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Abstract
As the use of fabrics containing spandex for apparel applications is expanding, developing eco-friendly technologies to
recycle the industrial as well as post-consumer waste for spandex blended fabrics becomes increasingly important. As is
known in the industry and demonstrated in this study, spandex may be removed from blended fabrics by dissolving it in
solvents such as N,N-dimethylformamide, but the use of such solvents is undesirable for economical and environmental
reasons. The main focus of this study was to develop an alternative process for removing the spandex component in a
nylon/spandex blended fabric (NSBF) by selective degradation so that the nylon component can be recovered for
recycling. In this process, the fabric first underwent a heat treatment step, followed by a washing process. For the
heat treatment, the effect of temperature, water-to-fabric ratio, and pressure were studied. Treatment at 220 C for
2 hours under atmospheric pressure was found to be very effective, allowing the degraded spandex residues to be readily
washed off in ethanol, while the nylon component retained its original morphology. With the removal of spandex in
NSBF, a decrease in -CON- absorption peaks in the Fourier transform infraredattenuated total reflectance spectra of
the fabrics was observed.
Keywords
Waste recycling, selective degradation, blended fabrics, spandex, nylon 6
1
School of Materials Science & Engineering, Georgia Institute of
Technology, USA
2
Key Laboratory of Eco-Textile, Ministry of Education, School of Textiles
and Clothing, Jiangnan University, China
Corresponding author:
Youjiang Wang, Georgia Institute of Technology, 801 Ferst Drive, Atlanta,
GA 30332, USA.
Email: youjiang.wang@mse.gatech.edu
Yin et al.
the waste disposal problem for the garment manufacturing process as well as post-consumer textiles needs
to be addressed. Nylon in a nylon/spandex blended
fabric (NSBF) represents the main component,
whereas spandex represents a small portion in
NSBF. It is therefore logical to focus on the recovery
of nylon from NSBF waste so as the recovered nylon
can be processed into engineered plastics by melt processing or into virgin-quality monomers by depolymerization, if nylon can be recovered from the
waste steam with reasonable purity. Currently, there
is no suitable technology to recycle NSBF waste
other than by solvent extraction using, for example,
N,N-dimethylformamide (DMF). Although solvent
extraction of spandex from NSBFs with DMF or
N,N-dimethylacetamide (DMA) is technically feasible,
environmental and economic concerns limit its use in
commercial applications.
The spandex ber is usually produced by the dry
spinning process, in which the polymers are prepared
via polytetramethylene glycol (PTMG) with -CONend-groups reacting with diamine in DMF or DMA.9
Spandex is a polyurethanepolyurea copolymer,8,10,11
in which the polyurea component synthesized from diisocyanate and diamine contains a urea linkage that is
easier to depolymerize than the amino linkage in nylon
by hydrolytic actions.1214 Therefore, in this study the
main focus is to nd conditions that selectively degrade
spandex by hydrolysis without signicantly aecting
the nylon component. A reaction chamber capable of
heating water to 250 C was used for the heat treatment
of NSBF, and the process variables studied included
temperature, water-to-fabric ratio (WFR), and pressure. After the heat treatment, the treated fabrics
were washed with solvents such as water, ethanol, and
acetone. Direct solvent extraction of spandex from
NSBF was also carried out to determine the mass
ratio of spandex as well as to demonstrate its feasibility
for recycling NSBF.
17
Experimental details
Materials
NSBF (223.8 g/m2, knitted, brown), nylon 6 (polyamide 6) ber and spandex ber obtained from
Aqual USA, Inc., were used in this experiment.
Ethanol, acetone, and DMF were analytical reagent
grade and supplied by Sigma-Aldrich Co. LLC.
Heat treatment
A pressure vessel is needed in order to heat liquid water
to a temperature range of 200250 C. In this study, a
simple pressure vessel was constructed to be used with a
4-ton press, as illustrated in Figure 1. The press controlled the heating prole of the test vessel, which had a
cavity of 10 cc. NSBF and ber samples were washed
with deionized water, and then dried in a vacuum dryer
at 60 C for 24 h to allow for accurate measurement of
sample weights. The stainless steel reaction chamber
was rst heated to the preset temperature, and then
the pre-washed fabric sample was placed in the reaction
chamber with predetermined amount of deionized
water. The WFR varied from 0 to 4, and the test chamber was either closed or open during the heat treatment,
as follows.
