Waste Management 97 (2019) 88–96

Contents lists available at ScienceDirect

Waste Management
journal homepage: www.elsevier.com/locate/wasman

Upcycling of cotton polyester blended textile waste to new man-made

cellulose fibers
Simone Haslinger a, Michael Hummel a, Adina Anghelescu-Hakala b, Marjo Määttänen b, Herbert Sixta a,⇑
a
Department of Bioproducts and Biosystems, Aalto University, Espoo, P.O. Box 16300, FI-00076 Aalto, Finland
b
VTT Technical Research Centre of Finland Ltd, Espoo, P.O. Box 1000, FI-02044 VTT, Finland

a r t i c l e i n f o a b s t r a c t

Article history: The creation of a circular economy for cellulose based textile waste is supported by the development of
Received 13 February 2019 an upcycling method for cotton polyester blended waste garments. We present a separation procedure
Revised 31 May 2019 for cotton and polyester using [DBNH] [OAc], a superbase based ionic liquid, which allows the selective
Accepted 30 July 2019
dissolution of the cellulose component. After the removal of PET, the resulting solution could be
Available online 5 August 2019
employed to dry-jet wet spin textile grade cellulose fibers down to the microfiber range (0.75–2.95 dtex)
with breaking tenacities (27–48 cN/tex) and elongations (7–9%) comparable to commercial Lyocell fibers
Keywords:
made from high-purity dissolving pulp. The treatment time in [DBNH] [OAc] was found to reduce the ten-
Dry-jet wet spinning
Ioncell
sile properties (<52%) and the molar mass distribution (<51%) of PET under certain processing conditions.
Ionic liquid Ó 2019 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND
Polyethylene terephthalate license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
Textile recycling
Cellulose PET separation

1. Introduction hydrolysis of cotton employing hydrochloric acid to generate a

microcrystalline cellulose powder, which can be separated from
Ever since fast fashion has attempted to satisfy the demands of a the remaining polyester fabric. The recovered polyester is
rapidly growing population (Hämmerle, 2011), the global waste pol- re-spun to PET yarns that can then be used to manufacture new
lution has increased tremendously. Europe disposes 75% (4.3 million textiles (Sun et al., 2018a, 2018b).
tons) of textiles waste annually due to the absence of viable recy- Less destructive methods utilize ionic liquids (ILs) or NMMO to
cling strategies. (Briga-Sá et al., 2013) Interwoven cotton polyester dissolve the cotton component. Negulescu et al. prepared a 1–2%
blends represent one of the most prominent mixtures on the market, cellulose solution from cotton polyester blends, and removed the
which are difficult to recycle because of their heterogeneity. Con- polyester residue by filtration. Afterwards, the cellulose solution
ventional fiber spinning processes can partly reuse pure cellulose was further concentrated up to 15–17% using cotton material from
waste (Shen and Patel, 2010), but they are unable to handle blended an alternative feedstock (Negulescu et al., 1998). A recent patent
waste garments. Therefore, the recycling of cotton polyester blends further elaborates this approach. An amine oxide solvent such as
has yet demanded either the depolymerization or dissolution of NMMO is supposed to dissolve the cellulose component of various
either component. The dissolution of polyester usually involves blended textile products to yield cellulose solutions of up to 35%
toxic solvents and elevated temperatures (DMSO), which can influ- (Brinks et al., 2013). Similarly, 1-allyl-3-methylimidazolium
ence the properties of the cellulose component (Serad, 1993). chloride ([AMIM] [Cl]) and 1-butyl-3-methylimidazolium acetate
Accordingly, polyester is preferably subjected to alcoholysis, hydrol- ([BMIM] [OAc]) have been described to foster the recycling of
ysis, or glycolysis reactions (Barot and Sinha, 2015; Oakley et al., blended textile waste. The process steps are comparable to NMMO.
1992; Palme et al., 2017; Shen et al., 2013). The ionic liquid dissolves the cellulose component, while filtration
Similar approaches have also been used to degrade cellulose removes the polyester residue, and subsequent coagulation recov-
under acidic conditions (Cowan, 1981; Gruntfest and Turner, ers the cellulose (de Silva et al., 2014). Although both NMMO and IL
1974; Ouchi et al., 2010; Shen et al., 2013). An example is the based approaches highlight the potential of the generated cellulose
solutions to be used in a film or fiber spinning process, neither of
⇑ Corresponding author at: Vuorimiehentie 1, 02150 Espoo, Finland. them provides any relevant data that could serve as a proof of
E-mail addresses: [email protected] (S. Haslinger), michael.hummel@ concept.
aalto.fi (M. Hummel), [email protected] (A. Anghelescu-Hakala),
[email protected] (M. Määttänen), [email protected] (H. Sixta).

https://doi.org/10.1016/j.wasman.2019.07.040
0956-053X/Ó 2019 The Author(s). Published by Elsevier Ltd.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
 S. Haslinger et al. / Waste Management 97 (2019) 88–96 89

