Journal of Cleaner Production 318 (2021) 128569

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Journal of Cleaner Production

journal homepage: www.elsevier.com/locate/jclepro

Flotation separation of hazardous polyvinyl chloride from waste plastics

based on green plasma modification
Yue Zhao a, *, Fengrong Han b, Linyi Guo a, Sharanjit Singh c, Haidong Zhang a, Jun Zhang a
a
Shaanxi Key Laboratory of Disaster Monitoring & Mechanism Simulating, College of Geography and Environment, Baoji University of Arts and Sciences, Baoji, 721013,
China
b
College of Engineering, Universiti Malaysia Pahang, Pekan, 26600, Malaysia
c
Key Laboratory of Organic Optoelectronics & Molecular Engineering, Department of Chemistry, Tsinghua University, Beijing, 100084, China

A R T I C L E I N F O A B S T R A C T

Handling editor: Prof. Jiri Jaromir Klemeš Flotation has a great potential in the separation of complicated poly-mixtures to obtain qualified resins for
recycling, but it remains a technological challenge for selective wetting between components. This study pro­
Keywords: vided a combined flotation process with the prepositive plasma modification, separating hazardous polyvinyl
Clean plasma chloride (PVC) from recyclable high-density polyethylene (HDPE) and polyethylene terephthalate (PET). The
Free radicals
plasma process was characterized by surface morphology, molecular weight, contact angle, surface free energy
Plastic flotation
and spectrum. The results suggested that amorphous low molecular weight oxidic substances can be selectively
Plastic recycling
Surface modification introduced on these polymers through the hydrogen extraction and Norrish І type radical pathways in plasma
zone, leading to a desired surface wetting. Under the optimal unit activating energy of 12.0 kJ/m2 (PVC-HDPE)
and 15.0 kJ/m2 (PVC-PET), separated PVC can reach above 93% of both recovery and purity. Benefiting from the
green and mild operation in plasma unit, this study paves a new way to effectively separate waste plastics as an
alternative to traditional surface modification with chemical reagents.

on diverse recycling approaches have been published in this regard. For

1. Introduction
Waste plastics, associated with the short lifetime and long degrada­
tion time of their commercial products, have brought adverse environ­
mental impacts and a groundswell of plastic limit order on a global scale
(Tyuftin and Kerry, 2020). According to statistics of a material flow
assessed by the U.S. Environmental Protection Agency, waste plastics
are treated by traditional disposal mainly in landfills and incineration,
leaving less than 9.3% for recycling (Law et al., 2020). Before any
possible promotion of the alternative functional materials, recycling
waste plastics still has the maximum economic and environmental
benefits according to a life cycle assessment (Gu et al., 2017). It cannot
only save raw materials, chemical monomers and energy but also help in
lowering the harmful effects during disposal (Majumdar et al., 2020).
High-density polyethylene (HDPE), polyethylene terephthalate
(PET) and polyvinyl chloride (PVC) tend to occupy a dominate pro­
portion (>15%) in the common solid streams, such as the municipal
solid waste (MSW) (Zhang et al., 2020a) and waste electrical and elec­
tronic equipment (WEEE) (Wang et al., 2019a). HDPE and PET have
been proved with remarkable potentials for reusing, and many studies
example, Caniato et al. reported an eco-friendly foam made of waste
micro-PET incorporated into a bio-matrix, and this novel open-cell
material can be used as acoustic and thermal insulation for industrial,
civil and maritime applications (Caniato et al., 2021). Cetin proposed a
series of plastic paving materials including the granular recycled poly­
ethylene (Cetin, 2015) and PET (Cetin, 2013), in favor of the sustainable
landscape architecture construction.
PVC is reported to destroy the quality of master batch (Zhang et al.,
2020b) or pyrolysis oil (Thanh Truc and Lee, 2019) during the recycling
operation even at a low dosage of its contamination. On account of its
non-ignorable halogen content, PVC faces to a hidden risk for the indi­
rect releasing of persistent organic pollutants, acidic HCl gas and
carcinogenic dioxins during reusing (Zhou et al., 2020). Waste plastics
collected from different solid streams belong to the “poly-mixtures” with
a low-grade specification, separating them into “single resin” type is the
most vital step before recycling (Wang et al., 2019a). For the purpose of
cleaner production, hazardous PVC needs to be treated as the priority to
separate from HDPE and PET, which contributes to promoting the whole
recycling chain as well (Ye et al., 2021). In the secondary recycling
station of waste plastics, manual sorting according to the signs

* Corresponding author. College of Geography and Environment, Baoji University of Arts and Sciences, Gaoxin Road #1, Gaoxin District, Baoji, 721013, China.
E-mail addresses: zhaoyue2061@bjwlxy.cn, hippozhaoyue@163.com (Y. Zhao).

