' Chapter 10/Part 2: The Application of Ionic Dyes to Ionic
Fibers: Nylon, Silk and Wool and Their Sorption of Anions
By J. R. ASPLAND. School of Textiles, Clemson University, Clemson, S. C.
T 0 repeat the objectives of this chap-
ter, the sorption of anionic dyes will
be examined including acid, mordant
(chrome), premetallized and reactive
dyes. Disperse dyes cover chemical barre
well on nylon, and for this reason are used
for a significant portion of the textile
business where outstanding light- and
wetfastness are not required. The subject
was treated in Chapters 7 and 8. Reactive
groups can either be added to a disperse
dye structure or an acid dye structure and
their uptake properties, as opposed to their
fixation properties, will be determined
accordingly.
It is already possible to write a useful
general formula for all anionic dyes:
Dye"-. n . Naf
which simply indicates the dye anions have
n charges associated with them ( n is
normally from one to four), and that these
anions are normally accompanied by an
equivqlent number of sodium cations.
Since we have already seen that protein
and polyamide fibers (PA) can have an-
ABSTRACT
Acid, mordant (chrome) and
premetallized dyes are introduced and
the chemical nature of metal-dye
complexes is considered. The
mechanism of dyeing protein and
polyamide fibers with anionic dyes is
discussed in terms of the Langmuir and
Nernst sorption isotherms. A qualitative
picture of the action of leveling or
restraining agents is developed.
KEY TERMS
Acid Dyes
Anionic Dyes
Chrome Dyes
Leveling Agents
Mordants
Nernst Isotherms
Nylon
Premetallized Dyes
Silk
Wool
M a r c h 1993 CCO
ionic and cationic charges associated with
them, it is to be anticipated that ionic
attractions might occur between oppo-
sitely charged species in the dyebath and in
the fiber. But first, a look at the kinds of
dyes used for these fibers.
Acid and Mordant Dyes
The name acid dyes is derived from the
fact that for centuries some water soluble
dyes have been more readily applied to
wool and silk from aqueous dyebaths
containing acids than from neutral dye-
baths ( I ) . Those acid dyes of natural
origin-Le., which predate 1856 and Per-
kin-have been combined with other nat-
ural coloring matters and are now listed as
naturaldyes in theColour Index ( 2 ) .Most
synthesized acid dyes depend on pendant
sulfonate salt groups, -SOjNa, for their
solubilityas do thedirect dyes.
The name mordant dyes refers only to
those water soluble acid dyes which con-
tain groups which are capable of reacting
in the presence of the tiber with selected
metallic cations, known as mordants, to
give metal-dye complexes with increased
molecular size and improved fastness.
This is the conventional definition of
mordant dyes, but strictly speaking mor-
dants can complex with other classes of
dyes and do not have to be cationic or
metallic. For example, basic dyes (cat-
ionic) can be dyed onto silk treated with a
tannin (anionic) mordant. But, leaving the
general question of what is a mordant, let
us answer another more specific question.
What is a metallic mordant?
Metal Compounds as Mordants
Centuries before the development of sys-
tematic chemical knowledge, man had
discovered that pretreating or post-treat-
ing the available textile fibers with differ-
ent earths in the dyebath could lead to the
production of a range of different hues
from the same natural dye. Not only that,
but someof thecombinations of earths and
dyes produced colors with more desirable
properties than others. And so, inevitably,
patterns began to emerge. Eventually it
became known that metallic compounds
of aluminum, cobalt, copper, iron and
others were responsible for the improve-
ments in the properties of the dyeings.
These compounds became known as mor-
dants, from the Latin word meaning to
bite. The mordant bites into the dye and
the fiber and holds on.
However, around 1850, chromium salts
were discovered, and as far as the mordant
dyeing of wool was concerned, the other
mordants fell rapidly behind. The extent
to which this happened is shown in Ref. (3)
in which Bird calls his chapter on mordant
dyeing, Chrome Dyes. There are virtually
no wool mordant dyes in use today that do
not use chromium compounds.