List of acronyms

[AMIM] [Cl] 1-allyl-3-methylimidazolium chloride IL ionic liquid

[BMIM] [OAc] 1-butyl-3-methylimidazolium acetate LiCl lithium chloride
[DBNH] [OAc] 1,5-diazabicyclo[4.3.0]non-5-enium acetate MMCFs man-made cellulose fibers
[M1] modified separation experiment 1 using [DBNH] [OAc] MMD molar mass distribution
with excess HOAc Mn number average molar mass, Da
[M2] modified separation experiment 2 using 2 separation Mw mass average molar mass, Da
experiments to increase the cellulose concentration ƞ0* zero shear viscosity, Pa s
[R] raw-material/reference N2 nitrogen
[S1] separation experiment 1 with 1 washing step NMMO N-methylmorpholine N-oxide
[S2] separation experiment 2 with 2 washing steps NMR nuclear magnetic resonance
A acid washing N* complex viscosity, Pa s
COP crossover point PDI polydispersity index
CP-MAS cross-polarized magnetic angle spinning PET polyethylene terephthalate
DBN 1,5-diazobicyclo(4.3.0)non-5-ene RI refractive index
DMAc N,N-dimethyl acetamide SEM scanning electron microscopy
DMSO dimethyl sulfoxide TGA’ thermogravimetric analysis
DP degree of polymerization vextr. extrusion velocity of the dope, cm3 min
1
DR draw ratio vtake-up take-up velocity of the godet rollers to collect the fibers,
Ew alkaline washing m min
1
ftotal total orientation Z ozone pretreatment
G’ storage modulus, Pa Dn birefringence value
G’’ loss modulus, Pa x angular frequency, s
1
GPC gel permeation chromatography
HFIP 1,1,1,3,3,3-hexafluoro-2-propanol
HOAc acetic acid

It is evident that there is a strong need to further develop 2. Materials and methods
recycling strategies for textile industry. A viable, ecofriendly
concept for circular economy should allow quantitative and 2.1. Synthesis of [DBNH] [OAc]
‘‘green” recycling of all material components without the gener-
ation of additional waste streams, or an increase in energy con- The synthesis of [DBNH] [OAc] is a neutralization reaction of an
sumption resulting from complex processing steps. In many equimolar amount of 1,5-diazabicyclo(4.3.0)non-5-ene (DBN) and
cases, the approaches discussed so far involve the degradation glacial acetic acid. During the addition of acetic acid, permanent
of either cotton or polyester, and therefore impede the simulta- cooling is necessary because of the exothermic nature of the reac-
neous upcycling of both components within one process. Even tion. The resulting ionic liquid shows a melting point close to 65 °C
more significantly, however, they fail to show the conversion and therefore requires stirring at elevated temperatures (80 °C,
of textile waste to new-value added products, i.e. to employ tex- 1 h) in order to ensure a complete conversion.
tile waste as a feedstock to spin new man-made cellulose fibers
(MMCFs). 2.2. Cotton polyester blend
In previous studies, we demonstrated the usage of [DBNH]
[OAc] to convert cellulose based waste material such as cotton, The cotton polyester blend was supplied by SOEX (Germany)
cardboard, and paper to new high-tenacity Ioncell fibers (Asaadi consisting of white postconsumer textiles, which were shredded
et al., 2016; Ma et al., 2018; Ma et al., 2016). [DBNH] [OAc] does and blended to obtain a mixture with an overall concentration of
not require the addition of any stabilizers and allows to adjust 50 wt% cotton and 50 wt% polyester. The sample was pretreated
the process conditions at temperatures 30 °C lower than for spin- by VTT (Finland) using an ozone based sequence Ew-disk
ning solutions prepared from NMMO. In a current patent, we have refining-Z-P-A. The target of the alkaline washing stage (Ew) was
also been able to show that this solvent enables the selective dis- to remove silicate, whereas ozone (Z) and hydrogen peroxide (P)
solution of cellulose in cotton polyester blends without any severe were used to both adjust the viscosity (DP) and to bleach the mate-
degradation of polyester, if adequate process conditions are rial. Acid washing (A) aimed to decrease the metal content. Disk
applied (Haslinger et al., 2017). Utilizing this concept, the research refining targeted to homogenize the sample mixture and to
disclosed herein aims to foster the creation of a circular economy improve the reactivity for the following pretreatment and dissolu-
for textile industry by transforming blended cellulosic waste mate- tion stages. The molar mass distributions (MMD) of both cellulose
rial to new textile grade MMCFs. After filtration, the resulting cel- and the polyester fractions were determined by size exclusion
lulose solution could thus be used directly as a spinning dope for chromatography, respectively, as described below. All samples
dry-jet wet spinning (Michud et al., 2015b; Parviainen et al., were further disintegrated by the means of a Wiley Mill.
2015; Sixta et al., 2015; Stepan et al., 2016) to obtain Lyocell-
type fibers ranging from 0.7 to 3.0 dtex. The degradation of the
2.3. Molecular mass distribution (MMD) and intrinsic viscosity of
recovered PET was studied dependent on treatment time and tem-
cellulose
perature. A detailed analysis on the further recyclability of PET
such as in melt spinning was however beyond the scope of this
The MMD of the raw material and the spun fibers was deter-
study.
mined by gel permeation chromatography (GPC) using a 5 column
90 S. Haslinger et al. / Waste Management 97 (2019) 88–96

