Received: 7 December 2018 Revised: 11 May 2019 Accepted: 13 June 2019

DOI: 10.1002/pc.25333

RESEARCH ARTICLE

Thermoplastic foaming mechanism and Pb2+ adsorption of

poly(vinyl alcohol)/shell powder porous composite

Lian Pu | Yeping Xie | Wenting Qiu | Li Li

State Key Laboratory of Polymer Materials

Engineering, Polymer Research Institute of
Sichuan University, Chengdu, People's
Republic of China
Correspondence
Li Li, State Key Laboratory of Polymer
Materials Engineering, Polymer Research
Institute of Sichuan University, Chengdu
610065, People's Republic of China.
Email: powerlily@scu.edu.cn
Abstract
Combining the respective advantages of PVA and shell in wastewater treatment,
poly(vinyl alcohol)/shell powder (PVA/SP) porous composite suitable for the
removal of heavy metal ions from wastewater was prepared via thermoplastic
foaming technology using water as both plasticizer and physical blowing agent. The
effects of SP content on the thermoplastic foaming mechanism including interactions
among components, water states and water evaporation behaviors, as well as cell
structure and Pb2+ adsorption property of the porous composite were studied. The

Funding information
National Natural Science Foundation of
China, Grant/Award Number: 51720105012;
Program of Innovative Research Team for
Young Scientists of Sichuan Province,
Grant/Award Number: 2016TD0010; State
Key Laboratory of Polymer Materials
Engineering, Grant/Award Number: sklpme
2014-1-04
results showed that SP could form different hydrogen bonding or coordination inter-
actions with water and PVA, making free water in system reduced and nonfreezing
water increased, thus realizing the controllable foaming of water and avoiding the
formation of the big cells caused by intensive evaporation of water. SP particles
could also act as heterogeneous nucleating agents to effectively increase the number
of heterogeneous nucleating points in the system, resulting in the formation of denser
and more uniform cells. With the increase of SP content, the adsorption capacity of
porous composite on Pb2+ increased, and reached the maximum at 10 wt%, that is,
31.1 mg/g, higher than that of pure SP powders, that is, 23.4 mg/g, ascribing to the
good dispersion of SP in PVA matrix as well as the high hydrophilicity of PVA
porous material.

KEYWORDS
adsorption capacity, cell structure, poly(vinyl alcohol), shell powder, thermoplastic foaming

1 | INTRODUCTION used adsorption materials, for example, activated carbon and

Water pollution caused by heavy metal ions has always been
one of the major environmental issues all over the world,
and has posed a significant threat to the environment, public
hygiene and human health,[1,2] due to the strong stability and
high toxicity of heavy metal ions even at low concentration.
Adsorption method is one of the most widely applied tech-
nologies to remove the heavy metal ions from waste water,
for its easy operation and no secondary pollution, by using
the adsorption material with large adsorptive capability and
high adsorptive rate. However, the cost of the commonly
carbon nanotube, are so high that the development of a new
adsorption material with high efficiency and low price is
urgently needed.[3]
Poly(vinyl alcohol) (PVA) is a highly hydrophilic and
nontoxic polymer with excellent comprehensive properties,
such as good mechanical strength, thermal stability, chemi-
cal stability, biocompatibility, as well as certain adsorption
on heavy metal and organic matter.[4] Compared with PVA,
PVA porous material has higher adsorption capacity ascrib-
ing to its ultrahigh specific surface area, thus having more
potential applications in the removal of heavy metal ions,

4658 © 2019 Society of Plastics Engineers wileyonlinelibrary.com/journal/pc Polymer Composites. 2019;40:4658–4668.