https://doi.org/10.1016/j.jclepro.2021.128569
Received 1 March 2021; Received in revised form 28 July 2021; Accepted 4 August 2021
Available online 5 August 2021
0959-6526/© 2021 Elsevier Ltd. All rights reserved.
Y. Zhao et al.
Nomenclature
CA contact angle
Cox/unox oxidized to unoxidized carbon ratio
Ej unit activating energy
FT-IR Fourier transform infrared spectrum
HDPE high-density polyethylene
L electrode length
LMWOMs low molecular weight oxidic substances
MSW municipal solid waste
MW molecular weight
Mn number-average MW
Mw weight-average MW
Mip mass of corresponding i plastic in product
Mit mass of corresponding i plastic in tailing
OC1 optimal conditions 1
OC2 optimal conditions 2
OH hydroxyl radical
P corona discharge power
dominates in current methods, which is low efficiency and not suitable
for the vast majority polymers without clear type identification (Wang
et al., 2015a). The lack of customized, cost-effective and industrialized
separation technologies should be attended to.
Former researches have demonstrated that the flotation technology
can be utilized as a separation approach for plastic mixtures, and it at­
tracts more extensive attentions due to the successful precedent of in­
dustrial application in minerals engineering (Wang et al., 2015a). The
basic principle of flotation is established on the hydrophilic difference
between materials, using stable foams as the carrier to achieve a positive
(floated product) or reverse (sunken tailing) separation (Mallampati
et al., 2016). The similar surface hydrophobicity of common polymers
cannot provide enough distinction. For instance, the natural hydrophi­
licity range of PVC normally overlap those of HDPE and PET, resulting in
unsatisfactory separation performance for the unitary flotation (Wang
et al., 2019a). To create a sufficient difference in the hydrophilicity of
polymer components, the initial strategies rely on the usage of wetting
reagents. Zhao et al. reported that the HDPE, PET, and PVC all prefer to
gather in floated product, the adsorption of common mineral inhibitors
(sodium carboxymethylcellulose, lignosulfonate and tannic acid)
through weak hydrogen bonding. Such weak adsorption is accompanied
by destabilization, resulting in less selectivity during flotation process
(Zhao et al., 2019a). Selective wetting of polymers becomes a great
challenge for their flotation separation, a series of surface modification
technologies are developed to solve this bottleneck.
Zhang et al. used ClO2 (Zhang et al., 2020a) and (NH4)2S2O8 (Zhang
et al., 2020b) oxidants with heating operation to modify the surface of
plastics, achieving the separation of PVC component in a simple flota­
tion unit. Similar oxidation processes can also be activated by the Fenton
(Wang et al., 2019b) or ultrasound irrigation system (Thanh Truc and
Lee, 2019), leading to the dividing hydrophilic states through the
introduction of oxygen-containing groups on polymer surface. Zhao
et al. developed a surface micro-alcoholysis modification towards
PET-PVC mixtures, the PET can turn to sunken tailing for separation due
to the superficial generation of hydrophilic oligomers after ester ex­
change reaction (Zhao et al., 2019b). These surface modification
methods bring creative inspirations for the enhanced flotation separa­
tion of waste plastics, but show limitations in cleaner production and
sustainability including: (ⅰ) additional cost of modification reagents and
longtime temperature control; (ⅱ) catalytic conditions involving some
soluble metal ions (Fe3+), transition metal ions (Zn2+), pH and polar
solvents, which cause a secondary burden for reclaimed water. Green
and mild alternative technologies will be the wave of the future.
2
Journal of Cleaner Production 318 (2021) 128569
Pi purity of i plastic in product
PET polyethylene terephthalate
PVC polyvinyl chloride
RC⋅ organic carbon radical
Ri recovery of i plastic in product
SEM scanning electron microscope
SSA specific surface area
TP terpineol
v feeding transmission speed
WEEE waste electrical and electronic equipment
XPS X-ray photoelectron spectrum
Greek Symbols
θa CA value between plastic and detection liquid
γs surface free energy
γsLW dispersion component of γs
γsAB polar component of γs
γ s+ Lewis acid component of γs
γ s- base component of γs
Non-thermal plasma can be produced by electrical discharge at at­
mospheric pressure and air supply. It has been major applied as a pre­
treatment in printing and package industry to achieve the ink-adhesion
enhancement onto polymers and plywood. (Wascher et al., 2017). As the
fourth state of matter, the plasma is rich in highly reactive radicals and
preserving dry electrical neutrality (Sheng et al., 2020), which is regard
as a rapid in-line, reagent-free-addition (Klímek et al., 2016), and green
inducer for many potential reactions (Li et al., 2014). Its application has
crossed to the mineral flotation, improving the separation performance
of traditional feedstock like low-rank coal (Zhen et al., 2019), arseno­
pyrite and pyrite (Ran et al., 2019). From a wetting functional point of
view, a hypothesis is novel and meaningful that the combination of
plasma and flotation units may promote the separation of waste plastics,
but few evidences can be accessed from literature before. The aim of this
study is to examine such a plasma surface modification towards the
flotation of plastics, minimizing the mentioned negative impacts (ⅰ & ⅱ)
and bringing into high separation performance. Due to the promising
separation results and data support, the future disposal of waste plastics
can be expected in a more practical, effective, and cleaner way.
2. Experimental
We performed the following three main tasks on the hypothesis of
basic process combination: (1) experimental establishment of a whole
separation flowsheet with detailed parameters for PVC-HDPE and PVC-
PET mixtures; (2) utilization of multi-characterization tests for a
mechanism discussion, which consisted of plausible reaction pathways;
(3) a clean recycling assessment through the comparison with analogous
technologies. To provide the reader guidance on comprehension of these
tasks, a flowchart of the main covering methodologies is presented in
Fig. S1.
2.1. Materials and reagents
Protogenetic plastic sheets (400 × 120 × 5 mm) with different colors,
including high-density polyethylene (HDPE), polyvinyl chloride (PVC),
and polyethylene terephthalate (PET), were purchased from SK HOLD­
INGS Co., Ltd. (South Korea). Terpineol (TP), as a commercial kind of
frother for ore flotation, was obtained from KEDE Chemical Co., Ltd.
(China). Deionized water (18 MΩ cm), acted as flotation medium, was
also employed to rinse any surface contaminant of plastics prior to use.
Basic physicochemical properties of the mentioned materials and re­
agents are summarized in Table S1. Other reagents used in
Y. Zhao et al. Journal of Cleaner Production 318 (2021) 128569

