Original article

Textile Research Journal

2016, Vol. 86(16) 1738–1749

Release behavior and kinetic evaluation ! The Author(s) 2015

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of formaldehyde from cotton clothing DOI: 10.1177/0040517515606356
trj.sagepub.com
fabrics finished with DMDHEU-based
durable press agents in water and
synthetic sweat solution

Bing Li1, Yongchun Dong1,2, Peng Wang1 and Guixin Cui1,3

Abstract
The durable press-finished cotton fabrics were prepared with dimethylol dihydroxy ethylene urea (DMDHEU) and
methylated DMDHEU, and tested for formaldehyde release in distilled water or synthetic sweat at pH 5 or 8 to simulate
the extraction of formaldehyde by sweat under similar wearing conditions. The release mechanism of formaldehyde was
studied and compared using three diffusion kinetic models. The effect of release conditions and finishing process on the
formaldehyde release was also investigated. The results indicated that the release process of formaldehyde from the
finished fabric includes a burst release phase and a slow release phase, which is explained by five different sources. The
formaldehyde release mechanism followed the Fickian mode, and could be described by Higuchi, Double phases and
Korsmeyer–Peppas kinetic equations, respectively. Higher formaldehyde release was found at pH 8 than that at pH 5.
Formaldehyde showed a lower release rate in synthetic sweat solution than that in water under the same conditions.
Increasing water volume or temperature enhanced the formaldehyde release, suggesting that a high sweat rate and skin
temperature may accelerate the formaldehyde release. When finishing the fabrics, a higher concentration of finishing
agent and the addition of softener accelerated the formaldehyde release. However, increasing catalyst concentration and
curing temperature could reduce the formaldehyde release. It is concluded that formaldehyde release can be effectively
reduced by optimizing the durable press finishing process of cotton fabrics, thus possibly decreasing risk of allergic
contact dermatitis from formaldehyde in textiles.

Keywords
durable press finishing, formaldehyde release, dimethylol dihydroxy ethylene urea, kinetic model

Durable press agents (DP agents) are generally used to

improve the wrinkle resistance of various clothing
fabrics during wear and laundering. However, the
majority of DP agents often contain significant levels
of formaldehyde because they are created from the
condensation product of formaldehyde with urea or
melamine. Formaldehyde is a known human carcino-
gen,1,2 which is released from the cotton clothing fab-
rics finished with formaldehyde-based DP agents in the
last decades. Previous study3 has found that large
amounts of formaldehyde were concentrated in skin
next to the durable press garment and relatively small
amounts enter the body when rabbits were used as the
test subjects. In the 1950s and 1960s, allergic contact
1
Division of Textile Chemistry & Ecology, School of Textiles, Tianjin
Polytechnic University, China
2
Key Laboratory of Advanced Textile Composites, Ministry of Education,
Tianjin Polytechnic University, China
3
Jiangnan Branch, China Textile Academy, Shaoxing, China
Corresponding author:
Yongchun Dong, Division of Textile Chemistry & Ecology, School of
Textiles, Tianjin Polytechnic University, 399 Bingshui West Road, Xiqing
District, Tianjin 300387, China.
Email: dye@tjpu.edu.cn, or teamdong@sina.cn
Li et al.
dermatitis (ACD) from formaldehyde in textiles was
commonly reported, especially in Europe. Repeated
exposure to fabrics treated with N-methylol durable
press agents served as the primary sensitizer in many
of the cases.4,5 The first sign of ACD is the presence of a
rash or skin lesion at the site of exposure.
Since the 1960s dimethylol dihydroxy ethylene urea
(DMDHEU) with lower levels of formaldehyde has
gradually become a popular DP agent. In the last
30 years, modified DMDHEU (e.g. methylated or gly-
colated DMDHEU) was used to further reduce formal-
dehyde amounts. These values are well below the levels
of 500–750 mgg1 estimated to be able to elicit ACD in
patients who are allergic to formaldehyde.6
Additionally, the use of scavengers such as urea and
carbohydrazide in durable press finishing systems of
cotton fabrics has also been shown to be an effective
way of reducing the formaldehyde release.7 Despite
this, there are still several US clinical studies being
reported8–12 about US patients suffering from ACD
to formaldehyde in textiles. Some countries such as
Japan, Finland and China have legally limited the for-
maldehyde content in textile products to reduce the risk
of ACD since 1973. The international lower limit
(75–120 mgg1) for highly formaldehyde sensitive
patients to develop dermatitis for the textiles in direct
contact with the skin has also been proposed by de
Groot and Maibach et al.5,6
However, the threshold level for formaldehyde in
clothes that may cause ACD in sensitized individuals
is unknown. It is necessary to investigate the transfer
mechanisms of formaldehyde from the finished fabric
to human skin to ascertain how much formaldehyde
is actually released to cause ACD. Hollies et al.13
reported that three mechanisms of transfer to skin
require consideration: (1) direct transfer of solid mater-
ial arising from contact between fabric and skin; (2)
direct transfer of vapor released by the fabric under
conditions of use; (3) direct transfer in the liquid
phase of chemicals leached from the fabric by sweat.
In the case of durable press-finished fabrics, it was
found that the release of formaldehyde from cotton
fabric through the first and second mechanism is very
low (<10 ngg1).2 Other researches7,14,15 found that the
formaldehydes released from the finished fabrics
include free formaldehyde and hydrolysable formalde-
hyde from its precursors (the formaldehyde-containing
compounds). If these precursors are present in the fin-
ished fabrics, they can be hydrolyzed by sweat on the
skin surface to release free formaldehyde.
In practice, clothes, especially the underclothes, have
frequent contact with skin and sweat. In general, two
groups of people including workers involved in the
production of finished textiles and consumers are con-
sidered to have the risk of formaldehyde contact allergy
1739
because both of them have close contact with the fin-
ished textiles. Thus, the third mechanism described
above should be considered as the main route for the
release of formaldehyde from the finished fabric to skin
through sweat extraction. However, little is known
about the transfer mechanism of formaldehyde
molecules from the finished fabric to the human skin.
Hence, the main objective of this work is to obtain the
release rate and quantity of formaldehyde from the fin-
ished cotton fabrics with DMDHEU-based agents to
simulate the extraction of formaldehyde by perspiration
under similar wearing conditions. Moreover, the equi-
librium and kinetic data of the release process in differ-
ent aqueous media were evaluated and compared using
three diffusion models (Higuchi, Double phases and
Korsmeyer–Peppas equations) to study the release
mechanism of the formaldehyde molecules from the
finished fabric to the human skin. Some important vari-
ables including release condition (the ratio of the
release a medium volume to mass of the finished
fabric and temperature) and finishing process (DP
agent concentration, catalyst concentration and curing
temperature) on the formaldehyde release were investi-
gated. In addition, this work also discussed the poten-
tial impact of ACD from formaldehyde release varied
with sweat production on human skin.
Experimental methods
Durable press finishing of cotton fabrics
Commercially scoured, bleached and mercerized plain
weave loom-state 100% cotton fabric with 32 yarncm1
density, 30 yarncm1 weft density and 112.3 gm2 aver-
age area density were used in this investigation, and
further treated with an aqueous solution containing
2.0 gL1 Na2CO3 and 2.0 gL1 anionic detergent at
100 C for 25min, and then thoroughly washed with
cold distilled water and dried at room temperature.
DMDHEU and methylated DMDHEU as two com-
mercial DP agents were provided by China Textile
Academy. Methylated DMDHEU was prepared by
partial modification with methanol (equation (1)).
These DP agents were chosen for study because they
are widely used by the textile industry, especially in
China. The contents of free formaldehyde of
DMDHDU and methylated DMDHEU were deter-
mined to be 0.09% and 0.15%, respectively, by a
method from the National Standard of China GB/T
27593-2011: Textile dyeing and finishing auxiliaries-
free formaldehyde content of amino resin agent. A con-
ventional pad-dry-cure process was adopted for the
durable press finishing of the cotton fabric. It was
impregnated with a finishing solution containing vari-
ous concentration of DMDHEU or methylated
1740 Textile Research Journal 86(16)