PU ET AL.
the fix of activated sludge, the treatment of eutrophication
wastewater and oily wastewater, etc. For example, the phos-
phate in eutrophic water body could be removed by using
PVA hydrogel as adsorbent, and the maximum adsorption
capacity was 11.5 mg-P/g.[5] However, PVA alone can usu-
ally not achieve the quite good adsorption. To improve the
adsorption capacity of PVA on heavy metal ions, a lot of
fillers, such as SiO2,[6] TiO2,[7] and MWCNT[8] and
CaCO3[9] have been used. Recently, shell, the outer skin of
mollusk, is attracting attentions for its nature porous struc-
ture and quite low price.
Shell is a kind of organic/inorganic hybrid material with spe-
cial cross-layered structure.[10] The calcium carbonate (CaCO3)
layers with the mass ratio of 95% in shell are connected by
extremely thin organic layers (protein, trace inorganic elements,
phospholipids, and polysaccharides). This unique layered struc-
ture can hamper the development of crazes or cracks when suf-
fering intense impact, thus endowing shell with quite high
strength and toughness, for example, its tensile strength is 3000
times more than that of the geological mineralized CaCO3.[11]
Now, shell is being extensively studied in the fields of
biochemistry,[12] food industry,[13,14] biomedicine,[15] bionic
materials,[16] and bioenergy.[17,18] But the most attractive thing
for shell is its rich irregular porous surface and regulating ability
on pH value,[19] which are not belong to CaCO3, although the
main component of shell is CaCO3. Accordingly, shell has been
used as an ideal carrier for microorganism attachment and
heavy metal ions. For example, Ting-chu Hsu[20] adopted oyster
shell to adsorb Cu2+ and Ni2+ in industrial wastewater and
found that the adsorption fitted good to the isotherm of Lang-
muir, Freundlich, and Dubinin-Kaganer-Radushkevich; Solmin
Jung[21] studied the feasibility of oyster shell in wastewater
treatment, and found that oyster shell could remove the methy-
lene blue in water and inhibit the growth of bacteria with the
synergistic effect of metal oxide; NA Oladoja[22] adopted the
thermal treated shell with greater specific surface area to achieve
the high adsorption efficiency for phosphate; etc. But in these
studies, shells were almost used in the form of powders for
maximizing their adsorption effects, making them quite difficult
to be collected and reused, and consequently limiting their large
scale applications in waste water treatment.
To realize the large-scale and reasonable applications of
shells, simultaneously considering the respective advantages
of PVA and shell in wastewater treatment, in this article, a
novel porous adsorbing material composed of PVA and shell
powders (SP) was prepared by using our self-developed
thermoplastic foaming technology for PVA, that is, using
water as both plasticizer and blowing agent.[23–26] The
effects of SP content on the foaming mechanism including
interactions among the components, water states in system,
water evaporation behaviors, cell structure as well as adsorp-
tion properties and adsorption mechanism of the porous
4659
composite on heavy metal ion, for example, Pb2+, were stud-
ied. The adsorption properties of PVA/SP porous composite,
SP, and other studies were also compared.
2 | EXPERIMENTAL
2.1 | Materials
PVA (degree of polymerization: 1750 ± 50, hydrolysis degree:
99%) was purchased from Sichuan Vinylon Works, SINOPEC
(China). Abandoned oyster shell was obtained from Zhaoan
(Fujian Province, China). Lead nitrate was purchased from
Kelon Chemical Reagent Factory (Chengdu, China). Deionized
water was used throughout the whole experiment.
2.2 | Sample preparation
Abandoned oyster shells were first washed, dried and pre-
grinded on an airflow crusher (Xin Zhen Enterprise Co., Ltd.,
China) to obtain SP with the average particle size of 17 μm.
Then, quantified water and SP were mixed under the effect of
ultrasonic oscillation to form stable suspension. After that, a
certain amount of dried PVA was added and uniformly
blended. The mixture was sealed at ambient temperature until
the solution was completely swelled into PVA.
The swelled PVA/SP blends with 25 wt% water were then
filled into an airtight rectangle metal frame (12 × 12 × 2 mm,
self-made) and heated at 170
C on a hot press machine (Sima
Weili Rubber & Plastics machinery factory Co., Ltd., China).
The clamping force was 10 MPa. After melting for 15 minutes,
the clamping force of the hot press was immediately released
to atmospheric pressure to make the blends foamed. All the
samples were prepared under the same conditions to avoid the
extra impact factor to the morphology of the porous composite.
The fabrication process was shown in Figure 1.
2.3 | Characterization
2.3.1 | Differential scanning
calorimetry (DSC)
A TA-Q20 thermal analyzer (TA Instrument, Co.) was used
to explore the melting behaviors of water in water-swelled
PVA/SP systems. About 5 mg samples were heated up from
−40
C to 40
C at a rate of 5
C/min under a nitrogen atmo-
sphere with a flow rate of 50 mL/min.
2.3.2 | Thermal gravity analysis (TG)
Isothermal mass loss of the system was studied by using a TA
Q50 thermogravimetric analyzer (TA Instrument, Co.) under
a nitrogen atmosphere with a flow rate of 50 mL/min. The
samples were first quickly heated from room temperature to
4660
150
C at a heating rate of 40
C/min and then fixed at 150
C
to record the relationship between mass loss and time.
2.3.3 | Fourier transform infrared
spectroscopy (FTIR)
Interactions in system were tested by Nicolet 6700 IR spec-
trometer (Thermo Scientific Company) in the ATR mode at
room temperature. The tested samples were obtained by hot
pressing the water-swelled systems into films on a semi-
automatic pressure molding machine (Sima Weili Rubber &
Plastics machinery factory Co., Ltd., China) at 130
C. In
order to keep the consistency of water content in all samples,