set up with one precolumn (PLgel Mixed-A, 7.5  50 mm) and four (1 mm gap size, 25 mm plate diameter). Initial dynamic strain
analytical columns (4  PLgel Mixed-A, 7.5  300 mm) equipped sweep tests were performed to define the linear-viscoelastic
with an RI-detector (Shodex RI-101). The samples were dissolved domain. A strain of 0.5% was chosen for the following frequency
in a 90 g l
1 LiCl/N,N-dimethylacetamide (DMAc) solution and tests. All samples were subjected to a dynamic frequency sweep
diluted with pure DMAc in order to obtain a sample concentration over an angular frequency (x) range of 0.01–100 s
1 at relevant
of 1 mg ml
1 in 9 g l
1 LiCl/DMAc. 100 ml of the respective solution temperatures (40–100 °C). The complex viscosity (N*) and dynamic
were injected at a flow rate of 0.750 ml min
1 (9 g l
1 LiCl/DMAc moduli (G0 , G00 ) were recorded as a function of the shear rate. The
eluent) at 25 °C. The calibration was conducted with pullulan stan- zero shear viscosity (ƞ0*) was calculated using the cross model
dards (Mw: 343–708,000 Da) based on a direct-standard- assuming that the Cox-Merz rule was valid (Sammons et al.,
calibration model, in which the molar mass distribution was 2008). The cross over points of storage and loss moduli were also
corrected according to the molar masses of cellulose equivalent determined.
pullulan standards (Berggren et al., 2003; Borrega et al., 2013;
Michud et al., 2015a). 2.7. Fiber properties and total orientation
The limiting viscosity of the raw material before and after its
pretreatment was determined according to the SCAN-CM 15:88 Linear density (dtex), elongation at break (%), and tenacity (cN
standard for viscosity in cupri-ethylenediamine solution. dtex
1) of all spun fibers and of 3.3 dtex PET filaments were mea-
sured by a Vibroskop and Vibrodyn 400 set up (Lenzing Instru-
2.4. Selective dissolution of cotton and recovered PET ment, Austria) according to DIN 53816 standard (20 mm gauge
length, 5.9 ± 1.2 mN/tex pretension, 20 mm/min test speed). The
The cotton polyester blend was mixed with [DBNH] [OAc] (1 h, samples were conditioned prior to the measurement (20 °C, 65%
80 °C) using a vertical kneader system (cf. experiments [S1], [S2], humidity) and were tested in both dry and wet state (fiber count:
and [M2] in Table 1) to yield a cellulose solution of 6.5 w%. For 10). The young modulus (GPa) was calculated from the slope of the
[M1], [DBNH] [OAc] was prepared with an excess amount of HOAc average stress strain curve based on the ASTM standard D2256/
in a ratio of 1:1.3 to reduce the degradation of PET. Subsequently, D2256.
the undissolved polyester fraction was separated from the cellu- The total orientation of the spun fibers was determined by a
lose solution via hydraulic pressure filtration (70 °C, 1–8 MPa, polarized light microscope (Zeiss Axio Scope) with a 5k Berek com-
metal filter mesh with 5–6 mm absolute fineness, Gebr. Kufferath pensator. The birefringence (Dn) was calculated from the retarda-
AG, Germany). In experiment [M2], the filtered solution was trans- tion of the polarized light divided by the fiber thickness assuming a
ferred back to the kneader system and mixed with an additional density of 1.5 g cm
3 for cellulose. In order to obtain the total ori-
amount of the cotton polyester blend (1 h, 80 °C) to obtain a final entation factor ft, Dn was divided by the maximum birefringence
cellulose concentration of 10.5 wt% after filtration. Whereas the value (0.062) of cellulose (Adusumalli et al., 2009).
resulting cellulose solutions could be subjected to dry-jet wet spin-
ning directly after solidification (storage at 8 °C for a couple of 2.8. Scanning electron microscopy (SEM)
days), the recovered polyester fibers required further purification
as they were still contaminated with residual cellulose. Therefore, The cross sections of the spun fibers were observed on a Zeiss
the polyester residue was extracted with fresh ionic liquid (1 h, Sigma VP, Zeiss FE-SEM. An acceleration voltage of 1.5 kV was used
80 °C, vertical kneader). Afterwards, the solvent was removed by and all samples were sputter coated with Au prior to the
filtration and subsequent washing with deionized water. This step measurement.
was repeated for experiments [S2], [M1], and [M2].
2.9. Degradation experiments of PET filaments
2.5. Dry-jet wet spinning
Virgin 3.3 dtex PET filaments (Swerea IVF, Sweden) were trea-
The solidified cellulose solution was placed into a customized ted with [DBNH] [OAc] (6 wt% PET, 0.5–4 h, 80 °C) under perma-
laboratory dry-jet wet piston spinning unit (Fourné Polymertech- nent stirring. Afterwards, the filaments were rinsed with
nik, Germany) and heated up according to its rheological proper- deionized water and their tensile strength was determined as
ties. The melted spin dope was extruded through a multi hole described in the cellulose section above.
spinneret (36 holes, 0.1 mm diameter, 0.02 mm capillary length)
with a constant extrusion velocity of 1.6 cm3 min
1. The resulting 2.10. Gel permeation chromatography of PET
filaments were stretched in an 1 cm air gap by varying
take up velocities to achieve draw ratios (DR) between 1–8.8 The molar mass distribution (MMD) of polyester was deter-
(DR = vtake-up/vextr) and coagulated in a water bath (10 °C). mined by gel permeation chromatography (VTT, Finland) using a
3 column setup with one precolumn (Styragel WATT054405) and
2.6. Rheology of the spinning solution two analytical columns (Styragel HR 4E 7.8  300 mm and Styragel
HR5 7.8  300 mm) equipped with a RI-detector (40 °C). The anal-
The shear rheology of all spinning dopes was analyzed with an ysis was conducted with an 1,1,1,3,3,3-hexafluoro-2-propanol
Anton Paar MCR 300 rheometer with a plate and plate geometry (HFIP)/5mM salt (sodium trifluoroacetate) eluent at a flow rate of