DMDHEU (50–150 gL1) and MgCl26H2O (0.5– adding acetylacetone at 40 C for 30 min. The absorb-
20 gL1) with or without softener at room temperature. ance of the solution was measured at 412 nm using a
The impregnated fabric was then padded by a labora- UV-2401 Shimadzu spectrophotometer (Shimadzu
tory padding mangle (Mathis AG, Switzerland). The Corp., Japan). All the experiments were carried out in
wet pick-up was 75–80%. After being padded, the triplicate. The results were expressed as the mean value.
fabric was immediately dried at 80 C for 3 min and Standard deviation is less than 5% of the mean value.
cured in an oven at a different temperature (140–
190 C) for 1.5 min. All the finished fabrics were sealed
using plastic bags in the dark at 5 C before fabric
Study of formaldehyde release kinetics
evaluation. To investigate the mode of formaldehyde release from
the finished fabrics, the release data were fitted to the
O
O following model equations:
C H+ C
HOH2C N N CH2OH + CH3OH H3COH2C N N CH2OCH3
ð1Þ 1. Higuchi equation:20–22
HO OH HO OH

DMDHEU Methylated DMDHEU

Qt ¼ kH t0:5 ð2Þ

where Qt is the concentration of formaldehyde released

from the finished fabric at time t, and kH represents the
Preparation of synthetic sweat solutions
Higuchi release rate constant. Higuchi describes for-
The constituents of sweat on human skin mainly con- maldehyde release from the finished fabric as a square
tain inorganic salts and organic compounds. Sweat pH root of the time-dependent process on the basis of
is varied in its composition. The greater the sweat Na+ Fickian diffusion.
concentration, the greater the sweat pH.16,17 The alka- 2. Double phases equation:23,24
line synthetic sweat (pH ¼ 8.0) and acid synthetic sweat