the films were first dried in a vacuum drying oven at 80
C
until the constant weight, and then were supplied with 35 wt
% moisture. The average thickness of the films was 80 μm.
2.3.4 | Scanning electron microscopy (SEM)
Cell morphology of the porous composite was observed on
an Inspect SEM Instrument (FEI Co., Ltd.) at accelerating
voltage of 5 kV. The samples were freeze-fractured in liquid
nitrogen and then sputtered with gold before test.
2.3.5 | Expansion ratio
The expansion ratio (Φ) of the porous composite was evalu-
ated as a specific ratio of the final thickness and frame thick-
ness by the following equation:
hf
ϕ= ð1Þ
hm
Where hf (mm) and hm (mm) are the thicknesses of the
expanded foam and metal frame, respectively.
2.3.6 | Cell density
Cell density (cell/cm3) was assessed according to the follow-
ing formula equation[27]:
 2 32
nM
Cell density = ×ϕ ð2Þ
A
Where n is the number of cells in the SEM micrograph,
A (cm2) and M (cm2) are the area and magnification factors
of the micrograph, respectively.
PU ET AL.
FIGURE 1 Schematic
illustration of the fabricating process
of PVA/SP composite foam. PVA,
poly(vinyl alcohol); SP, shell powder
[Color figure can be viewed at
wileyonlinelibrary.com]
2.3.7 | Porosity
Porosity of the porous composite was determined by ethanol
extraction method.[28] The mass (m [g]) and apparent volume
(V [cm3]) of the sample were measured after drying, and the
mass (m1 [g]) was measured by filling the density bottle with
ethanol. After loading the weighed sample into the density bot-
tle, the ethanol is vacuumed to enter the sample, and finally
filled into the density bottle to measure its mass (m2 [g]). The
porosity (%) is calculated by the following equation:
V − ½m1 − ðm2 −mÞ=ρ
Porosity = × 100% ð3Þ
V
Where ρ (g/cm3) is the density of ethanol.
2.3.8 | Specific surface area
Specific surface area of the porous composite was tested on
QUANTACHROME MERCURY POROSIMETERS 33 (Anton
Paar, Ltd, Austria) with pressure up to about 220 MPa, Hg sur-
face tension of 480 erg/cm2 and Hg contact angle of 140
.
2.3.9 | Adsorption performance
PVA/SP porous composites containing different SP content
(0%, 1 wt%, 5 wt%, 10 wt%, 15 wt%) (1 g) were immersed in
a conical flask containing 100 mL of Pb2+ solution (the initial
concentration is 350 mg/L). The best adsorption pH value was
adjusted by adding 0.1 mol/L hydrochloric acid and sodium
hydroxide solution. After oscillation and adsorption on a
shaker at a speed of 150 rpm for 24 hours at room temperature
(25
C), the ion concentration changes in the solution before
and after adsorption were measured via atomic absorption
spectroscopy (AAS, SpectrAA 220FS, VARIAN Company).
The isotherm adsorption of PVA/SP porous composite
with 10 wt% SP was obtained with the same steps. The con-
centrations of Pb2+ solution were 100, 200, 300, 400, and
500 mg/L, respectively, and the pH value was 3.
3 | R E S U L T A N D DI S C U S S I O N
3.1 | Intermolecular interactions in system
In our foaming system, water took the role of both plasti-
cizer and physical blowing agent, so the studies on its state,
PU ET AL.
which directly decided its evaporation behavior, that is,
foaming behavior, were quite important. Water state was
mainly influenced by the interactions between water and
other components in system.[29,30] Figure 2 showed the FT-
IR spectra of SP and water-swelled PVA/SP, and the
enlarged spectra of the peaks in the range of 3000 to
3800 cm−1 and 1340 to 1500 cm−1 were respectively shown
in Figure 3. For water-swelled PVA (Figure 2), ascribing to
the multi-hydrogen bonding formed between PVA and
water, a fairly wide hydroxyl stretching band, consisting of
free and bound OH, appeared in the range of 3000 to
FIGURE 2 FT-IR spectrum of SP and water-swelled PVA/SP
(a. SP, SP content of b-f: 0, 1, 5, 10, 15 wt%). FT-IR, Fourier transform
infrared spectroscopy; PVA, poly(vinyl alcohol); SP, shell powder
[Color figure can be viewed at wileyonlinelibrary.com]
F I G U R E 3 FT-IR spectrum of water-swelled PVA/SP from A, 3000 cm−1 to 3800 cm−1 and B, 1340 cm−1 to 1500 cm−1. (Shell content of
b-f: 0, 1, 5, 10, 15 wt%). FT-IR, Fourier transform infrared spectroscopy; PVA, poly(vinyl alcohol); SP, shell powder [Color figure can be viewed at
wileyonlinelibrary.com]
4661
3800 cm−1.[31,32] With the further incorporation of SP parti-
cles, Ca2+ in SP formed coordination interactions with the
hydroxyl groups of PVA and hydration with water, which
might be weaker than the hydrogen bonding between PVA
and water, making the band in 3000 to 3800 cm−1 shifted to
higher wavenumber, and the more the SP content, the more
the deviation of this band (Figure 3A). Meanwhile, a peak at
about 1420 cm−1, corresponding to the overlapping peak of
the characteristic vibrations of CO32− in SP and C H in
PVA, gradually appeared (Figure 3B), enhanced and shifted
to lower wavenumber with the increase of SP content. This
could be attributed to the coordination interactions between
Ca2+ in SP and the hydroxyl groups of PVA, which made
the electron cloud density of C O bond in PVA moved to
O and the electron cloud density of C H bond reduced,
finally leading to the shift of both the characteristic absorp-
tion peak of C H as well as CO32− to lower wavenumber,
reflected in FT-IR spectra by that the whole overlapped peak
moved to low wavenumber. According to the results of FT-
IR, 4 interaction models could be proposed in water-swelled
PVA/SP system, that is, PVA-water, PVA-water-SP, water-
SP, and PVA-SP.
3.2 | Water state in system
Water state in PVA was influenced by lots of elements,
including the initial water content, added modifiers, foaming
conditions, etc. Here, in order to ensure the reliability of data
and reduce the impact factors as far as possible, all the
foaming parameters, except the SP content, were consistent.
Figure 4 showed the influence of SP content on water states
in PVA, and the corresponding thermal data were listed in
4662 PU ET AL.