characterization tests were all above analytical purity. mass-volume (feed/medium) ratio 2 %, air flow rate 200 L/h, size
fraction 3–5 mm and flotation time 5 min, which were feasible and
2.2. Plasma modification reliable to get the stable fluid dynamic environment. The floated product
was automatically scraped off, and then be collected to weight after air
Non-thermal plasma was ignited at local atmospheric air pressure for dry and manually classified. Based on the total mass balance, recovery
surface modification (Fig. 1), using an in-line industrial corona equip­ and purity of plastics were calculated by Eqs. (2) and (3).
ment (FR-33, HEFENG, China). Two parallel plate electrodes (length × Mip
width × interval: 500 × 1 × 1.5 mm) were vertically placed on a Ri = × 100% (2)
Mip + Mit
conveyor belt made of 96% Al2O3, which was connected with feeding
rolls to provide an infinitely variable transmission speed range of 2–15 Mip
m/min to pass discharge zone. The corresponding plasma exposure time Pi = × 100% (3)
Mip + Mjp
was under controlled within 1600–12000 ms, which was sufficient to
common low-energy surface (Klímek et al., 2016). The electronic control where Ri and Pi are the recovery and purity of i plastic in product. Mip
system was powered by input sinusoidal voltage of 220 VAC/50 Hz, and Mit represent the mass of corresponding i plastic in product and
discharge polarity and maximum output power of 1 kW were free to tailing. Component j is the plastic except for component i, and there only
switch via a combination of transformer and gate logic circuit. Circu­ exists one index for single-component feeding, flotation percentage,
lating transformer oil provided the electrical insulation and dissipation which is equal to Ri.
of heat originated in plasma. The discharge polarity, power and expo­
sure time were chosen as influencing factors of the plasma modification
process, and a designed matrix of the independent variables are pre­ 2.4. Surface characterization tests
sented in Table S2. To quantitatively evaluate the plasma process (Sheng
et al., 2020), the unit activating energy (Ej) was determined according to To further clarify the mechanism of proposed separation process,
Eq. (1). multiple characterization tests of the poly-mixtures, including surface
morphology, molecular weight (MW), contact angle (CA), surface free
P energy (γs), Fourier transform infrared (FT-IR) and X-ray photoelectron
Ej = (1)
L×v (XPS) spectrums were employed under the original and optimal condi­
where P is the corona discharge power. L represents electrode length, tions. The surface morphology was conducted using a KYKY-2800B
and v is the feeding transmission speed. scanning electron microscope (SEM, KYKY Technology co., Ltd.,
China). Specific surface area (SSA) was determined on a Nova 1000
surface area analyzer (Quantachrome Instruments, U.S.A.) according to
2.3. Flotation experiments
the Brunauer-Emmett-Teller method (Cheng et al., 2020). The MW was
determined by a HP-1100 Gel permeation chromatograph (GPC, Agilent
After double-sided plasma modification, the plastic sheets were
Technologies Inc., U.S.A.) carrying a Phenogel mixed column and
crushed using a pulverizer (DFT-200A, JIUPIN, China) and screened
G1362A RID detector. The CA was determined by a SL200KS static op­
with sieves to obtain granules within the same size fraction. Two stra­
tical system (Kino Inc., U.S.A.). The γs including its dispersion (γsLW),
tegies for flotation feeding, including single-component and PVC-
polar (γsAB), Lewis acid (γs+) and base (γs-) components were calculated
contained binary mixtures (PVC-HDPE, PVC-PET), were set using com­
based on the Owens-Wendt method (Wang et al., 2015b), using the
binations of the obtained granules. All flotation experiments were per­
following Eqs. (4) and (5).
formed in a self-designed flotation column (Fig. 1), which was 280 × 70
√̅̅̅̅̅̅̅̅̅̅
mm (height × inner diameter) in a specific size. A sand core installed at γ s = γLW
s + γAB LW
s = γs + 2 γ+s γs
− (4)
the column bottom in cooperation with an adjustable air pump (CTP-
[√̅̅̅̅̅̅̅̅̅̅̅̅̅̅ √̅̅̅̅̅̅̅̅̅̅ ]
16000, QIUSHI Engineering Co., Ltd., China) and frother injection to √̅̅̅̅̅̅̅̅̅̅
γ l (1 + cosθa ) = 2 γ LW γ LW
+ γ + γ− + γ −s γ+ (5)
generate homogeneous-size bubbles as the carrier of floated product. s l s l l

Based on our previous plastic flotation studies (Zhao et al., 2019a), the
operating conditions were set as TP concentration 25 mg/L, where θa represents the CA value between plastic and detection liquid

Fig. 1. Flow chart for separation process.