Chromium, in the form of sodium (or
potassium) bichromate, NalCrl07, has
been optionally applied to wool either
before, during or after dyeing with mor-
dant dyes; but the first two choices, known
as the chrome mordant and the meta-
chrome methods respectively have been
superseded by the afterchrome method.
Here, the mordant dyes are applied as
normal acid dyes to the wool, and enough
acid is added to exhaust the bath. The
temperature is lowered to ca. 70C ( 1 60F),
0.2-3.0% sodium bichromate, depending
on the depth of shade, is added and the
temperature raised to the boil for 30-60
minutes.
During the process the bichromate ion,
Cr207=, is absorbed by the wool, the
hexavalent chromium (written Cr6+ or Cr
VI) is reduced (gains three negative elec-
trons) to trivalent chromium (writen Cr3+
or Cr 111) by a complex series of interac-
tions with sulfur containing (cystine)
groups in the wool, and chromium-dye
complex compounds are formed in the
fiber.
Mordant (chrome) dyes are still in use
today-the AATCC Buyer's Guide lists
about 40 dyes ( 4 ) . The afterchromed
dyeings have outstandingly good wash-
and lightfastness on wool, although the
colors are generally rather dull, with
blacks, navies, browns and dull yellows
easily predominating. It is interesting to
note that C.I. Mordant Black 11 is one of
the most widely used dyes in the world.
However, several questions remain un-
answered. For example, what is the nature
of the chromium-dye complexes and what
happens to the chromium? The next sec-
tion will address these questions. Do any of
the environmentally undesirable chro-
55
Nylon, Silk and Wool
mium salts end up in the effluent? The
answer to this question is yes. And since it
is estimated that of all the dyes being used
for wool worldwide, chrome dyes repre-
sent about 36%, the answer yes represents
a substantial problem.
Although there has been much effort
expended to reduce the amount of chro-
mium in the aqueous ,effluent, it is still
undesirably high. However, a more tanta-
lizing environmental question is what hap-
pens to chrome-containing goods when
they end up as solid waste in landfills.
Metal-Dye Complexes
The present state of chemistry enables us
to understand what properties of certain
metallic compounds (mordants) and se-
lected acid dyes (mordant dyes) contrib-
ute to the formation of metal-dye com-
plexes, known also as co-ordination com-
pounds.
The metallic compounds which are still
used to form metal-dye complexes are all
from a group known as the transitional
metals. In simple terms, this means that
their metallic cations (+) not only attract
anions (-) but also have electronic config-
urations which enable them to form com-
plexes with particular numbers of chemi-
cal groups, whether the groups are anionic
or nonionic. Such groups are known as
ligands. These metal ions are like property
owners who have rooms to rent to singles.
So long as the tenants can pay (with
electrons) the owners like to keep their
by an arrow pointing from the donor atom,
or by a dotted line, Fig. 1.
Certain structures and configurations of
individual dye molecules enable them to
provide metal (mordant) ions with not
only one but two, three and even four
ligands; e.g., the copper phthalocyanine
structure shown in Chapter 2, Part 11.
Such dyes are known as polydentate
ligands (with many teeth). They are also
known as chelating agents, from the Greek
word for (crab) claw. Thechelating agents
used to tie up the free metal ions in
water-e.g., EDTA-do indeed act in the
same way, and are quite capable of wres-
tling some metal ions from premetallized
dyes.
Fig. 2a shows the single most important
dye structural feature for the formation of
metal-dye complexes, although there are a
number of others ( 4 ) . It is called the o,o’ -
dihydroxyazo group, which simply means
that two hydroxy groups are situated on
carbon atoms adjacent to those holding the
azo group, one on either side.
Fig. 2b shows how this dye structure can
provide three ligands to a trivalent chro-
mium ion ( C N = 6). Two come from
ionized hydroxy groups in the dye mole-
cule, Fig. 2a; cf. the ionization of naph-
thols in alkaline solution, Chapter 6 ( 5 ) :
R - OH + OHO- R - oo+ H ~ O
These two anionic ligands will also effec-
tively neutralize two of three positive
charges on the metal ion, leaving it with
only one positive charge. The third comes
from a donation of electrons (to share)
from an azo nitrogen (+). In the process,
wool fibers, although it is hard to establish
whether they do or not.
