Typical
contributions of
structure. The
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Isolation of
the
Factor
dipole
dyes
by
Analysis
Subsequent
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Nonionic
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