(pH ¼ 5.0) were often used to simulate the actual sweat Qt ¼ Qe  AekBtþ BekSt ð3Þ
in some studies.17–19 Two synthetic sweat solutions
were prepared according to ISO standard test 105- where Qe is the concentration of formaldehyde released
E04 described in this work.18,19 In order to produce from the fabric sample at equilibrium. Formaldehyde
the synthetic sweat solution, 0.50 gL1 L-histidine release can be divided into two phases: burst release
monochloride monohydrate, 5.0 gL1 NaCl and phase (denoted as B phase) and slow release phase
2.20 gL1 NaH2PO4.12H2O were mixed in distilled (denoted as S phase). kB and kS are the release rate
water. Subsequently, the pH value of this solution constants for B and S phases, respectively.
was adjusted to 8.0 using 0.10 molL1 NaOH for the 3. Korsmeyer–Peppas equation:20,25,26
alkaline synthetic sweat or 5.0 using 0.10 molL1 HCl
for the acid synthetic sweat, and measured using a Qt ¼ kKP tn ð4Þ
DHS-25C digital pH meter (Shanghai Jingmi
Instrumental Co., China). All the solutions were kKP is the release rate constant and n is the release
stored in the dark at 5 C before usage. exponent, which is used to characterize the mechanism
of the formaldehyde release and listed in Table 1.
Release of formaldehyde from finished fabrics
The dried finished fabric was cut into small pieces
(about 0.50 cm  0.50 cm), and thoroughly mixed Table 1. Release mechanism with variation of n values
together. The pre-weighed fibrous pieces were placed
Rate as a
into the fixed volume of the distilled water or synthetic
n value Release mechanism function of time
sweat solution at atmospheric pressure (1.013  105 Pa)
and a certain temperature under gentle shaking. The n < 0.5 Quasi-Fickian diffusion t0.5
ratio of volume (ml) of release medium to mass (g) of n ¼ 0.5 Fickian diffusion t0.5
the finished fabric (denoted as Rvm) was kept to be 100 0.5 < n < 1.0 Anomalous tn-1
(unless otherwise stated). After specified time interval, (non-Fickian) diffusion
the fibrous pieces were removed by filtration. The con- n ¼ 1.0 Non-Fickian case II Zero order
centration of the formaldehyde present in the aqueous release
medium at different time interval was then determined n > 1.0 Non-Fickian super case II tn-1
according to method of Japanese Law 112-1973 by
Li et al.
450
B phase S phase
400
350
300
Qt(µ gg )
250
-1
Distilled water
200
Synthetic sweat
150
100
50
(DMDHEU)
0
0 60 120 180 240 300
t (min)
Figure 1. Release curves of formaldehyde from two finished fabrics in different aqueous media. Finishing process: DMDHEU or
methylated DMDHEU: 100 gL1, MgCl26H2O: 18 gL1, Curing: 170 C  1.5 min. The values were given as the mean. Standard devi-
ation is less than 5% of the mean value. DMDHEU: dimethylol dihydroxy ethylene urea.
Results and discussion
Formaldehyde release behavior
Cotton fabric was finished with DMDHDU or methy-
lated DMDHEU by the pad-dry-cure process described
above. Formaldehyde release from the obtained fin-
ished fabric was then carried out in different aqueous
media at 35 C, and the experimental results are shown
in Figure 1.
Figure 1 shows that there is a sharp increase in
release quantities of formaldehyde from two finished
fabrics (Qt) as time increasing at the initial release
stage of 60 min. An insignificant increase of Qt values
was observed after 60 min, and the increasing tendency
of Qt values becomes level when release time is beyond
180 min. This is attributed mainly to several sources of
released formaldehyde from the finished fabric. The
first source is free formaldehyde adsorbed by the fin-
ished fabrics. This formaldehyde is generally defined as
the uncombined monomeric formaldehyde present in
finish solutions because its sources are stoichiometric
excesses that may have been included in the resin man-
ufacturing step.3 Free formaldehyde can quickly move
from the fabric to water as soon as the fabric comes
into contact with aqueous medium. The second source
is the most labile cellulose hemiacetal, which readily
revert back to formaldehyde (equation (5)) because cel-
lulose often picks up formaldehyde from the atmos-
phere.27 The third source may be formed by the
hydrolysis of the N-CH2OH groups from unreacted
DMDHEU or from pendant N-CH2OH groups of
DMDHEU molecules that have reacted with cellulose
through only one N-CH2OH group. These linkages are
1741
250
B phase S phase
200 pH = 5.0
Distilled water
pH = 8.0
pH = 5.0
Synthetic sweat
150 pH = 8.0
Qt(µ gg )
-1
pH = 5.0
pH = 8.0
pH = 5.0 100
pH = 8.0
50
0 (Methylated DMDHEU)
360 420 0 60 120 180 240 300 360 420
t (min)
rather labile and easily revert back to their
starting materials (equation (6)). It is difficult to cure
all the DMDHEU molecules which are applied
and make sure there are no pendant N-methylol
groups left. It is clear that this formaldehyde
exhibits a relatively slower release rate than free formal-
dehyde since the hydrolysis of the N-CH2OH
groups depends on the relative stability of their C-O
and C-N bonds.
The fourth source is the formaldehyde released from
the breaking of the crosslinks between DMDHEU and
cellulose molecules, which was revealed by the gradual
disappearing of ether group (1108 cm1) as well as the
formations of absorbing bands of -CH2OH (1027 cm1
and 1077 cm1) for DMDHEU and absorption peak of
-OH for cotton fiber in their IR spectra.28,29 This will
provide an additional N-CH2OH group, which can
hydrolyze, thus resulting in a slow formaldehyde release
(equation (7)). It was reported that the methylated
DMDHEU is more resistant to both acid and alkaline
hydrolysis than those from DMDHEU.30 As a result,
methylated DMDHEU will give the fabrics low formal-
dehyde release. In addition, formaldehyde can be
released directly from N, N0 -oxydimethylene linkages
formed by condensation of methylol groups of
DMDHEU in the finished fabric (equation (8)).31 It
should be noticed that the formaldehyde from pendant
N-CH2OH groups (third source), cellulose crosslinks
(fourth source) and N, N0 -oxydimethylene linkages is
regarded as the hydrolysable formaldehyde, the
released amounts of which are variable and larger
than the amount of free formaldehyde.14 Accordingly,
the release curves of formaldehyde can be divided into a
1742 Textile Research Journal 86(16)