Table 1
Experimental design. Summary of the conducted experiments describing the total concentration of cotton and polyester (CO/PET) before separation, the resulting cellulose
concentration (Cellulose) in the spinning dope, the solvent used, and the washing steps employed for the polyester residue.

Exp. CO/PET (wt%) Cellulose (wt%) Solvent Washing of PET

[S1] 13 6.5 [DBNH] [OAc] 1x [DBNH] [OAc]
[S2] 13 6.5 [DBNH] [OAc] 2x [DBNH] [OAc]
[M1] 13 6.5 [DBNH] [OAc] + HOAc (molar ratio: 1:1.3) 2x [DBNH] [OAc] +HOAc (molar ratio: 1:1.3)
[M2] 21 10.5 [DBNH] [OAc] 2x [DBNH] [OAc]
 S. Haslinger et al. / Waste Management 97 (2019) 88–96 91

0.5 ml/min. The system was calibrated with polymethyl methacry- Table 2
late standards. GPC of PET. Number average molar mass Mn, mass average molar mass Mw, and
polydispersity index (PDI = Mw/Mn) of polyethylene terephthalate before the pre-
treatment, and after every pretreatment step.
13
2.11. C CP-MAS NMR
Mn (kDa) Mw (kDa) PDI
PET before treatment 9.8 ± 0.3 21.4 ± 0.2 2.1 ± 0.2
The concentration of the residual cellulose in the recovered
PET after alkali (E) 9.8 ± 0.3 22.4 ± 0.2 2.3 ± 0.2
polyester fraction was estimated by 13C CP-MAS NMR. All samples PET after disk refining 10.1 ± 0.3 22.5 ± 0.2 2.2 ± 0.2
were analyzed on a Bruker AVANCE III spectrometer with a probe PET after ozone (Z) 9.4 ± 0.3 21.8 ± 0.2 2.3 ± 0.2
size of 4 mm employing an UltraShield Plus 400 MHz magnet run- PET after peroxide (P) 9.3 ± 0.3 21.6 ± 0.2 2.3 ± 0.2
ning at 100.6 MHz. The spectra were recorded at a spinning speed PET after acid (A) 9.5 ± 0.3 21.6 ± 0.2 2.3 ± 0.2

of 8 kHz using a relaxation delay of 5 s and a CP contact time of

2 ms. 8000 scans with an acquisition time of 34 ms were mea-
sured. During contact time, a variable crosspolarization increasing
from 50% to a maximum amplitude of 85 kHz was used. A SPINAL- last pretreatment step with 21.6 kDa and 9.5 kDa, respectively.
64 1H decoupling aimed to decouple the protons during The PDI changed from 2.1 to 2.3 implying a slight broadening of
acquisition. the molar mass distribution. These alterations reflect the overall
A sigmoidal calibration model was employed to quantify the heterogeneity of the waste material, rather than a significant trend,
cellulose content in the polyester residue. The ratios of the peak indicating a negligible impact of the pretreatment of cellulose on
areas of C1 (cellulose) and C1-8 as well as C2-3-4-5-6 (polyester) the properties of PET.
were plotted as a function of the cellulose concentration
(Haslinger et al., 2019). 3.2. Dissolution of cellulose and fiber spinning