3
Y. Zhao et al.
(refer to deionized water, glycerinum and glycol). γ lLW, γl+ and γl- are the
dispersion, Lewis acid and base components of detection liquid, which
can be accessed in Table S3. The FT-IR and XPS spectrums were recorded
by a Nicolet 6700 (Thermo Fisher SCIENTIFIC, U.S.A.) and ESCALAB
250Xi (Thermo Fisher SCIENTIFIC, U.S.A.) spectrometers.
2.5. Quality guarantee
All used instruments for characterization, based on the mature and
reliable detection principles, were calibrated before usage. Each nu­
merical data found in characterization tests was the average of three
replicates, and each sample run was always being accompanied by five
equally repeats in both plasma modification and flotation experiments.
The average value was used in corresponding contents, and the relative
standard deviation value did not exceed 5%.
3. Results and discussion
3.1. Determination and verification of process parameters
3.1.1. Effect of plasma modification on flotation
As seen in Fig. 2 (a), the flotation percentage of unmodified plastics is
all about 95% due to their originally approximate hydrophobicity,
which means the separation of PVC from HDPE and PET is difficult. After
initiatory plasma modification at 300 W for 6000 ms, the PVC and PET
can retain high flotation percentage, while its value for HDPE decreases
Fig. 2. Effect of discharge polarity (a), power (b) and exposure time (c &d) on the floatability of plastics.
4
Journal of Cleaner Production 318 (2021) 128569
to around 30% and 50% during the discharge process with different
polarity. The positive discharge seems to be more effective in changing
the flotation percentage of HDPE. With the increasing of discharge
power to 600 W (Fig. 2 (b)), the flotation percentage of PVC is below 2%,
while for PET it is around 60%. By continuous prolonging of the expo­
sure time at different power levels (300 and 600 W), the flotation per­
centage of each polymer finally exists obvious decline (Fig. 2 (c) & (d)).
Under optimal conditions of positive discharge, power 300 W and
exposure time 8000 ms (denoted as OC1), the flotation percentage of
PVC and HDPE is 89.28% and 2.39%. The flotation percentage of PVC
and PET, under optimal conditions of positive discharge, power 600 W
and exposure time 5000 ms (denoted as OC2), is observed to be 5.09%
and 88.31%. The flotation separation of PVC-contained binary mixtures
may be accomplished under the corresponding OC1 and OC2. Some
macromolecule substrates, such as plywood and polymer films, have
been proved to be a printing ink-adhesion enhancement through a
similar plasma process (Li et al., 2014). It is speculated that the electrons
among generated plasma with energy higher than binding energy, hit
the material breaking molecular bonds and lead to its surface modifi­
cation (Klímek et al., 2016). Such surface modification obviously
changes the original hydrophobicity of polymers, resulting in a
following variant flotation performance.
3.1.2. Correlation between Ej and floatability
Although the main control parameters for plasma modification are
considered as discharge power and exposure time, the robustness is
Y. Zhao et al. Journal of Cleaner Production 318 (2021) 128569

limited by design size of different corona equipment, and Ej can elimi­
nate the above limitation that has a practical reference value (Tyuftin
and Kerry, 2020). As shown in Fig. S2, there is a certain linear rela­
tionship (R2 > 0.78, Table S4) between flotation percentage of each
polymer and Ej with different ranges. The sequence of required mini­
mum Ej level for flotation percentage decreasing is HDPE (6.0 kJ/m2) <
PVC (10.5 kJ/m2) < PET (15.0 kJ/m2), which also reflects the corre­
sponding tolerance of plasma modification. The OC1 and OC2 can be
transferred into Ej level of 12.0 kJ/m2 and 15.0 kJ/m2. It is worth noting
that the flotation percentage of HDPE and PVC increases to around 20%
at high Ej level above 24 kJ/m2 (Fig. S2 (c)). This phenomenon belongs
to an over processing of polymers and may be related to the
up-migration of additives from subjacent substrate layer, which should
be avoided during plasma modification (Klímek et al., 2016).
3.1.3. Separation of PVC-contained binary mixtures
Given that the mass fraction of PVC is always different in diverse
solid waste streams, the flexibility of the achieved OC1 and OC2 are
verified to separate PVC-contained binary mixtures with different mix­
ing ratios, which is exhibited in Table 1. When the mass ratios of PVC in
feeds are 30%, 50% and 70%, the recovery of PVC in floating product
has a maximum of 93.06% under OC1 (Ej = 12.0 kJ/m2). The corre­
sponding purity can orderly reach up to 91.63%, 94.33% and 96.65%.
For the separation of PVC-PET mixtures under OC2 (Ej = 15.0 kJ/m2),
the recovery and purity of PVC in submerged tailing are still up to
91.23% and 91.38%. The result reveals that the selective separation of
PVC can be accomplished by the aid of plasma modification for flotation.
The purity of PVC both in product and tailing is observed to be
decreasing as the mass fraction of PVC decreases, which may be
attributed to the entrainment with other components, and heteroge­
neous aggregation deteriorates the flotation performance (Zhang et al.,
2020a). Quadratic optimization in the fluid dynamic environment of
flotation may further help in promoting separation of poly mixtures with
a comparable low mass fraction of PVC.
Table S5, further proof that the surface roughness of HDPE and PVC
increase under corresponding OC1 and OC2, while for PET it is barely
change. The sharp decreasing of number-average and weight-average
MW (Mn and Mw) only occur on HDPE and PVC surface. Their ratio
(Mw/Mn) increases to reflect long-chain fracture and short-chain doping
of polymers (Musil and Zatloukal, 2011). It is presumed that hydro­
phobic main-chain encapsulation of HDPE or PVC may be destroyed and
water molecular can more easily infiltrate into amorphous regions (Zhao
et al., 2019b), leading to a predictable improvement of surface wetting.
3.2.2. Wettability analysis
As shown in Fig. 4 (a), the CA values for all three original plastics are
approximately 90◦ , which verifies the similar hydrophobicity that
cannot be separated in flotation process. The CA of HDPE decreases by
above 31◦ after plasma modification under OC1, while for PVC it is
almost unchanged (<3◦ ). With the increasing of Ej level to OC2, the CA
of PVC drops to less than 71◦ while it still maintains over 88◦ for PET.
These results are also consistent in corresponding variation of flotation
percentage in Fig. 2. The values of γs for plastics before and after plasma
modification, including the detailed components, can be further
explained on wettability, which is illustrated in Fig. 4 (b). It is clearly
visible that the plasma modification with proper Ej level can cause the
increase of polar γ sAB for HDPE and PVC, as well as simultaneous
decrease in its γsLW. Only trace amounts of changing surface free energy
are observed in PET surface under OC2. According to the Van Oss-
Chaudhary-Good wetting theory (Brajkovic et al., 2014), an increase
of γs is favorable in view of the improvement of the substrate wettability,
which is always accompanied by a significant reduction of CA between
polarity detection liquid and surface. Comparing the two results of CA
and γs, the wetting sensitivity by plasma modification is HDPE > PVC >
PET. Due to the corresponding increments of γ s- both exceed 22 mJ/m2,
it is expectable that the plasma process may introduce some hydrophilic
polar groups on HDPE and PVC surface along with the long-chain
fracture.