burst release phase (denoted as B phase) and a slow polymer network, which makes the polymeric segments
release phase (denoted as S phase), as illustrated in more rigid and restricts their relaxation upon contact-
Figure 1. The burst release phase may be explained ing with incoming solvent molecules.21,22 The
by first source, second source, and partial hydrolysable DMDHEU-based DP agents can react with hydroxyl
formaldehyde. The rest of hydrolysable formaldehyde groups of cellulose chains to produce the crosslink
should be responsible for the slow release phase. structures on the surface of the finished fabrics. On
A similar result was reported by Cooke.3 the other hand, the formaldehyde release can be best
expressed by Double phases model, as the fitting results
Cell OCH2OH Cell OH + CH2O ð5Þ showed a higher regression coefficients (>0.98). This
indicates that the formaldehyde release has been com-
O posed of a burst release phase and slow release phase.
C
Cell OH2C N N CH2OH
This is in good agreement with the result obtained
according to Higuchi equation. To further confirm
HO OH
ð6Þ the release mechanism, the data were also fitted into
O Korsmeyer–Peppas equation for calculating the diffu-
C
Cell OH2C N NH 2CH2O
sion exponent (n). Two finished fabrics showed better
regression coefficients (>0.90), with slope (n) values
HO OH
ranging from 0.10 to 0.30, indicating that the formal-
O
dehyde release follows Fickian mode.20,25,26 Besides,
C MRE and AIC values of these fitted model equations
Cell OH2C N N CH2O Cell Cell OH were in their reasonable ranges. According to Fick’s
HO OH
first law, the flux goes from regions of high concentra-
ð7Þ tion to regions of low concentration, with a magnitude
O O that is proportional to the concentration gradient.
C C Consequently, it is believed that formaldehyde will
HOH2C N N CH2OH HN NH + 2CH2O move from a region of high concentration on the fabric
HO OH HO OH to a region of low concentration in the aqueous solu-
tion across a concentration gradient. Formaldehyde
O O release from the DMDHEU or methylated
C C DMDHEU finished fabrics has the same mechanism
OH2C N N CH2 O CH2 N N CH2O
at pH 5 and 8 in water or synthetic sweat solution.
HO OH HO OH Moreover, it is also noticed that kHB is much higher
ð8Þ than kHS for each of the formaldehyde release curves
O O
for two DP agents in water or synthetic sweat solution.
C C This confirms that formaldehyde has a significant burst
OH2C N N CH2 N N CH2O + CH2O release phase once the finished fabric is immersed with
HO OH HO OH water or synthetic sweat solution.
In addition, it is evident in Tables 2 and 3 that kHB,
kKP and Qe values at pH 5 are lower than those at pH 8
for two finished fabrics in water or synthetic sweat solu-
tion, which demonstrates that formaldehyde release has
Mechanism of formaldehyde release more difficulty at acid medium than at alkaline medium
In order to understand the mechanism of formaldehyde under the same conditions. This is mainly owing to the
release kinetics from the finished fabrics, the data pre- relative stability of the C-O and C-N bonds of the
sented in Figure 1 were regressed according to the three N-CH2OH in DMDHEU or methylated DMDUEU
model equations, and the regression results are listed in and its crosslinks with cellulose molecules. It was
Tables 2 and 3. reported that the rate of cleavage of the C-O bond is
As shown in Tables 2 and 3, the data are found to fit much faster than that of the C-N bond under acidic
well with the Higuchi equation with all regression coef- conditions, thus the latter determines the release rate
ficients >0.90, illustrating that the formaldehyde release of formaldehyde. Moreover, the rate of cleavage of
from the finished fabrics can be described using the the C-N bond was relatively lower under acid condition
Higuchi equation based on Fickian diffusion by two and higher under alkaline condition,3 which therefore
stages. This is because the Higuchi diffusion-controlled enhanced the formaldehyde amount released from the
release model is suitable for the highly crosslinked finished fabric at alkaline medium. The cleavage of C-O
Li et al. 1743

Table 2. Kinetic parameters of formaldehyde release from DMDHEU finished fabric

Kinetic Correlation
Medium pH Models Fitted model equations parameters coefficient MRE (%) AIC

Water 5 Higuchi Qt ¼ 10.40t0.5 kHB ¼ 10.40 RHB ¼ 0.9014 7.648 193.7

Qt ¼ 0.594t0.5 kHS ¼ 0.594 RHS ¼ 0.9728
Double phases Qt ¼ 96.52  (42.06e0.699t Qe ¼ 96.52 R ¼ 0.9962 14.13 209.0
+54.28e0.063t)
Korsemeyer–Peppas Qt ¼ 52.63t0.117 kKP ¼ 52.63 RKP ¼ 0.9134 18.3 125.2
n ¼ 0.117
8 Higuchi Qt ¼ 40.42t0.5 kHB ¼ 40.42 RHB ¼ 0.9866 35.74 176.9
Qt ¼ 1.491t0.5 kHS ¼ 1.491 RHS ¼ 0.9651
Double phases Qt ¼ 389.1  (288.6e0.027t Qe ¼ 389.1 R ¼ 0.9988 72.27 185.8
+94.32e29.86t)
Korsemeyer–Peppas Qt ¼ 121.1t0.211 kKP ¼ 121.1 RKP ¼ 0.9505 32.96 264.5
n ¼ 0.211
Synthetic sweat 5 Higuchi Qt ¼ 8.61t0.5 kHB ¼ 8.61 RHB ¼ 0.9950 17.57 105.4
Qt ¼ 0.859t0.5 kHS ¼ 0.859 RHS ¼ 0.9693
Double phases Qt ¼ 79.66  (20.07e0.007t Qe ¼ 79.66 R ¼ 0.9962 26.43 213.6
+53.51e0.052t)
Korsemeyer–Peppas Qt ¼ 20.29t0.240 kKP ¼ 20.29 RKP ¼ 0.9547 4.53 125.0
n ¼ 0.240
8 Higuchi Qt ¼ 29.12t0.5 kHB ¼ 29.12 RHB ¼ 0.9721 10.64 202.5
Qt ¼ 3.413t0.5 kHS ¼ 3.413 RHS ¼ 0.9790
Double phases Qt ¼ 282.4  (105.8e0.012t Qe ¼ 282.4 R ¼ 0.9926 43.66 182.8
+152.5e0.110t)
Korsemeyer–Peppas Qt ¼ 92.51t0.200 kKP ¼ 92.51 RKP ¼ 0.9635 25.48 236.4
n ¼ 0.200
kHB (min0.5) and kHS (min0.5) are Higuchi release rate constants at B phase and S phase, respectively. kKP (minn) is the release rate constant for
Korsemeyer–Peppas model. Qe (mgg1) is the concentration of formaldehyde released from the fabric sample at equilibrium. The values were given as
the mean. Standard deviation is less than 5% of the mean value. MRE (maximum relative error) is express as: MRE ¼ (1-Qfit/Qexp)  100%, where Qex
and Qfit are experimental data and fitted value of formaldehyde release quantity. AIC (akaike information criterion) can be calculated as: AIC ¼ N(ln
SSR) + 2p, where N is number of experimental data points, SSR is the sum of the squared residuals and p is the number of parameters. The smaller the
value of AIC, the better the model adjusts the data.32

bond and C-N bond of the N-CH2OR under acidic formaldehyde,33,34 and their reaction is described by
condition is expressed in equation (9). equation (10).