The resulting structure in Fig. 2b is a
1:1, meta1:dye co-ordination complex (see
the section on premetallized dyes). The
overall charge on the complex will depend
on whether the nondye ligands were
nonionic or anionic. Unfortunately, the
resonance ensures that the resulting ionic
charge is delocalized and spread about
within the structure, making it hard to
find.
Fig. 2c shows that two suitable mole-
cules of dye-e.g., of the type shown in
Fig. 2a-could each provide three ligands
and satisfy C N = 6, to give a 1:2, met-
a1:dye co-ordination complex. These may
alternatively be called 2:l dyemetal com-
plexes. Now there are four anionic ligands,
R-0-, whose negative charges, when
added to the three positive charges on the
chromium cation, leave the complex with
one negative charge; Le., anionic. The
product is resonance stabilized by four
aromatic rings, and the anionic charge is
delocalized. Some 1:2 metal-dye com-
plexes have been extracted from mordant
dyed, afterchromed wool. It seems likely
that both 1 : 1 and 1:2 meta1:dye complexes
may be present on the wool.
H\o/H
‘O+C” 4 2 +‘ 0 , 7
H’ .f ’ H
‘

rooms occupied. The maximum number of
ligands (tenants) is known as the co-
ordination number (CN) and varies from
metal to metal.
Two metallic ions widely used in dye
technology are the trivalent chromium
and divalent copper ions (Cr3+, Cu2+)
which have C N = 6 and C N = 4, respec-
tively. Cobalt and nickel derivatives are
also used and have C N 6 and 4 respec-
tively.
A simple example of a co-ordination
complex is to be found in the solid and
solutions of the widely known blue
compound, copper sulfate (hydrate),
CuSO4.5H20. When the water is driven
off, the anhydrous copper sulfate, CuSO4,
is almost white.
When copper sulfate is dissolved in
water, it gives a characteristic blue solu-
tion, but it does not dissociate into cupric
copper, Cu2+, and sulfate ions, SO4=, as
might be expected. The sulfate ions are
there, but the cupric copper ion is sur-
rounded (hydrated) by four molecules of
water. These all act as ligands, with their
oxygen atoms each donating a share in two
electrons, to satisfy the co-ordination
number, C N = 4, of the cupric ion. This
contribution is known as dative-covalence
and is, like hydrogen bonding, represented
two new ring structures are formed, one H /o\H
with six and the other with five members. Fig. 1. Blue hydrated cupric ion.
Most other stable aromatic ring structures
are made up of five and six-membered
rings. There is also a bald spot left on one a) 0.0’dihydroxy azo dye
side of the chromium atom which will be
referred to in the next section.
Stability of Aromatic Rings
Aromatic five and six-membered rings add
stability to molecules because of a phe-
nomenon known chemically as resonance.
Resonance is simply the movement of
bonding electrons from one atom to an-
other within a molecule. Structures which
provide electrons with a wide choice of
interconnected alternative places to con- b) 1:l chrome:dye complex
gregate are said to be resonance stabilized.
The classical examples are benzene and
naphthalene, Chapter 2, Fig. 1 (6). The
multiplicity of ways in which the bonds
may be drawn are indicative of resonance.
In Fig. 2b the metal still requires three
further ligands to satisfy the C N = 6
requirement, and fill the bald spot. These
could come from any available nondye,
ligand forming molecule or anion. They
could come from water, as in Fig. 1, but c) 1:2 chrome:dye complex
they could also come from alkaline solu-
tions as hydroxide ions, or from the amino, Fig. 2. Tridentate dye ligands forming 1:1 and
thiol, hydroxy or carboxylic acid groups in I :2, metakdyeco-ordination complexes.

56 0.3 Vol. 25, No. 3

'(.
Examples of meta1:dye complexes have
been given in previous chapters. I t is
interesting to think that nomadic carpet
dyers and weavers in ancient Persia (Iran)
knew how to use this chemistry before the
birth of Christ.