3.2.3. Functional group analysis

3.2. Analyses of multi-characterization tests
3.2.1. Surface morphology analysis
As shown in Fig. 3, the original surface of HDPE, PVC and PET is
relatively smooth except for limited machining marks. Obvious cracks
and pits appear on the surface of HDPE and PVC after plasma modifi­
cation under OC1 and OC2. The plastics seem to obtain a selective
etching during plasma process, as there are only some shallow folds
appear on PET surface under the same OC2. The SSA values, listed in
Fig. 5 displays an overview of original and plasma treated plastics on
the FT-IR spectra to determine the possible change of functional groups.
For original polymers, HDPE reveals CH2 rocking, deformation, anti-
symmetric and symmetric vibrations at 720, 1470, 2916 and 2946
cm− 1 (Musil and Zatloukal, 2011); PVC exhibits characteristic peaks of
C–Cl stretching at 688 cm− 1, C–H twisting at 960 cm− 1, C–C stretching
at 1100 cm− 1, C–H rocking, deformation and stretching at 1265, 1390
and 2924 cm− 1 (Zhang et al., 2020b); PET has an intense band (500-700

Table 1
Flotation separation of PVC-contained binary mixtures.
Plasma condition Plastic mixture Flotation component Yield (%) Purity (%) Recovery (%)

PVC Others PVC Others

OC1 PVC 30 wt% + HDPE 70 wt% Feed 100 30 70 – –

Product 30.47 91.63 8.37 93.06 3.64
Tailing 69.53 2.99 97.01 6.94 96.36
OC1 PVC 50 wt% + HDPE 50 wt% Feed 100 50 50 – –
Product 45.60 94.33 5.67 86.03 5.17
Tailing 54.40 12.84 87.16 13.97 94.83
OC1 PVC 70 wt% + HDPE 30 wt% Feed 100 70 30 – –
Product 61.66 96.65 3.35 85.13 6.89
Tailing 38.34 27.15 72.85 14.87 93.11
OC2 PVC 30 wt% + PET 70 wt% Feed 100 30 70 – –
Product 68.47 3.84 96.16 8.77 94.05
Tailing 31.53 86.79 13.21 91.23 5.95
OC2 PVC 50 wt% + PET 50 wt% Feed 100 50 50 – –
Product 49.32 10.40 89.60 10.26 88.37
Tailing 50.68 88.53 11.47 89.74 11.63
OC2 PVC 70 wt% + PET 30 wt% Feed 100 70 30 – –
Product 31.79 24.13 75.87 10.96 80.41
Tailing 68.21 91.38 8.62 89.04 19.59