O O
k2 k1 OH OH

CH2OH
N CH2 O R + H+ HO R + N NH2 N N
CH2OH ð10Þ
ð9Þ + CH2O
N N
+ H2O
H CH2OH
N CH2 N H + CH2O

In order to verify the reaction of formaldehyde with

On the other hand, formaldehyde release shows
larger kHB, kKP and Qe values in the case of water
than in the case of synthetic sweats at the same pH
level. The main reason may be that the NH or NH2
groups in L-histidine molecule can react with
L-histidine in synthetic sweat, each component of syn-
thetic sweat was added into three aqueous formalde-
hyde solution (initial concentration: 5.0 mgL1),
respectively. And then the resulting mixtures were
kept at pH 5 or pH 8 and 30 C for 30 min under
1744 Textile Research Journal 86(16)

Table 3. Kinetic parameters of formaldehyde release from methylated DMDHEU finished fabric

Kinetic Correlation
Medium pH Models Fitted model equations parameters coefficients MRE (%) AIC

Water 5 Higuchi Qt ¼ 7.801t0.5 kHB ¼ 7.801 RHB ¼ 0.9613 18.76 180.4

Qt ¼ 1.829t0.5 kHS ¼ 1.829 RHS ¼ 0.9522
Double phases Qt ¼ 90.82  (42.04e0.014t Qe ¼ 90.82 R ¼ 0.9845 13.01 216.6
+48.40e0.773t)
Korsemeyer–Peppas Qt ¼ 38.46t0.151 kKP ¼ 38.46 RKP ¼ 0.9866 16.87 156.0
n ¼ 0.151
8 Higuchi Qt ¼ 22.13t0.5 kHB ¼ 22.13 RHB ¼ 0.9456 31.61 182.8
Qt ¼ 2.706t0.5 kHS ¼ 2.706 RHS ¼ 0.9354
Double phases Qt ¼ 223.7  (79.79e0.011t Qe ¼ 223.7 R ¼ 0.9939 13.94 138.3
+129.56e0.156t)
Korsemeyer–Peppas Qt ¼ 84.71t0.171 kKP ¼ 84.71 RKP ¼ 0.9643 29.53 217.7
n ¼ 0.171
Synthetic sweat 5 Higuchi Qt ¼ 4.29t0.5 kHB ¼ 4.29 RHB ¼ 0.9881 15.24 128.2
Qt ¼ 0.388t0.5 kHS ¼ 0.388 RHS ¼ 0.9522
Double phases Qt ¼ 47.84  (31.65e0.021t Qe ¼ 47.84 R ¼ 0.9969 38.42 203.5
+16.22e0.614t)
Korsemeyer–Peppas Qt ¼ 15.89t 0.198 kKP ¼ 15.89 RKP ¼ 0.9540 12.40 84.03
n ¼ 0.198
8 Higuchi Qt ¼ 12.55t0.5 kHB ¼ 12.55 RHB ¼ 0.9419 7.753 95.17
Qt ¼ 0.801t0.5 kHS ¼ 0.801 RHS ¼ 0.9135
Double phases Qt ¼ 114.2  (39.81e0.018t Qe ¼ 114.2 R ¼ 0.9991 32.74 140.7
+75.61e0.169t)
Korsemeyer–Peppas Qt ¼ 47.56t0.117 kKP ¼ 47.56 RKP ¼ 0.9156 96.45 233.9
n ¼ 0.117