Premetallized Dyes
Dye manufacturers have long exploited
the stability of meta1:dye complexes, and
the products are spread broadly through-
out dye and pigment technology. How-
ever, the name premetallized dyes is usu-
ally reserved for those dyes which can be
applied to wool, in a similar manner to the
acid dyes, to achieve dyeings with fastness
properties which approach those of the
mordant (chrome) dyes, and without sig-
nificant free metallic ions in the effluent.
The 1:l premetallized dyes are 1:l
meta1:dye complexes. A number of them
were introduced in 1919. The structure of
the complex part of the molecule is shown
in Fig. 2b in which (in the absence of ionic
ligands filling the bald spot) the metal is
shown to carry a cationic charge. In
addition, these dyes normally have either
one or two sulfonate groups, -s03O
somewhere on the dye chromophore for
solubility. This would normally be ex-
pected to create two different kinds of dye.
When there is one metallic cationic charge
(+) and one sulfonate anion (-), the dye
molecule should have no overall charge;
i.e., it should behave as if it were nonionic.
However, if there is one cationic and two
anionic charges, the overall charge on the
dye molecule should be negative; Le., the
dye is anionic. But these mono- and
disulfonated dyes do not behave differ-
ently in practice.
This raises unanswered questions about
whether other anionic ligands can attach
themselves to the nondye side of the metal
(or the bald spot) in dyebath conditions.
Certainly the dyebath properties of these
dyes are somewhat abnormal, for they can
be dyed on wool at the very low pH of ca. 2
(8% sulfuric acid owg) and still level well.
This leveling a t low pH is most uncharac-
teristic of other acid dyes with good
wetfastness because such a low pH gener-
ally increases acid dye substantivity very
markedly. More recently, a range of 1:1
premetallized dyes has become available
which dyes wool a t pH 3.5-4, but it does
call for a special complex forming addi-
tive.
Whatever is really going on with these
dyes in the bath and on the fiber, they do
dye from acid baths to give fastness
approaching that of chrome dyes, with
relatively good leveling. For these reasons
they have a distinct market niche for wool
dyeing and constitute about 7% of the
market.
The 1:2 premetallized dyes are 1:2
meta1:dye complexes which were not in-
troduced until about 1951. Like most
other acid dyes of very good wetfastness
March 1993 Oca
(see later) they dye wool, silk and nylon
from almost neutral solution, but with
poor leveling properties. They have excel-
lent lightfastness but like all premetallized
dyes (but not all dye-metal complexes)
they have a shade gamut which is re-
stricted by the absence of bright colors.
Incidentally, metallization usually moves
the hue bathochromically and dulls the
shade.
Such dyes are illustrated by the struc-
ture shown in Fig. 2c, and since this
structure is already anionic, these prod-
ucts do not generally contain additional
sulfonate groups. However, they are large
molecules, of relatively low solubility, and
groups which can hydrogen bond to water
are used to improve this property; e.g.,
-S02-CH3 and -SOz-NH?, methyl
sulfonyl and sulfonamido groups, respec-
tively. These dyes have achieved consider-
able importance in applications where
very high lightfastness is desirable; e.g., in
nylon automotive carpets.
Lest we forget, some of these 1:2 metal-
dye complexes are cobalt derivatives, from
Co3+, and are very similar to the corre-
sponding chromium derivatives. They do
tend to be duller in shade, slower to dye
and have better lightfastness. Inciden-
tally, it is not necessary for the dye
chromophore on both sides of the metal to
be the same.
Mechanism of Acid Dyeing
Early work on the mechanism of acid dye
uptake by wool gave rise to the hypothesis
that under acid conditions, the cationic
hydrogen ions, being small and able to
diffuse readily, are first sorped from the
dyebath by the water swollen fiber and
become associated with the amino groups
in the wool to give cationic ammonium
groups, -NH3+. The electrical neutrality
of the fiber phase must be maintained, so
any anions present in the bath-such as
those associated with the acid, with any
salts present and with the dye-begin
simultaneously to diffuse into t h e fiber to
neutralize the charge on the -NH3+
groups. The dye anions, being rather large,
diffuse relatively slowly into the fiber, but
because they alone are substantive, they
will eventually displace all the smaller and
less or nonsubstantive anions which
rushed in first.