Table 1. In order to intuitively analyze the changes of each per unit mass (333.5 J/g)[34]; Ww is the weight of the whole
kind of water in system, the equations below were adopted initial water and Ws is the weight of the swelled PVA.
to calculate the mass of free water (Wf), freezable bound Furthermore, the weight ratio of different water to whole
water (Wfb) and nonfreezing water (Wnb), respectively.[33] initial water was calculated by the following equation:

W fb = ðW s × ΔH fb Þ=ΔH 0 ð4Þ V i = W i =W w ð7Þ

Where i represents free water (f ), freezable bound water

W f = ðW s × ΔH f Þ=ΔH 0 ð5Þ (fb) or nonfreezing water (nf ). The calculated data were
listed in Table 1.
Apparently, water in PVA showed two endothermic
peaks in DSC curve within the scope of −35
C to 35
C
W nf = W w −W fb −W f ð6Þ
(Figure 4), respectively representing the phase transition
peaks of free water at about −0.6
C and freezable bound
where ΔHfb and ΔHf represent the phase transition enthalpy
water at about −11
C. With the addition of SP particles,
difference of freezable bound water and free water in
compared with PVA, the better hydrophilicity, smaller vol-
swelled PVA during the heating-up process, respectively;
ΔH0 is the phase transition enthalpy difference of pure water ume and larger specific surface area of SP particles endowed
them with greater chance to interact with water, making the
number of water that directly interacted with PVA reduced.
The water-SP interaction was weaker than PVA-water inter-
action, leading the thermodynamic properties of water that
a
only interacted with SP more like bulk water. In this way,
the phase transition peak of free water in PVA/SP only had a
b slight shift to lower temperature and the peak area had a
minor increase, that is, free water content increased a little.
c
The residual water surely got more chance to directly inter-
Endo

d act with the hydroxyl groups of PVA via hydrogen bonding,

resulting in the increase of the content of nonfreezing water
e in system. When the residual water further interacted with
SP to form the interaction model of PVA-water-SP, water
could be restricted to a deeper extent, also contributing to
the increase of the nonfreezing water content. Correspond-
ingly, the freezable bound water reduced. This was reflected
-30 -20 -10 0 10 20 30
in DSC curves by that the phase transition peak of water at
Temperature(°C)
about −11
C weakened with the increase of SP content and
FIGURE 4 DSC curves of water-swelled PVA/SP (SP content of even disappearing when SP content reached 15 wt%. The
a-e: 0, 1, 5, 10, 15 wt%). DSC, differential scanning calorimetry; PVA, changes of water states with the addition of SP were benefi-
poly(vinyl alcohol); SP, shell powder [Color figure can be viewed at cial to the controllable foaming of the water-swelled PVA
wileyonlinelibrary.com] system.