Under standardized conditions, 13–15 wt% of cellulose is dis-

2.12. Thermogravimetric analysis (TGA)
solved in [DBNH] [OAc] at 80 °C resulting in a highly viscous spin-
ning dope. Even when prepared from pure cellulose streams, the
The TGAs were performed on a TA Instruments Q500 in a tem-
solutions need to be filtered prior to their spinning due to certain
perature range of 25–800 °C with a heating rate of 10 °C/min under
impurities and undissolved residues. The filtration is demanding
a N2 atmosphere. 5–10 g of sample were used per measurement.
and usually requires special equipment (i.e. hydraulic press filtra-
tion units) to facilitate the purification of a solution in a highly vis-
3. Results and discussion cous state (Asaadi et al., 2016; Ma et al., 2018, 2016; Michud et al.,
2015b). These challenges increase in case of multicomponent
3.1. Cotton polyester based textile waste as a raw-material materials, such as cotton polyester blends, and therefore demand
adjusted processing conditions.
In previous studies, we were able to demonstrate the conver- These obstacles have yet tried to be overcome by the choice of
sion of pure cellulose waste to new MMCFs, if the material’s prop- either ionic liquids with low viscosities, or considerably low con-
erties classified it as spinnable (Ma et al., 2018; Ma et al., 2016). centrations of cellulose (Negulescu et al., 1998; de Silva et al.,
Any recycling concept relying on the dry-jet wet spinning of cellu- 2014). To compromise between facilitated processing and
lose is challenged by heterogeneous substrates such as textile spinnability, we evaluated dope concentration of 6.5 wt% and
waste. Besides the removal of residual contaminants, i.e. synthetic 10.5 wt% cellulose implying that the same amount of PET remained
fibers and metals, the cellulose fractions need to undergo certain undissolved in the ionic liquid solution. The concentration of a
pretreatments to achieve both an adequate average degree of poly- spinning solution correlates directly with the properties of the
merization ([N] ffi 450 ml g
1) and a broad molar mass distribution spun fibers. Higher concentrations usually lead to fibers with
(MMD) (Michud et al., 2015a). The properties of pre-consumer cot- higher tensile strength, but also require higher draw ratios (DRs)
ton waste are usually far beyond these criteria due to its high to achieve filaments with titers low enough to be used in textiles
intrinsic viscosity and considerably narrow MMD, which makes (t < 3.0 dtex). This implies that a spin dope concentration of
pretreatments essential. In postconsumer textiles, laundering 6.5 wt% can already yield microfibers (t < 1.0) at a DR 8, while
induces a certain degree of degradation, leading to an increased the same DR for a concentration of 10.5 wt% is just enough to reach
polydispersity index (PDI) and a lower intrinsic viscosity, thus a titer of about 2.0 dtex.
allowing milder pretreatments (Palme et al., 2014). As stated before, the employed dissolution parameters mainly
Consequently, the origin of the waste substrate governs the targeted to improve the processability of a blended waste substrate
choice of the pretreatment. Whereas enzymes such as endoglu- on a lab-scale, and to reduce the continuous degradation of PET
canase hydrolyze cellulose dependent on the amount of amor- throughout the process. We used shorter dissolution times for cel-
phous regions in the polymer, acids, e-beam radiation, and lulose in [DBNH] [OAc] (1 h, 80 °C), and tried to add an excess
hydrogen peroxide cleave cellulose chains with a minor effect on amount of acetic acid (30%) to the ionic liquid (cf. [M1]) to prevent
the MMD (Pérez et al., 2002). Moreover, ozone and hydrogen per- a possible degradation of PET (cf. PET section).
oxide also enable a bleaching of the waste substrate. Both the concentration of cellulose and the presence of addi-
In this work, white postconsumer cotton polyester textiles were tives in the spinning solution influence the rheological properties
treated with an alkaline-disk refining-ozone-peroxide-acid of a spin dope. A summary of the zero shear viscosities (N0*) and
sequence to decrease the intrinsic viscosity [N] of the cellulose frac- the dynamic moduli (G0 , G00 ) at their crossover point (COP) close
tion from 850 ± 50 ml g
1 to 450 ± 50 ml g
1. Although the latter to the spinning temperature (60 °C) can be found in Table 3. The
represent optimum conditions for dry-jet wet spinning, the effect complex viscosities (N*) and the dynamic moduli (G0 , G00 ) as a func-
of the pretreatment on PET should not be ignored. tion of the shear rate of all tested solutions are depicted in Fig. 1.
Table 2 displays a summary of Mn, Mw and the PDI of PET At lower concentrations, cellulose solutions in ionic liquids typ-
throughout the pretreatment sequences. ically show a Newtonian plateau at lower an angular frequency
The PET fraction in the raw-material showed a Mw of 21.5 kDa range (Gericke et al., 2009; Yao et al., 2014). As both, shear stress
and a Mn of 9.8 kDa, which remained almost unchanged after the and concentration increase, shear thinning occurs because
92 S. Haslinger et al. / Waste Management 97 (2019) 88–96

Table 3
Rheology data. The zero shear viscosities N0* were calculated using the cross model, and the crossover point (COP) of the dynamic moduli (G’,G’’) was determined as function of
the shear rate x. All values were calculated for 60 °C representing the measured temperature closest to the spinning temperature.