The chemical behavior of wool parallels
that of water soluble amino acids. Hydro-
gen ions can be sorped at least until the
largest majority of the carboxylate groups
are in the free acid form, -COOH. A t this
stage almost all the charged ammonium
groups, -NH3+, areavailable for eventual
neutralization by dye anions (see Eq. 1).
NH?-(X)-COOH -
OH -
H+
0-H-
N H -(x)-coo@
~ -.
H+
NHz--(X)-COO@ Eq. 1
This understanding gave rise to the notion
that the ammonium groups could be con-
sidered as dye sites for anionic dyes.
Further, the maximum possible concen-
tration of ammonium groups, which is
equal to the concentration of amino groups
present initially (in dry fiber), might also
represent the upper limit of dye anion
concentration which might be sorped to
saturate the fiber. Let this fiber saturation
concentration be written: (S)F
Carrying the idea a step further, the rate
of dyeing would be governed not only by
the concentration of dye in the bath but
also by the concentration of unoccupied
dye sites in the fiber:
Rate of dyeing = kdyeX (Dye),
x [(Q-(DY4fI Eq.2
Similarly, the rate of stripping can be
given:
Rate of stripping
= kstrlp x (DYe)f Eq. 3
At equilibrium the rates of dyeing and
stripping are equal and therefore:
(Dye)/. = k X (Dye),
x [(Q-(DY4f)l Eq.4
where k is equal to the constant, kdye +
kstrlp.Here kdyeand kdye and kstripare the
rate constants for dyeing and stripping
respectively. The last equation can be
rearranged to give an expression for the
concentration of dye in the fiber, (Dye)f, in
terms of that in the solution, (Dye),:
(Dye)f = k X (S)f X (Dye),
+
+ 1 k X (Dye), Eq.5
57
 This is the equation which governs the
shape of the so-called Langmuir sorption
isotherm. When k X (Dye), is much
larger than unity-Le., at high dye con-
centrations in the bath-Eq. 5 reduces to
(Dye)f = (S>f.
Langmuir Sorption Isotherms
If the equilibrium uptake of acid dyes by
wool, silk or nylon were governed solely by
the electrostatic or coulombic interaction
between the dye anions and the fiber
cations, then the sorption isotherms would
have shapes of the Langmuir type, Fig. 3b.
The curves should tend to level out to a
constant (Dye)f value which indicates the
maximum amount of dye which it is
I possible to get on these fibers and which is
equivalent to the concentration of avail-
able amino groups in the fiber.
Some acid dyes do show such behavior
on wool, but since the advent of nylon,
many more do not. In fact, the hypothesis
of attraction of anionic dyes to cationicdye
sites is an oversimplification. But it should
not be rejected out of hand, since it enables
other well known technical phenomena to
be explained in a simple, qualitative way.
Leveling Agents
The leveling agents used in wool and nylon
dyeing are usually of the type whose
effectiveness relies on controlling the rate
of dye uptake, so that adequate circulation
of the dye liquor can ensure that dyeings
are uniformly level from the start.
There are two principle types of leveling
agents-anionic and cationic-and the
action of both types can be understood by
examining the two concentration terms in
Eq. 2.
0 Anionic leveling agents control the
t r
Fig. 3. A graphical representation of how the Langmuir and Nernst
isotherms can be combined to reflect the equilibrium acid dyeing
characteristicsof wool, silk and nylon.
58
rate of dyeing by controlling the available
dye sites, [ (S)f- (Dyeh) I. Any other
anion, which can compete with the dye
anions for the available sites, effectively
lowers the value of this term, and by so
doing lowers the rateof dyeing (Eq. 2).
In acid wool dyeing it is quite usual to
dye in the presence of 2-3% owg sulfuric
acid, but it is normal to include 10% owg
sodium sulfate as a leveling agent. The
large concentration of sulfate anions com-
petes economically and effectively with
the dye anions for the cationic groups
within the fiber, although ultimately the
dye will prevail by virtue of its added
property-substantivity .