5
Y. Zhao et al.
Fig. 3. SEM of plastics before (a) and after (b) plasma modification.
Fig. 4. CA values (a) and surface energy parameters (b) for plastics before and after plasma modification.
cm− 1) of glycol unit, bands ranging from 725 to 867 cm− 1 are related to
the ortho or para orientation of benzene and a broad peak at 1650-1900
cm− 1 is produced by C– – O (Zhao et al., 2019a). After plasma modifi­
cation under OC1, two new peaks for HDPE emerge at near 3500 and
1740 cm− 1, which are deemed to be OH (Zhang et al., 2020b) and
O–– C–O (Zhang et al., 2019). Similar peaks are also observed on PVC
after promoting Ej level to OC2, while there is no obvious difference on
PET. These results further support that hydrophilic polar groups (OH,
O–– C–O) generate on the surface of HDPE and PVC to enhance their
wettability, resulting in the inhibition of corresponding flotation per­
centage. FT-IR mainly acts on the substrate under a depth of 102–103
nm, which may miss some shallow changes during the surface modifi­
cation (Wang et al., 2019b), it is necessary to further detect the chemical
bonds in more superficial layer of 1–10 nm by XPS.
3.2.4. Chemical bond analysis
A high-resolution XPS scan on the C1s region for original and plasma
treated plastics is displayed in Fig. 6 to discuss the types and amounts of
carbon-oxygen bonds present, the assignment of peaks is provided in
6
Journal of Cleaner Production 318 (2021) 128569
Table S6. As seen in Fig. 6 (a) and (b), the C1s spectrum of original HDPE
is composed of Aliphatic C–C/C–H (285.0 eV) and C–OH (286.2 eV). The
latter is caused by the inevitable natural weathering of polyolefin and its
relative ratio is only 3.43% (Stark and Matuana, 2004). After plasma
modification under OC1, it is observed that the peak of C–OH is
strengthened and two new peaks are additionally matched, including
C–– O (288.0 eV) and O– – C–O (289.5 eV) (Zhang et al., 2020b). As
shown in Fig. 6 (c) and (d), the original and OC1 treated PVC are in
accordance with the following almost unchanged peaks (Wang et al.,
2019b): Aliphatic C–C/C–H, C–Cl (287.0 eV) and O– – C–O. The existence
of O–– C–O suggests a certain head-to-head structure during halogenated
syndiotactic polymerization (Lu et al., 2020). The new peak of C–OH
occurs in Fig. 6 (e) after increasing plasma modification level to OC2. By
considering the area integration under each peak, an oxidized to
unoxidized carbon (Cox/unox) ratio is calculated to present in Fig. 6 (f). Its
value increases to 0.28 and 0.15 for HDPE and PVC, implying occurred
surface oxidation under corresponding OC1 and OC2 (Stark and
Matuana, 2004). Oxidation degree of the latter is comparative low under
the same OC1 level due to its close to 9% C–Cl is maintained.
Y. Zhao et al.
Fig. 5. FT-IR spectra of HDPE (a), PVC (b) and PET (c) before and after plasma modification.
Combined with the MW results from surface morphology analysis, it
is demonstrated that the amorphous low-MW oxidic substances
(LMWOMs) emerge on the upper layer of plastics through plasma
involving reactions, which should be the essence of flotation behavior
change. The increasing of C–OH and decreasing of Aliphatic C–C/C–H
(Table S6) are counted to be the leading features for the generation of
LMWOMs (Wang et al., 2019b), which is also exactly consistent with the
characteristic of hydrogen extraction reaction by hydroxyl radicals
(⋅OH) (Luo et al., 2020). PET expresses the difficulty in generating
LMWOMs even under OC2, since its spectrum do not show any new
chemical bonds (Fig. S3, Table S6). Its inherent Aromatic C–C/C–H
(284.5 eV), Aliphatic C–C/C–H, C–O (286.5 eV) and O– – C–O have a
limited variation in relative content (Wang et al., 2020). When
compared with the pure polyolefin unit in HDPE or PVC, the glycol unit
of PET seems to be inert in chain scission of Aliphatic C–C/C–H. The π-π*
shake up, caused by the transition of the benzene ring electron system,
has a slight increase in relative ratio (>5%) and an interesting shift of its
binding energy (291.5 → 292.7 eV), which may be associated with the
electron donor conjugated (Jiang et al., 2021) and steric hindrance ef­
fects (Hayat et al., 2019).
7
Journal of Cleaner Production 318 (2021) 128569
3.3. Mechanism of plasma-induced surface modification
3.3.1. Pathway 1 for pendant group oxidation
Specific to the generation of LMWOMs from original polymers, Fig. 7
shows a plausible mechanism diagram of plasma-induced surface
modification. The pathway 1 is a hydroxyl radical (⋅OH) process, leading
to the oxidation of C pendant group. An atmospheric plasma occurs in
the corona discharge and abundant in high-energy particles, among
which the (⋅OH) has prominent activities and can be traced in terms of
Eq. (6) (Banaschik et al., 2018), (7) (Klímek et al., 2016) and (8) (Lee
et al., 2006).
O2 + Plasma→2(O ⋅ ) (6)
H2 O + Plasma → (⋅OH) + (H ⋅ ) (7)
(O ⋅ ) + H2 O→2(⋅OH) (8)
The (⋅OH) primarily attacks the Aliphatic C–H of HDPE and PVC
surface through hydrogen extraction. The (⋅OH) quenching is accom­
panied by proton exchange and charge transfer (Zhang et al., 2020b),
the polar –OH is introduced to the pendant group (Krueger et al., 2017).
The C–Cl bond of PVC surface exists a site occupation of the hydrogen
Y. Zhao et al. Journal of Cleaner Production 318 (2021) 128569

Fig. 6. XPS spectra of plastics: (a) original and (b) OC1 treated HDPE; (c) original, (d) OC1 and (e) OC2 treated PVC; (e) corresponding Cox/unox values.