Table 4. Formaldehyde concentrations in different concentration in the solution or synthetic sweat syn-
solutions after reaction thetic sweat.
Comparing the kinetic parameters of formaldehyde
Formaldehyde
concentrations (mgl1) release listed in Tables 2 and 3, kHB, kKP and Qe values
for DMDHEU-finished fabric are remarkably higher
Systems pH ¼ 5 pH ¼ 8 than those for methylated DMDHEU-finished fabrics.
This is because that the alkylation of DMDHEU can
5.0 gl1 NaCl 4.99 4.92
significantly reduce the formaldehyde release by
2.2 gl1NaH2PO4.12H2O 4.97 4.95
improving the stability of C-O bond of its N-CH2OR
0.50 gl1 L-histidine 3.50 3.62 group during the hydrolysis. Moreover, the resistance
Synthetic sweat 3.54 3.57 to hydrolysis also seems to depend on the extent of
alkylation of DMDHEU.30 Another possible reason is
that DMDHEU has a higher content of free formalde-
continuous agitation. For comparison, a control experi- hyde than methylated DMDHEU, as described above.
ment was also performed with synthetic sweat. Finally, Thus, more free formaldehyde molecules may be
the formaldehyde concentrations in four solutions were transported to the fabric when DP finishing being
measured and are presented in Table 4. conducted with DMDHEU. Hence, it is believed that
Table 4 shows that the formaldehyde concentration there is higher formaldehyde concentration on
in the solution containing L-histidine or synthetic sweat DMDHEU-finished fabric than that on methylated
is much lower than 5.0 gl1. By contrast, the formalde- DMDHEU-finished fabric. On the basis of Fick diffu-
hyde concentrations in the other two systems without sion law, formaldehyde molecules move more quickly
L-histidine are close to 5.0 gl1 under the same condi- from DMDHEU-finished fabric than methylated
tions. These results confirm that L-histidine has reacted DMDHEU-finished fabric into the aqueous solution.
with formaldehyde, thus reducing the formaldehyde More importantly, it should be pointed out that Qe
Li et al.
400
DMDHEU
350 pH = 5.0
pH = 8.0
300
Qe(µ gg )
-1
250
200
150
100
50
0 20 40 60 80 100
Rvm
Figure 2. Relationship between Rvm and Qe values. Finishing process: DMDHEU or methylated DMDHEU: 100 gL1, MgCl26H2O:
18 gL1, Curing: 170 C  1.5 min. Error bars are the standard deviation of the mean values shown. DMDHEU: dimethylol dihydroxy
ethylene urea.
values (79.66 mgg1 for DMDHEU and 47.84 mgg1 for
methylated DMDHEU) in acidic synthetic sweat for
two finished fabrics are lower than the international
lower formaldehyde limit (75–120 mgg1) for the textiles
in direct contact with the skin.5,6 Correspondingly, Qe
values (282.4 mgg1 for DMDHEU and 114.2 mgg1 for
methylated DMDHEU) in alkaline synthetic sweat sig-
nificantly exceed this limit. Accordingly, from the view
point of reducing formaldehyde release, it is necessary
to decrease the application of two DP agents, especially
DMDHEU in wrinkle-resistant finishing of cotton
fabrics.
Effect of release conditions
It is well known that the amount of sweat secreted from
the pores of the human body or the sweat rate is highly
varied and dependent upon daily activity, emotional
state and environmental temperature. Moreover,
human sweat production may increase to 3.0 Lh1 by
short-term exercise in warm environment.35 To exam-
ine the formaldehyde release from the finished fabric in
different amount of sweat secreted, cotton fabric was
finished with DMDHEU or methylated DMDHEU
using the pad-dry-cure process, and then tested for for-
maldehyde release in distilled water at 35 C and differ-
ent Rvm for 400 min. The released quantity of
formaldehyde at equilibrium (Qe) was calculated by
Double phases equation and provided in Figure 2.
Figure 2 shows that little change in Qe value at pH 5
was observed when Rvm level increased from 10 to 100.
This result proposes that in practice, formaldehyde
released is hardly affected by increasing the amount
of sweat on the surface of human skin. In contrast,
1745
180
Methylated DMDHEU
150
pH = 5.0
pH = 8.0
120
Qe(µ gg )
-1
90
60
30
0
0 20 40 60 80 100
Rvm
increasing Rvm level is accompanied by proportionally
increasing Qe value at pH 8. Furthermore, Qe values
with higher Rvm levels (Rvm > 10 for DMDHEU or
Rvm > 50 for methylated DMDHEU) are higher
than the international lower formaldehyde limit
(75–120 mgg1) for the textiles in direct contact with
the skin. This indicates that higher sweat amount may
enhance the formaldehyde release from the fabric when
sweat pH becomes neutral or alkaline with the
increased sweat rate, which may increase the risk of
formaldehyde contact allergy, due to the fact that
sweat of low sweat rates is acid, whereas that of high
sweat rates is basic.36 Besides, it is well recognized that
sweat rate and pH are not uniform over the skin sur-
face. The sweat rate and pH at chest, scapula and lower
back are significantly higher than those at other skin
regions, especially abdomen and upper arm.16 Hence, it
is believed that these skin regions may easily cause for-
maldehyde contact allergy at the same conditions. In
addition, DMDHEU-finished fabric exhibits much
higher Qe value than methylated DMDHEU-finished
fabric at the same Rvm level.
Sweat temperature is greatly determined by skin
temperature. The mean skin temperatures have been
tested to be between 33–38 C.37 To evaluate the effect
of sweat temperature on formaldehyde release, two fin-
ished fabrics described above were employed for releas-
ing formaldehyde into distilled water at different
temperatures for 400 min, and the results are shown
in Table 5.
Table 5 shows that kHB, kHS and Qe values at pH 8
gradually increase with rising temperature from 30 C to
42 C, whereas the three values at pH 5 vary insignifi-
cantly with temperature. These results demonstrate that
1746 Textile Research Journal 86(16)

Table 5. Effect of temperature on kHB, kHS and Qe values at pH 5 and 8

DMDHEU Methylated DMDHEU

Temperature ( C) 30 33 36 42 50 75 100 125

kHB (min0.5) pH ¼ 5 8.190 9.022 10.18 11.19 3.123 3.651 3.988 4.662
pH ¼ 8 21.50 24.73 28.41 32.36 10.19 12.89 14.45 16.03
kHS (min0.5) pH ¼ 5 1.591 1.521 1.047 1.244 1.649 1.799 1.914 2.001
pH ¼ 8 4.707 5.699 5.710 5.789 1.725 2.422 2.787 2.890
Qe(mgg1) pH ¼ 5 86.04 94.45 100.8 105.9 29.01 33.57 39.35 51.64
pH ¼ 8 228.0 260.9 296.5 324.4 98.73 121.9 138.46 153.8
Finishing process: DMDHEU or Methylated DMDHEU: 100 gL1, MgCl26H2O: 18 gL1, Curing: 170 C  1.5 min. Error bars are the standard deviation
of the mean values shown. The values were given as the mean. Standard deviation is less than 5% of the mean value.