CO (wt%) N0* (Pa s) x (s
1) G0 = G00 (Pa)

[S1] 6.5 1439 ± 12 6.9 1495
[S2] 6.5 686 ± 6 6.9 939
[M1] 6.5 175660 ± 3621 n.a. n.a.
[M2] 10.5 13294 ± 203 1.4 3224

Fig. 1. Rheology data. Complex viscosity (N*) and dynamic moduli (G0 , G00 ) of the solutions [S1] and [S2] with a concentration of 6.5 wt%, and [M2] with 10.5 wt% in [DBNH]
[OAc], as well as [M1] with a cellulose content of 6.5 wt% in a DBN:HOAc mixture with a molar ratio of 1:1.3 as a function of the angular frequency at 60 °C.

entanglements between the polymer chains tend to be disrupted The spinnability under standardized conditions has been
(Chen et al., 2009). Most samples studied herein correspond to this described as follows, DR < 2 non spinnable, 2–8 poor, 8–14 good,
trend. The critical shear rate for shear thinning decreases with a 14 < excellent (Asaadi et al., 2016). We redefined these criteria
broad MMD and the concentration being raised from 6.5 wt% to for cellulose solutions of lower concentrations to DR < 2 non spin-
10.5 wt%, while the measured complex viscosities potentiate. nable, 2–4 poor, 4–8 good, 8 < excellent, as they require lower DRs
Assuming that the Cox-Merz rule is valid for solutions of cellulose to reach fibers with textile grade properties. All samples prepared
in [DBNH] [OAc], the zero shear viscosities (N0*) can be determined from pure [DBNH] [OAc], i.e. [S1], [S2], and [M2], showed a good
based on the Carreau and the Cross model (Sammons et al., 2008). spinnability with maximum DRs of 8, 6, and 8.8, respectively. In
The high zero shear viscosity calculated for [M1] implies that the case of [S1], the spinning at a DR of 8 led to fibers with a titer of
excess amount of acetic acid reduced the ILs power to dissolve cel- 0.75 dtex, which classifies them as microfibers. The spinning of
lulose. Throughout the angular frequency range, [M1] also displays [M1] was accompanied by the formation of aggregates on the spin-
higher values for G0 than for G00 indicating the formation of a gel neret surface, which led to a maximum DR of 4. As mentioned
rather than a solution. The remaining samples show a viscous before, the excess amount of acetic acid reduces the solvent power
domain, whose range is dependent on the cellulose content (Chen of the IL and therefore the solubility of cellulose therein, which is
et al., 2009). The COPs of [S1] and [S2] (6.5 wt%) can be found at con- consequently reflected in the poor spinnability of [M1].
siderably high shear rates, whereas the COP of [M2] moves to lower Besides additives, both the spin dope concentration and the
angular frequencies with an increasing concentration (10.5 wt%). draw ratio influence the tensile properties of dry-jet wet spun
In this context, it is important to note that the spinning condi- fibers. Due to shear forces, the cellulose molecules experience a
tions are determined by the rheological properties of the solution. pre-orientation in the spinneret during extrusion and are further
In principle, any fluid is spinnable as long as the formed filaments aligned when stretched in the air-gap. As a result, the cohesive
can withstand the applied deformation and surface forces (Ziabicki forces within the cellulose network increase, which eventually fos-
and Takserman-Krozer, 1964a, 1964b). During spinning, a certain ter the formation of a dense fibrillar cellulose II structure (Fink
DR (vtu/ve) is exerted on the extruded filaments in order to align et al., 2001). A raise in the cellulose content can improve this effect.
the cellulose chains coaxially to obtain a higher fiber tenacity and The properties of the fibers presented in Fig. 2 confirm this
a lower fiber diameter (Hauru et al., 2014; Sixta et al., 2015). A cellu- principle.
lose solution in [DBNH] [OAc] should thus display a N0* of 20,000– Sample [M2] exhibits the highest tenacity followed by [S1], [S2]
30,000 Pas and a COP of 2000–5000 Pa to yield optimum spinning and [M1], which also corresponds to the draw ratios and concen-
conditions (Asaadi et al., 2016; Ma et al., 2018, 2016; Michud trations employed. These properties are comparable in conditioned
et al., 2015a, 2015b; Sixta et al., 2015). Besides varying concentra- and wet state, with their elastic moduli (15–20 GPa) exceeding
tion and MMD, these parameters can be reached through adjusting those of commercial Viscose and Tencel fibers as illustrated in
the spinning temperature. However, the melting point of [DBNH] the slope of the respective stress strain curves. The higher fiber
[OAc] restricts the spinning window of cellulose solutions of lower strength is also explained by a higher total orientation ftotal of
concentrations and is evident in the values summarized in Table 3. the fibers (s. Table 4) and an increase in the fibrillar density
 S. Haslinger et al. / Waste Management 97 (2019) 88–96 93

Fig. 2. Fiber properties and stress strain curves. Tenacity (cN tex
1), elongation at break (%), diameter (dtex), and stress strain curves of the fibers spun from the solutions [S1]
and [S2] with a concentration of 6.5 wt% and [M2] with 10.5 wt% in [DBNH] [OAc], as well as [M1] with a cellulose content of 6.5 wt% in a DBN:HOAc mixture with a molar
ratio of 1:1.3. All values were taken at their maximum DRs and commercial Viscose and Tencel fibers were added for reference.