proton (Wang et al., 2019b), hindering the hydrogen extraction to a 3.3.2. Pathway 2 for main chain scission
large extend (Mallampati et al., 2016). The extended-π key in tereph­ According to the Eq. (9) of Norrish І type reaction, a pathway 2 for
thalic acid unit of PET surface has a definite conjugated effect, its high main chain scission can proceed from organic carbon radical (RC⋅)
electron cloud density makes the directional ortho or meta of Aromatic precursor (Stark and Matuana, 2004). Among which, the formed per­
C–H preferentially react with (⋅OH) instead of Aliphatic C–H in the oxidation termination O– – C–O is capable of future derivatization (Li
glycol unit (Banaschik et al., 2018). The oxidation degree of polymers’ et al., 2014), gaining a spot group of C–
– O, C–O and COOH (Zhang et al.,
pendant group has a certain selectivity through the pathway 1 (HDPE > 2020b).
PVC > PET), which is also consistent with the FT-IR and XPS results.

8
Y. Zhao et al.
Fig. 7. Schematic mechanism plasma-induced surface modification of polymers.
(9)
O2
RC − CH2 − +Plasma→RC⋅ + ⋅CH2 − →RCOO⋅→RCOOH
RC ⋅ + ⋅OOCR→ROOR (10)
For HDPE and PVC with the α-olefin form of sp3 hybrid, a homolysis
is more liable to occur on the σ key of C–C (Feng et al., 2011), and the
generated (RC⋅) drives the original polymer migrate to a lower molec­
ular chain (Stark and Matuana, 2004). While as for PET there exists a
steric hindrance effect after polar –OH introduced to the terephthalic
acid unit (Hayat et al., 2019), section shrinkage of the glycol unit may
further impede its sensitivity for homolysis (Wu et al., 2019).
Throughout the full pathways of 1 and 2 by considering valid sites for
radical involving reactions, the capacities of amorphous LMWOMs
generated from different polymers are distinguishing at same Ej level
(HDPE > PVC > PET). Water molecules are beneficial to enter these
amorphous regions and break the original hydrophobicity of polymers
(Wang et al., 2015b). Selective wetting can be accomplished by ration
the Ej level in plasma process, leading to the macroscopical flotation
separation of PVC from HDPE or PET. It is worth noting that excessive Ej
Fig. 8. Evaluation of medium reuse (a) and ageing risk (b) on the flotation performance.
9
Journal of Cleaner Production 318 (2021) 128569
level may have a surplus of (RC⋅) in the pathway 2 (Correia et al., 2019),
turning the main reaction transfer from Norrish І to Norrish II type based
on Eq. (10) (Stark and Matuana, 2004). As the cross-linked product
(ROOR) will restore a certain amount of surface hydrophobicity (Correia
et al., 2019), the phenomenon of flotation percentage growth in Fig. S2
(c) then can be well explained.
4. Perspectives and assessment for clean recycling
4.1. Reusing of flotation medium
The flotation medium used in this study contains the only chemical
agent (frother TP) during the whole separation process, referring to none
of the interferential liquid phase reactions. To consider the environ­
mental and economical efficiencies of reclaimed water, a reuse of
flotation medium was investigated and the result is shown in Fig. 8 (a).
The flotation percentage of each single-component plastic is maintained
at the corresponding initial level within the second cycle. While for
reuse-times of 3, the flotation percentage for both OC2-treated PVC and
Y. Zhao et al. Journal of Cleaner Production 318 (2021) 128569

PET decline markedly (>5%), indicating that the coordinate flotation
system can be used at least three times with stable performance. The
effect of flotation becomes worse with the increasing numbers of reuse-
time, probably because the inevitable TP loss via solid phase adhesion
(Wang et al., 2015b). The continuous cycle in proper sense for industrial
scale flotation can be realized by adding the timing pump control of TP.
4.2. Ageing risk
limitation of corona equipment technologically, here it should be
emphasized that a certain sheet size of feeding is required in this study.
An additional pretreatment operation to achieve sheet through me­
chanical compression should also be taken account before its large-scale
application with real waste sources. Based on the established mecha­
nism, future studies may be expected to obtain a higher wetting selec­
tivity by purposive introduction of oxidation or inert gases (O2, Cl2, He)
during the plasma process, separating PVC from more types of plastics.