Table 6. Effect of DP agent concentration on kHB, kHS and Qe values

DMDHEU (gL1) Methylated DMDHEU (gL1)

DP agents 50 75 100 125 150 50 75 100 125 150

0.5
kHB (min ) pH ¼ 5 5.337 5.813 6.808 8.547 9.993 1.290 2.872 4.425 5.987 6.083
pH ¼ 8 17.95 26.16 41.19 63.75 93.88 9.333 12.09 16.11 20.09 24.92
kHS (min0.5) pH ¼ 5 0.335 0.536 0.690 1.030 1.311 1.234 1.627 1.923 2.298 2.661
pH ¼ 8 3.635 4.147 4.891 6.557 9.380 0.871 1.890 2.706 3.987 5.655
Qe(mgg1) pH ¼ 5 46.65 56.55 68.75 85.00 104.2 11.35 30.64 48.45 60.95 72.07
pH ¼ 8 192.8 261.1 406.6 664.1 908.6 103.97 125.36 167.46 215.57 232.57
The values were given as the mean. Standard deviation is less than 5% of the mean value.

raising temperature can significantly accelerate formal-
dehyde liberating from the fabric at burst release phase.
The reason may be that the release rate of free formal-
dehyde and the hydrolysis of pendant N-CH2OR are
promoted by rising temperature.3 Thus, it is predicted
that relatively higher skin temperature may be benefi-
cial for the transfer of formaldehyde from fabric to skin
surface, thus leading to formaldehyde contact allergy
more easily.
suggesting that higher concentration of DP agent in
the padding bath gives rise to a rapid formaldehyde
release from the finished fabric. This is mainly due to
the increasing amount of free formaldehyde and hydro-
lysable formaldehyde from the high content of the
unreacted DP agent on the finished fabric when larger
dosages of DP agent being applied. The resulting pen-
dant N-CH2OR groups can hydrolyze to produce
formaldehyde.

Catalyst concentration. MgCl2 is the most common Lewis

Effect of finishing process
DP agent concentration. DP agent can crosslink the adja-
cent cellulose chains for improving wrinkle resistance of
cotton fabric. In this work, cotton fabrics were finished
with various amounts of DMDHEU or methylated
DMDHEU and 18 gL1 MgCl26H2O by curing treat-
ment (170 C  1.5 min), and the formaldehyde release
from the obtained finishing fabrics was conducted in
distilled water at 35 C. Their kHB and kHS values
were then determined through the method mentioned
above and shown in Table 6.
Table 6 shows that kHB, kHS and Qe values, espe-
cially at pH 8, gradually increase as concentration of
DP agent increases from 50 gL1 to 150 gL1,
acid catalyst usable for durable press finishing. In
this experiment, the finished fabrics were prepared
with various amounts of MgCl26H2O and 100 gL1
DMDHEU or methylated DMDHEU by curing treat-
ment (170 C  1.5 min), and tested for formaldehyde
release in distilled water at 35 C. Their kHB, kHS and
Qe values were determined and are presented in
Table 7.
Table 7 shows that a higher concentration of catalyst
causes the significant decrease in kHB, kHS and Qe
values, particularly at alkaline medium. Moreover, a
Qe value lower than 150 mgg1 was found when
20 gL1 MgCl26H2O was used, since it can lead to
more intensive linkages of DP agent with cellulose
Li et al. 1747

Table 7. Effect of catalyst concentration on kHB, kHS and Qe values

DMDHEU Methylated DMDHEU

1
Catalyst (gL ) 0.5 5 10 15 20 0.5 5 10 15 20

kHB (min0.5) pH ¼ 5 18.73 15.62 13.27 10.96 3.721 19.04 14.75 13.12 6.026 20.50
pH ¼ 8 122.5 71.73 55.62 35.02 14.63 47.22 35.83 25.94 21.09 13.5
kHS (min0.5) pH ¼ 5 3.752 2.903 2.736 2.382 0.7126 3.893 2.942 2.323 1.059 3.842
pH ¼ 8 21.058 11.704 10.48 7.367 2.363 8.081 6.090 4.988 4.456 2.896
Qe(mgg1) pH ¼ 5 194.0 144.1 138.9 98.69 31.38 179.20 150.2 120.3 57.88 19.08
pH ¼ 8 1254 736.8 547.1 340.8 133.7 459.1 345.8 263.2 210.2 128.4
The values were given as the mean. Standard deviation is less than 5% of the mean value.

Table 8. Effect of curing temperature on kHB, kHS and Qe values

DMDHEU Methylated DMDHEU

Curing temperature ( C) 130 150 170 190 130 150 170 190

kHB (min0.5) pH ¼ 5 18.46 13.63 5.155 3.608 8.422 4.621 3.853 2.721
pH ¼ 8 58.47 31.63 12.63 8.379 20.46 16.72 6.072 4.836
kHS (min0.5) pH ¼ 5 3.950 2.281 0.991 0.754 1.519 0.789 0.731 0.553
pH ¼ 8 13.74 7.471 2.829 1.811 3.835 3.915 1.208 0.941
Qe(mgg1) pH ¼ 5 178.3 129.3 56.09 39.28 87.81 42.11 32.87 21.29
pH ¼ 8 579.2 300.1 110.2 79.21 199.2 167.7 67.34 47.22
The values were given as the mean. Standard deviation is less than 5% of the mean value.