(cf. cross sectional images in Fig. S3 in the supporting information) liquids, among them also [BMIM] [OAc], have been described to
based on the concentration and draw ratio applied. degrade and partly dissolve PET at elevated temperatures (Wang
Compared to commercial Tencel and Viscose fibers, the spun et al., 2009). These ionic liquids are supposed to catalyze the
fibers show a lower elongation, because of a missing air gap condi- hydrolysis of PET, whose effectiveness is strongly influenced by
tioning on our lab-scale equipment, which could apply moisture as the choice of their anion (Liu et al., 2009). Although reported in a
a plasticizer during the spinning process. Despite the difference in number of publications (Brinks et al., 2013; Negulescu et al.,
the fiber properties obtained, the processing conditions did not 1998; de Silva et al., 2014), a separation of cotton and polyester
have any significant impact on MMD of the cellulose fraction as without any degrading effect on the latter seems questionable.
displayed in Table 4 and Fig. 3a. Evidently, the Mn and Mw of the In initial degradation studies, the decrease in tensile strength of
starting material even seem to show lower values than the final virgin PET filaments (6 wt%) was monitored in [DBNH] [OAc] at
products, which is a good representation of the heterogeneity of 80 °C (s. Fig. 3b).
the waste substrate studied. Although no substantial weight loss of the PET filaments could
be observed, their tenacity was more than cut into half over a
3.3. The effect of [DBNH] [OAc] on PET treatment time of 4 h. The decrease from 38 to 18 cN tex
1 is expo-
nential, and exhibits the largest drop already after 0.5 h, while the
In preliminary trials, we could observe a visible degradation of degrading effect of the ionic liquid flattens out with an increased
the recovered PET after its processing in [DBNH] [OAc] at 80 °C treatment time.
because of a change in color. PET is usually hydrolyzed under the The recyclability of PET fibers strongly depends on its degree of
presence of water and temperatures higher than 100 °C polymerization and purity. Only a high-grade PET substrate is suit-
(Buxbaum, 1968). However, several imidazolium based ionic able to be re-spun in a melt spinning process, fractions with a

Table 4
Birefringence and molar mass distribution of the spun fibers. The birefingence values Dn and the total orientation ftotal dependent on the cellulose concentration (CO) and draw
ratio (DR) applied, the number average molar mass Mn, the mass average molar mass Mw, and the polydispersity index (PDI = Mw/Mn) of the cellulose fraction before separation
[R], and after the spinning trials [S1], [S2], [M1], and [M2].

CO (wt%) DR Dn ftotal Mn (kDa) Mw (kDa) PDI

[R] 68.3 ± 0.7 193.2 ± 5.1 2.8 ± 0.04
[S1] 6.5 8 0.0437 ± 0.0050 0.705 ± 0.080 91.1 ± 3.4 219.3 ± 3.2 2.4 ± 0.10
[S2] 6.5 6 0.0375 ± 0.0097 0.605 ± 0.156 71.1 ± 0.1 179.0 ± 3.6 2.5 ± 0.05
[M1] 6.5 4 0.0363 ± 0.0116 0.586 ± 0.187 90.0 ± 0.4 199.2 ± 0.9 2.2 ± 0.02
[M2] 10.5 8.8 0.0417 ± 0.0076 0.673 ± 0.122 84.4 ± 0.7 215.0 ± 0.3 2.5 ± 0.02
94 S. Haslinger et al. / Waste Management 97 (2019) 88–96

Fig. 3. (a) MMD of the cellulose fraction before separation [R], and after the spinning trials with 6.5 wt% ([S1] and [S2]) and 10.5 wt% ([M2]) in [DBNH] [OAc] solution, as well
6.5 wt% ([M1]) in a DBN:HOAc mixture with a molar ratio of 1:1.3. (b) Decrease of tensile strength of virgin 3.3 dtex PET fibers (6 wt%) in [DBNH] [OAc] at 80 °C as function of
the treatment time, (c) TGA of the raw-material [R] and the recovered PET fractions after the separation experiments [S1], [S2], [M1], and [M2], (d) Molar mass distribution of
PET of the raw-material [R], and after the separation experiments [S1], [S2], [M1], and [M2]. For figures b-d, [R] denotes the PET fraction in the raw-material, while [S1] and
[S2] respectively describe the PET obtained from 1 separation step and 1 or 2 washing steps with [DBNH] [OAc]. [M1] represents the PET residue from a modified extraction
procedure in DBN:HOAc with a molar ratio 1:1.3 (+2 washing steps in the same mixture), whereas [M2] denotes PET resulting from a two-step extraction procedure in
[DBNH] [OAc] (+2 washing steps in the same IL).