1. WFR 4: the chamber was lled with water after
placing the samples inside to obtain an approximate
18
WFR of 4:1. The valve was closed during heat treatment to allow internal pressure to build up as the
vessel was heated.
2. WFR 1: 2 g of water was added to the chamber
after placing a 2 g fabric sample inside, and the
valve was closed during heat treatment.
3. WFR 0 (Closed): no water was added to the chamber after placing the samples inside, and the valve
was closed during heat treatment.
4. WFR 0 (Open): no water was added to the chamber after placing the samples inside, and the valve
was kept open during heat treatment, at atmospheric
pressure.
After a series of extensive trials with dierent temperatures and time durations, a temperature range of 180
230 C was selected in this study, and the treatment
duration was kept at 2 h, which included time needed
to bring the test vessel to the desired temperature.
Figure 2 shows the internal pressure prole during the
test when no water was added and the chamber was
closed. The internal pressure directly correlated with
the actual temperature inside the chamber. For an
ideal gas in an enclosed chamber, the pressure is related
to the temperature change by the ideal gas law. Starting
from room temperature (T1) and atmospheric pressure
(P1), the internal pressure P2, measured by gage pressure, should increase with the internal temperature T2
as follows:
P2 P1 T2 =T1 1
Characterization
The treated ber and fabric samples after washing
and drying were analyzed for weight loss and
change in appearance using an optical microscope.
A Thermo Nicolet Nexus Fourier transform infraredattenuated total reectance (FTIR-ATR) spectrophotometer
(Thermo
Electron
Co.,
MA,
USA) equipped with an OMNI-Sampler was used
to study the chemical structure of the ber and
fabric samples.
Figure 2. Internal pressure of the sealed reaction chamber versus time, WFR 0 (Closed).
Yin et al.
19
Weight loss
Observation
Nylon
Spandex
NSBF
0.22%
100%
23.86%
No change in appearance
Spandex was completely dissolved
The elasticity of the treated fabric
decreased significantly
Figure 3. Appearances of nylon/spandex blended fabric after heat treatment at 220 C for 2 h under the four conditions:
(a) WFR 4; (b) WFR 1; (c) WFR 0 (Closed); and (d) WFR 0 (Open).
20
Figure 4. Weight losses of fabrics after heat treatment under the four conditions.
fabric structure, but adsorbed or adhered to the surface of nylon bers. Three solvents (water, ethanol,
and acetone) were used to remove the spandex residue by a washing process, and the amount of weight
reduction after washing is reported in Figure 5.
Water appeared to be an ineective solvent to
remove the spandex residual, and the weight losses
were lower than 8% for samples treated under all
the four conditions. This was likely because most of
the spandex residue was insoluble in water after the
heat treatment.
Yin et al.
When ethanol and acetone were used for washing,
the weight loss for samples heat treated with liquid
water (WFR 1 and 4) was lower than that for samples
treated without liquid water (WFR 0; Closed or
Open). There were two main reasons for the lower
mass loss after washing for the liquid water treated
samples. Firstly, some of the degraded spandex residue
was already removed by the liquid, which was reected
by the 56% weight loss after the heat treatment.
Secondly, due to the disintegration of the fabric structure, the fabric became clumps, causing some degraded
spandex residue to be trapped inside the clump, making
it dicult to wash away. It was therefore concluded
that heat treatment conditions with liquid water
(WFR 1 and 4) were not as eective as those without
liquid water.
Comparing the weight losses after washing in acetone and ethanol (Figure 5), the two solvents showed
nearly identical results for samples treated without
liquid water, all about 22%. Based on the content
of spandex in the NSBF (about 23.86%; Table 1)
and a weight loss of 1.31.8% after the heat treatment (Figure 4), these results show that the spandex
component was essentially fully removed by heat
treatment without liquid water followed by washing
with ethanol or acetone. For economical and environmental reasons, ethanol was clearly the preferred
choice. For eectiveness, simplicity, and lower operating cost, heat treatment at atmospheric pressure
(Open condition) was found to be a desirable processing method. Therefore, further studies were only
carried out at atmospheric pressure and using ethanol
as the washing solvent.