fibers to reduce the unreacted DP agent and pendant N-
methylol groups, thus inhibiting the formation of
hydrolysable formaldehyde.
Curing temperature. Cotton fabrics padded with
100 gL1 DMDHDU or methylated DMDHEU and
18 gL1MgCl26H2O were cured at different tempera-
tures for 1.5 min. Formaldehyde release of the finished
fabric in distilled water was then performed and their
kHB, kHS and Qe values are given in Table 8.
Table 8 shows that kHB, kHS and Qe values of the
finished fabrics decreased with elevation of curing tem-
perature. This result demonstrates that a higher curing
temperature is able to enhance the degree of linkage
between DP agent and cotton fiber, therefore resulting
in a reduced release of hydrolysable formaldehyde.
However, the free formaldehyde is the most independ-
ent upon curing temperature.
Softeners. Use of a softener in the durable press formu-
lation partially overcomes the loss of strength, stiffness
and resistance to abrasion of the finished fabric owing
to crosslinking of DP agent.38 In this work, three com-
mercial softeners including silicone softener AMS,
polyurethane softener DPU and polyethylene softener
PEN were selected to prepare three different
DMDHEU-finished cotton fabrics. Meanwhile, the fin-
ished cotton fabric was also prepared as a control
sample without softener using the same method. They
were then investigated for formaldehyde release. The
contact angle of a water droplet on the finished fabric
surface was measured using a liquid-solid contact angle
analyzer (DSA100; Krüss, Germany) equipped with a
high-speed camera and calculated by Tangent method 2.
The experimental results were presented in Table 9.
It can be seen from Table 9 that kHB, kHS and Qe
values of the finished fabrics with softener are higher
than those of control sample at the same conditions,
indicating that the addition of softener can enhance the
release rate of formaldehyde from the fabrics. This is
because formation of the softener film on the fabric
surface during cure treatment may block the crosslink
of DP agent with cotton fiber to increase the amount of
the unreacted DMDHEU or methylated DMDUEU
and pendant N-methylol groups, which can generate
the hydrolysable formaldehyde. On the other hand, it
is worth noticing that the film formed with softeners,
particular in silicone softener AMS can significantly
improve the surface hydrophilicity of the finished
cotton fabric. As seen in Table 9, according to their
water contact angle, four samples were ranked in this
order: AMS > DPU > PEN > Control. This indicated
1748 Textile Research Journal 86(16)

Table 9. kHB, kHS and Qe values and water contact angles of the finished fabrics with different softeners

DMDUEU Methylated DMDHEU

DP agents Softeners Control AMS DPU PEN Control AMS DPU PEN

kHB (min1) pH ¼ 5 7.673 9.393 11.98 14.71 4.532 6.342 8.391 10.02
pH ¼ 8 22.50 50.18 58.04 76.55 15.98 20.39 27.01 30.63
kHS (min1) pH ¼ 5 1.898 2.048 3.099 3.238 1.423 1.966 2.766 2.904
pH ¼ 8 6.503 7.587 8.903 11.38 2.391 2.502 3.541 4.223
Qe(mgg1) pH ¼ 5 75.48 95.35 111.1 135.1 42.88 69.54 80.37 101.5
pH ¼ 8 217.0 496.3 573.8 771.8 159.74 198.43 274.8 298.51
Water contact angle (O) 10.3 135.1 47.3 37.5 10.1 142.8 51.2 41.6
Finishing process: DP agent: 100 gL1, MgCl26H2O: 18 gL1, softener: 30 gL1, Curing: 170 C  1.5 min. The values were given as the mean. Standard
deviation is less than 5% of the mean value.

that the hydrophilicity is the lowest for Control, follow
by DPU and PEN, and the highest for AMS. As a
result of increasing hydrophilicity, the water wetting
and diffusion on the finished fabric are hindered;
hence this limits the production of hydrolysable formal-
dehyde and free formaldehyde moving from the fin-
ished fabric to water. Specially, the water contact
angle of the finished fabric with AMS is 135.3–142.8o,
much higher than those of the finished fabric with the
other softeners. Thus, it has a stronger limiting effect on
formaldehyde release than the other softeners under the
same conditions. The reason is that the Si-H group of
silicon polymer hydrolyzes to the silanol and condenses
to a three-dimensional resinous film, making the fabric
highly water repellent.38 Consequently, the presence of
softener in the durable press formulation obtains better
performance of the finished fabric, but promotes for-
maldehyde release at the same time.
Conclusions
The release process of formaldehyde from the finished
cotton fabrics with DMDHEU-based DP agents
included two stages, namely the burst release phase
and the slow release phase, which is explained by
five different sources. Formaldehyde has a higher
release rate at the burst phase than the slow phase
from the fabrics under the same conditions. More
importantly, the formaldehyde release mechanism fol-
lowed Fickian mode, and described using three differ-
ent kinetic equations including Higuchi, Double
phases and Korsmeyer–Peppas models, respectively.
Higher formaldehyde release was found in alkaline
medium than in acid medium. Formaldehyde showed
a lower release rate in synthetic sweat solution than
that in water under the same conditions due possibly
to the reaction of L-histidine with formaldehyde.
Although the methylated DMDHEU finished fabric
has the similar formaldehyde release mechanism to
the DMDHEU finished fabric, its release rate and
quantity at equilibrium are much less than those of
the latter under the same condition. The formaldehyde
release quantity of two finished fabrics in alkaline
synthetic sweat exceeds the lower limit for causing
the formaldehyde contact allergy, therefore the two
DP agents, especially DMDHEU should be limited
for the treatment of cotton fabric. Increasing water
volume or temperature enhanced the formaldehyde
release, suggesting that high sweat rate and skin tem-
perature may accelerate the formaldehyde release,
thus increasing the risk of ACD from formaldehyde
in textiles. Furthermore, formaldehyde release is sig-
nificantly affected by DP finishing process. Higher
concentration of DP agent and the addition of soft-
ener enhance the formaldehyde release. On the con-
trary, increasing catalyst concentration and curing
temperature can reduce the formaldehyde release.
Therefore, the formaldehyde release can be effectively
reduced by optimizing the DP finishing process of
cotton fabrics, possibly eliciting ACD in patients aller-
gic to formaldehyde under real wearing conditions.
Acknowledgement
The authors thank the Tianjin Municipal Science and
Technology Committee for a Research Program of
Application Foundation and Advanced Technology
(11JCZDJC24600).
Declaration of conflicting interests
The authors declared no potential conflicts of interest with
respect to the research, authorship, and/or publication of this
article.
Funding
The authors disclosed receipt of the following financial sup-
port for the research, authorship, and/or publication of this
article: This work was supported by the Natural Science
Foundation of China (grant number 20773093).
Li et al.
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