lower DP require alternative processing techniques results, 1 h appeared effective enough to ensure a complete disso-
(Venkatachalam et al., 2012). These circumstances inevitably lution of the cotton fraction, and to prevent an extensive degrada-
denote the most substantial challenge in the recycling of PET. tion of PET (Michud et al., 2015a). To remove any residual cellulose,
Any degradation occurring during a separation and recovery pro- the PET fraction was filtered off from the cellulose solution and
cess is categorically unwanted. Nevertheless, a fact that yet has washed with IL and water as described in the experimental section.
often been ignored is that virgin PET, which is converted into tex- Table 5 depicts the cellulose content in the recovered PET after the
tile fibers, already loses its ability to be re-spun during its first melt separation experiments. The respective NMR spectra can be found
spinning cycle. Various degradation reactions cause a decrease of in Fig. S4 in the supporting information.
the DP of PET before the spun fibers have even been worn once One washing step in [DBNH] [OAc] (1 h, 80°) was sufficient to
(Samperi et al., 2004). This makes it strictly speaking impossible decrease the concentration of residual cellulose to 2.5 ± 0.5 wt%
to recycle PET based textile waste to new fibers without applying (cf. [S1]). The addition of one more washing step further lowered
any chain extension (Awaja and Pavel, 2005) or depolymerization the amount of cellulose to 1.7 ± 0.4 wt% (cf. [S2]). The purity of PET
and repolymerization concepts (Sun et al., 2018a, 2018b). Alterna- is also confirmed by the TGA shown in Fig. 3c, and does not reveal
tive recycling strategies therefore suggest to separate the PET a major change in the onset temperature To of the recovered frac-
mechanically from the cellulose component in order to keep a fur- tions [S1] = 397 °C, [S2] = 398 °C, [M1] = 393 °C, and [M2] = 397 °C.
ther degradation as a low as possible (Sun et al., 2018b). As expected, the treatment time in [DBNH] [OAc] affected the
However, we still tried to avoid any unnecessary degradation of molar mass distribution of PET as shown in Fig. 3d and in Table 5.
PET by keeping its treatment time in [DBNH] [OAc] as short as pos- The MMD of the treated substrate noticeably decreased throughout
sible during the separation experiments. According to previous the different treatment steps and time until it almost reached a
 S. Haslinger et al. / Waste Management 97 (2019) 88–96 95

Table 5
Residual cellulose in PET and MMD of PET. Amount of cellulose (wt%) in the cotton polyester blend before separation [R], and after the separation experiments [S1], [S2], [M1], and
[M2] dependent on their total time of exposure to [DBNH] [OAc] or DBN:HOAc (1:1.3) according to 13C CP-MAS NMR, and molar mass distribution of the separated PET fraction
including number average molar mass Mn, mass average molar mass Mw, and polydispersity index (PDI = Mw/Mn).

Total time in IL (h) Cellulose (wt%) Mn (kDa) Mw (kDa) PDI

[R] 0 49.8 ± 6.7 9.2 ± 0.29 23.5 ± 0.17 2.6 ± 0.2
[S1] 2 2.5 ± 0.5 6.2 ± 0.20 17.4 ± 0.13 2.8 ± 0.2
[S2] 3 1.7 ± 0.4 4.4 ± 0.14 12.0 ± 0.09 2.8 ± 0.2
[M1] 3 2.0 ± 0.4 7.1 ± 0.23 19.5 ± 0.14 2.7 ± 0.2
[M2] 3 1.9 ± 0.5 5.9 ± 0.19 16.5 ± 0.12 2.8 ± 0.2

bisection of Mw and Mn after a total of 3 h in [DBNH] [OAc] (cf. [S1] Acknowledgements

and [S2]). [M2] exhibits a bimodal MMD, as it consisted of two sep-
arate PET fractions, which were added to the IL consecutively. The This project has received funding from the European Union’s
excess amount of acetic acid added to [M1] seemed to prevent the Horizon 2020 research and innovation programme under grant
degradation of PET to some extent. Although the acetic acid caused agreement No. 646226. The authors also gratefully acknowledge
the formation of a gel-like solution, the cellulose content could be Dr. Ali Harlin, Dr. Christiane Laine, and Dr. Sari Asikainen (VTT, Fin-
reduced in a similar manner as in the trials that employed pure land) for their support in material pretreatment and in the analysis
[DBNH] [OAc]. Neither of the approaches seemed to have a substan- of PET as well as Dr. Zengwei Guo (RISE IVF, Sweden) for his
tial impact on the PDI of the samples, implying that [DBNH] [OAc] expertise regarding the recyclability of PET. We also thank Hilda
most likely induced a uniform cleavage of the polymer chains. Zahra (Aalto University, Finland) for conducting the TGA
Alternatively, a reduction of the temperature during dissolution measurements.
to 75 °C or lower might further decrease the degradation of PET,
which is favorable especially on an industrial scale as larger knead- Appendix A. Supplementary material
ers utilize significantly shorter dissolution times (5–10 min).
Supplementary data to this article can be found online at
4. Conclusions https://doi.org/10.1016/j.wasman.2019.07.040.

The heterogeneity of textile waste represents both a challenge

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