Waste plastics owning their original surfaces are reported to be
weather ageing during usage and disposal, and such risk may be even
more worrying for a modified polymer surface (Zhang et al., 2020a). So
ageing was also considered in this study after the plasma modification
process, each single-component plastic was preserved in the same indoor
environment for different times and re-conducted in flotation tests. As
shown in Fig. 8 (b), the flotation percentage of OC1-treated HDPE and
OC2-treated PVC increase to above 50% at 60 days, manifesting an
obvious attenuation of the selective wetting induced by plasma modi­
fication and a tendency revert to the original hydrophobicity with the
increasing ageing time. Such lose efficacy can be associated with the
generated LMWOMs, owing to its possible solvation (Tyuftin and Kerry,
2020), thermal or photo-degradation (Correia et al., 2019), which makes
the substrates compete to migrating up and form a new layer (Stark and
Matuana, 2004). The emphasis here is timeliness of plasma modification
applied for plastic separation, which means it should be better to run
online in series with flotation. A change of perspective, it also has a
fault-tolerant to some extent and does not obstruct the reuse of waste
plastics.
4.3. Practical significances
The continuous parameterization flowsheet of this study is summa­
rized in Fig. S4 for potential industrial enlightenment. To compare with
recent PVC flotation studies assisted by various surface modification
methods, an initial cost estimation by the termwise parametric algo­
rithm (Zhang et al., 2020b) was performed and results are listed in
Table 2. More detailed process information can be accessed in Table S7.
As presented in Tables 2 and S7, the feasibility of this technology is
comparable to other modification technologies for aid of PVC separa­
tion. Since the plasma process is reagent-free-addition and rapid in-line,
this study has a great advantage in the total cost (450.03 USD/t), and its
environmental benefits are not taken into account. Although the upfront
investment cost of corona equipment is relatively high, a further cost
control can be achieved by sharing with the existing production lines in
the packaging and printing industry. Such a born industrialization
advantage exceeds other mentioned methods above. Due to the
5. Conclusions
The objective of this study was to use a novel plasma modification
combined with flotation for separating hazardous PVC form HDPE and
PET mixtures. It was done with an aim to promote the recycling of waste
plastics for their follow-up cleaner and sustainable disposal. This study
involved identification of plasma parameters, verification of flotation
separation, multi-characterization of polymer surface, speculation of
reaction mechanism, reusing of flotation medium, ageing risk and eco­
nomic analyses. The major conclusions of this study are summarized
below:
1. Plasma modification selectively suppressed the flotation perfor­
mance of polymers and corresponding sensitivity was observed as
HDPE > PVC > PET. The discharge power and exposure time under
positive polarity were identified as significant to control the sepa­
ration process.
2. Optimal Ej levels of plasma modification for PVC-HDPE and PVC-PET
mixtures were achieved as 12.0 and 15.0 kJ/m2. The maximum re­
covery and purity of separated PVC can reach above 93% in vali­
dation tests.
3. Amorphous LMWOMs emerged on the upper layer of polymers were
verified by multi-characterization, representing in varying degrees of
oxidation and chain scission induced by the plasma.
4. Mechanism of plasma modification was established based on
different radical pathways including the detailed hydrogen extrac­
tion and Norrish І type reactions, which provides a theoretical
reference for its application.
5. Flotation medium containing the frother TP can be used at least three
times with a stable performance. Ageing risk and economic analyses
demonstrated this method is economically feasible and with less
impacts to the recycled product.
The surface modification using plasma technique along with flota­
tion can be expected in the separation of waste plastics, improving their
recycling quality. This form of combined process broadens the way of
thinking for separation of plastic mixtures, which contributes to

Table 2
Comparison of recent surface modification methods for PVC flotation enhancement.
Method Separation Total cost Treatment Reagent Equipment Optimal index Reference
system (USD/t) time (min)

ClO2/heating PVC-PC 584.94 70.00 ClO2 effervescent tablet, Thermostat, Magnetic stirring, Purity 99.00%, Zhang et al.
TP. Flotation column. Recovery (2020a)
97.00%.
(NH4)2S2O8/ PVC-ABS, PVC- 476.67 30.00 (NH4)2S2O8, TP. Thermostat, Flotation column. Purity 99.70%, Zhang et al.
heating PS, PVC-PC. Recovery 100%. (2020b)
Surface micro- PVC-PET 1026.26 84.13 2-ethylhexanol, Zinc Microwave chemical reactor, Reflux Purity 99.25%, Zhao et al.
alcoholysis acetate, Methyl isobutyl condensation, Magnetic stirring, Recovery (2019b)
carbinol. Shielding gas, Flotation machine. 95.09%.
H2O2/ PVC-ABS, PVC- 431.08 30.00 H2O2, Methyl isobutyl Heating ultrasonic bath, Flotation Purity 100%, Thanh Truc
ultrasound PET, PVC-PC. carbinol. column. Recovery 100%. and Lee
irrigation (2019)
Fenton PVC-PMMA 493.49 6.00 H2O2, H2SO4, Ferrous Thermostat, Flotation column. Purity 97.61%, Wang et al.
oxidation sulfate, TP. Recovery 100%. (2019b)
Plasma PVC-HDPE, 450.03 <0.5 Air, TP. Industrial corona equipment, Flotation Purity 96.65%, This study
PVC-PET. column. Recovery
93.06%.

10
Y. Zhao et al.
reducing the resources crisis by recycling potential raw materials.
CRediT authorship contribution statement
Yue Zhao: Conceptualization, Methodology, Project administration,
Writing – original draft. Fengrong Han: Methodology, Software, Data
curation. Linyi Guo: Investigation, Data curation, Formal analysis.
Sharanjit Singh: Methodology, Writing – review & editing, Validation.
Haidong Zhang: Data curation, Formal analysis. Jun Zhang: Re­
sources, Funding acquisition.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
This study is supported by the Natural Science Basic Research Pro­
gram of Shaanxi (No. 2019JQ-899); the National Natural Science
Foundation of China (No.41672224); and the Research Foundation of
Baoji University of Arts and Sciences (Nos. ZK2018043, 209040071).
Special thanks are due to general manager Kewei Zhang and his Yunshi
Electronics (Shenzhen) Co. LTD for providing the available corona
equipment and for all his support during preparation.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.jclepro.2021.128569.
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