On the other hand, if a leveling agent
were chosen which was colorless, water
soluble and which dissociated into an
aipmatic anion with some substantivity,
the dye anion would have more serious
competition. Ideally such an agent should
diffuse more rapidly and have less substan-
tivity than the dye anion; otherwise the
normally high equilibrium exhaustion of
the dyebath could be in jeopardy.
0 Cationic leveling agents control the
rate of dyeing by controlling the effective
concentration of dye anion in the dyebath.
Eq. 2 shows that the rate of dyeing is
proportional to the dye concentration in
the bath, [Dye],.
When an organic leveler cation reacts
with an organic dye anion in water, the
result is an ionic complex. Such complexes
are in equilibrium with the free ions:
(Lev.') + (Dye-) 2 (Lev.+Dye-)
Here the concentration of added leveler
and the dissociation constant of the com-
plex will control the effective concentra-
tion of the free dye anion and hence the
rate of dyeing.
L
6 carbons'
Fig. 4.Comparison of repeat units in protein and polyamide fibers.There
are more than 16 different possibilities for R in wool; more than 1 1 for silk.
To ensure the solubility of such com-
plexes, the cationic leveling agents are
normally polyethoxylated quaternary
compounds which derive much of their
solubility not from their cationic character
but from their ethoxy groups,
- ( - C Z H ~ O - ) ~ -.
If only things were this simple! Many
proprietary leveling agents containing
both weakly acidic and weakly basic
groups (like amino acids) and whether
they are anionic or cationic in the dyebath
depends on the pH. Such compounds are
referred to as being amphoteric.
Dye-Fiber interactions
The danger inherent in generalizing about
dye and fiber molecules lies in assuming
that they are homogeneous. Certainly
wool, silk and nylon fibers have an ionic
character at some locations, as do acid
dyes, but this does not limit the interaction
between dyes and fibers to electrostatic
interactions.
Water soluble dyes have hydrophilic
locations, such as the sulfonate groups,
-SO3Na, but they also have regions which
are made up primarily of benzenoid and
aliphatic hydrocarbons, which gives them
a tendency to aggregate into dye-dye
micelles. The magnitude of this tendency
depends on the number and location of the
ionic groups and on the size and hydropho-
bic character of the rest of the molecule.
Wool fibers have a higher moisture
regain than cellulosic fibers, and they are
filled with ionic groups. But there are
locations where particular amino acid
substituents in the chain include phenyl
(benzenoid) and other hydrocarbon sub-
stituents. Nylon fibers are not very hydro-
philic overall (contrast wool) and they are
filled with hydrocarbon segments which
_t
1
__f
6 carbons -1n ca. 75
CCO Vol. 25, No. 3
are definitely hydrophobic. These are the
paraffinic hydrocarbon, -(-CH*-),, -,
groups where n = four, five or six (Fig. 4).
So in addition to ionic interactions some
level of hydrophobic, dye-fiber bonding is
to be expected, particularly between spar-
ingly water soluble dyes with large mole-
cules and nylon. But what is hydrophobic
bonding? It is a term which does not imply
a particular kind of bond, and has been
described as “the tendency of hydrophobic
groups . . . to associate together and es-
cape from an aqueous enyironment”(7).
The hydrocarbon regions dye-dye or dye-
fiber are held in close proximity by van der
Waals forces and are comparable with the
bonding between the hydrophobic dis-
perse dyes and polyester fibers.
The reality of acid dye to fiber bonding
is that it is heterogeneous overall, varying
from situation to situation, dye to dye. It
lies somewhere on a line between the
idealized electrostatic (coulombic) attrac-
tion of some acid dye molecules for wool
and nylon (Langmuir) and the idealized
hydrophobic bonding of disperse dyes for
nylon (Nernst). Bothsituations couldexist
to different extents within the same fibers.
Where on this line might one expect the
large, sparingly soluble 1:2 premetallized
dye molecules (with delocalized ionic
charge) to fall?
These two extremes have been repre-
sented in Fig. 3b and c as Langmuir and
Nernst sorption isotherms respectively
(8). There is an infinite number of inter-
mediate or combination sorption iso-
therms, one of which is illustrated in Fig.