21
In order to analyze the changes of the appearances
of nylon and spandex bers in detail, these bers were
treated at 220 C for 2 h. From Figure 7(a) and (c), the
appearances of nylon bers before and after the
treatment were identical. However, the spandex bers
changed signicantly after the treatment (Figure 7(b)
and (d)). The spandex had degraded into a wax-like
short-chain spandex residue, and this made it easily
removed from the remaining nylon structure of the
fabric.
22
Figure 6. Photographs of nylon/spandex blended fabric samples heat treated for 2 h at atmospheric pressure and different temperatures: (a) before treatment; (b) 180 C; (c) 190 C; (d) 200 C; (e) 210 C; (f) 220 C; and (g) 230 C.
fabric (Figure 10(e)). When the treatment temperature was increased to 230 C, many fragmented
nylon ber ends could be seen (Figure 10(f)). The degradation of nylon ber is undesirable, as it interferes with full removal of spandex residue, makes it
dicult to handle in recycling the nylon component,
and makes the nylon unsuitable for further melt
processing.
Yin et al.
23
Figure 7. Appearances of nylon and spandex fibers: (a) nylon and (b) spandex before treatment; (c) nylon and (d) spandex after
treatment at 220 C for 2 h at atmospheric pressure.
Figure 8. Weight losses after washing in ethanol at 60 C for 30 min for nylon/spandex blended fabric samples treated at different
temperatures.
24
Figure 9. Photographs of nylon/spandex blended fabric samples heat treated for 2 h at atmospheric pressure and different temperatures and washed with ethanol: (a) before treatment; (b) 180 C; (c) 190 C; (d) 200 C; (e) 210 C; (f) 220 C; and (g) 230 C.
The FTIR-ATR spectra of the original NSBF presented strong absorption peaks at 1650 and 1720 cm1
(Figure 12, curve a), corresponding to the -CONgroup, which was part of the urethane and urea linkages in spandex and the amide linkage in nylon. After
NSBF was heat treated at 220 C for 2 h, the absorption
peaks of -CON- of the sample decreased in intensity,
and this was likely caused by damages to the amino
group in spandex molecules as they were degraded
into oligomers. The weakened absorption peaks of
Yin et al.
25
Figure 10. Photographs of nylon/spandex blended fabric fragments (magnification 50) heat treated for 2 h at atmospheric pressure
and different temperatures and washed with ethanol: (a) 180 C; (b) 190 C; (c) 200 C; (d) 210 C; (e) 220 C; and (f) 230 C.
Figure 11. Fourier transform infraredattenuated total reflectance spectra of nylon fiber.
26
Figure 12. Fourier transform infraredattenuated total reflectance spectra of nylon/spandex blended fabric samples.
Conclusions
Eective and environmentally friendly methods to
remove the spandex component in a NSBF were studied to enable the recovery of nearly pure nylon for
further processing. The study showed that spandex separation via selective degradation was a promising route,
which involved heat treatment of the fabric followed by
a washing process. The samples were examined by
weight loss analysis comparing with the spandex content in the blended fabric, appearance analysis using an
optical microscope, and FTIR spectra analysis.
For the heat treatment, the eect of temperature,
WFR, and pressure were studied. The presence of
liquid water in a sealed chamber for the heat treatment
at elevated temperatures disintegrated the fabric structure and made removal of spandex dicult. Heat treatments in a sealed chamber and in an open chamber
yielded similar results in spandex degradation when
no liquid water was added to the chamber in the process. Without added liquid water, heat treatment at a
temperature of 220 C, just below the nominal melting
temperature of nylon 6, was found to have little eect
on the nylon ber but was eective to cause sucient
spandex degradation for the spandex residue to be
readily washed o. Removing the degraded spandex
residue after heat treatment was accomplished by a
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