3a. The relative importance of the ionic
and hydrophobic interactions may be as-
sumed to vary with the particular dye and
fiber involved (9).
The whole subject of the thermodynam-
ics of sorption of acid dyes by polyamides
has been approached with much more
scientific rigor by McGregor (IO) and
Sumner (11). Both use an approach based
onDonnan membrane equilibria (12). The
more rigorous approaches allow the effect
of changing the concentration of amino
and carboxylic acid end groups to be
studied, as well as the blocking effects,
where the greater substantivity of one dye
in a mixture can effectively prevent an-
other dye from being sorped by nylon.
Perhaps the biggest surprise to the
traditionalist is that whole families of
different sorption isotherms, resembling
curves Fig. 3a and b, can be predicted
without the need to assume either that
anionic dyes become associated with cat-
ionic dye sites or that addition of a
separate mechanism for making allow-
ance for hydrophobic dye-fiber bonding is
necessary.
In other words, “Ionic dyeing systems
are extremely complex” (10). Those who
wish to pursue this matter further should
consult the appropriate references (IO,
11).
Review
For some, the preceding sections may have
contained more than enough general back-
ground chemistry. However, it should now
be apparent that much chemical technol-
ogy has gone into the development of those
acid, mordant (chrome) and premetal-
lized dyes in use today.
A generalized mechanism for acid dye-
ing based primarily on the coulombic
(electrostatic) attraction of anionic dyes
by oppositely charged sites in the fibers has
the benefit of simplicity and can be used to
qualititatively explain the different ionic
types of leveling agents suitable for use
when dyeing wool, silk and nylon. But such
a mechanism is not entirely valid, and it
cannot fully explain the widely known
phenomena of overdyeing or the blocking
of one dye from the fiber by another.
The variety of colored anionic struc-
tures suitable for application to wool, silk
and nylon, with their localized hydropho-
bic and hydrophilic regions, coupled with
the mixture of hydrophobic and hydro-
philic locations within the fiber molecules,
calls for a dyeing mechanism which can
take into account both ionic and hydro-
phobic dye-fiber bonding.
These more comprehensive approaches
to modeling the dyeing system tend to be
dismissed as too complex. However, it is
now more than 50 years since the develop-
ment of nylon and it is not too soon to
attempt to raise the general level of under-
standing what is involved when dyeing
ionic fibers with anionic dyes.
References
(1) Colour Index, AATCC and the Society of
Dyers and Colourists, Vol. 1, Acid Dyes, Third Edi-
tion, 1971.
(2) Colour Index, AATCC and the Society of
Dyers and Colourists, Vol. 3, Natural Dyes, Third
Edition, 197I.
(3) Bird, C. L., Theory and Practice of Wool
Dyeing, Fourth Edition, Society of Dyers and Colour-
ists, Bradford, U.K., 1972.
(4) Buyer’s Guide for the Textile Wet Processing
Industry, published as the July issue of Textile
Chemist and Colorist,July 1992.
( 5 ) Aspland, J. R., Textile Chemist and Colorist,
Vol. 24, No. 9, September 1992, p74.
(6) Aspland J. R., Textile Chemist and Colorist,
Vol.23,No. 12,December 1991,p30.
(7) Giles C. H., The Theory and Coloration of
Textiles, Second Edition, Edited by A. Johnson,
Society of Dyers and Colourists, 1989, Chapter 2.
(8) Aspland J. R., Textile Chemist and Colorist,
Vol.24,No. 10,October 1992, p39.
(9) Iijima, T.et al., “Kinetic Behavior in Mixture
Dyeing: Acid Dye/Polyamide,” proceedings from
AATCC International Dyeing Symposium, Char-
lotte, N. C., June 1992, p23.
(IO) McGregor, R., “Ionic Dyeing Systems,” pro-
ceedings from AATCC International Dyeing Sympo-
sium, Washington, D. C., May 1977, p126.
( 1 1) Sumner, H. H., Ref. 7, Chapter 4.
( 1 2) Aspland, J. R., Textile Chemist and Colorist,
Vol. 24, No. 5, May 1992, p34.

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