TABLE 1 Classification of water states in water-swelled PVA/SP

Free water Freezable bound water

SP content Nonfreezing


per wt% Peak 1 ( C) Enthalpy per J/g Vf Peak 2 (
C) Enthalpy per J/g Vfb water Vnb
0 −0.61 11.75 0.14 −11.44 7.97 0.09 0.77
1 −0.62 13.52 0.16 −12.23 4.48 0.06 0.78
5 −0.65 11.15 0.14 −12.30 4.99 0.06 0.80
10 −0.66 12.17 0.16 −12.69 1.73 0.02 0.82
15 −0.76 8.57 0.15 / / / 0.83

Abbreviations: PVA, poly(vinyl alcohol); SP, shell powder.

PU ET AL. 4663

100 curves were presented in Figure 6. Apparently, each water

a
b evaporation curve could be divided into two stages, that is,
90
c rapid evaporation stage (stage 1) and slow evaporation stage
d (stage 2). At the first stage, the evaporation of free water
80
e
with no interactions with PVA or freezable bound water with
Weight Loss /%

70 weak interactions with PVA dominated due to their low

evaporation energy barrier, so water presented rapid evapo-
60
ration. While at the second stage, more and more energy
50
was absorbed by system, leading more nonfreezing water
transferred into freezable bound water even free water to
40 Stage 1 Stage 2 evaporate. This was a complicate and long process, so the
water evaporation rate gradually reduced and last reached
30
0 5 10 15 20 25
zero. With the addition of SP, the hydrogen bonding and
Time (min) coordination interactions among PVA, water and SP chan-
ged the water state in system and further inhibited the water
FIGURE 5 Evaporated water content vs initial water content in evaporation, which was reflected in the TGA curves by that
water-swelled PVA/SP at 150
C. (SP content of a-e: 0, 1, 5, 10, 15 wt%). both the water evaporation rate and the evaporation capacity
PVA, poly(vinyl alcohol); SP, shell powder [Color figure can be viewed
reduced. This further confirmed that the addition of SP was
at wileyonlinelibrary.com]
beneficial to realize the controllable foaming of water.

Stage 1 Stage 2
0 5 10
Time (min)
F I G U R E 6 DTG curve of water-swelled PVA/SP at 150
C.
(SP content of a-e: 0, 1, 5, 10, 15 wt%). DTG, derivative
thermogravimetry; PVA, poly(vinyl alcohol); SP, shell powder [Color
figure can be viewed at wileyonlinelibrary.com]
3.3 | Evaporation behavior of water in system
To further analyze the effect of SP on the evaporation of
water, the isothermal weight loss behaviors of water-swelled
PVA/SP at 150
C were studied. Considering the high
decomposition temperature of PVA and SP (>200
C), the
weight loss at 150
C could only cause by the water evapora-
tion. So, we removed the weight of PVA and SP, and got
the pure water evaporation curves, as shown in Figure 5.
The corresponding derivative thermogravimetry (DTG)
a
3.4 | Cell morphology of PVA/SP porous
b composite
c
Figure 7 showed the cell morphologies of PVA/SP porous
d
e
composites, and the corresponding expansion ratio, cell size,
cell density as well as specific surface area were presented in
Figure 8. The cell formation usually includes three stages:
initial nucleation, cell growth and cell solidification.[34] The
initial nucleation stage is an important stage in the whole
foaming process because it determines the final cell density,
expansion ratio and cell size. For water-swelled PVA sys-
tem, the cell was mainly formed through homogeneous
nucleation after the pressure relief. The high free energy bar-
rier of homogeneous nucleation resulted in the low cell num-
15 20 bers and uneven cell size, as shown in Figure 7A. With the
addition of SP, a heterogeneous nucleating agent, the
foaming process transformed from homogeneous nucleation
to heterogeneous nucleation. The lower surface free energy
barrier of the heterogeneous nucleation and the good disper-
sion of SP in system created more nucleation sites, making
more bubbles formed during the process of pressure relief
and resulting in a smaller cell size (Figures 7B,C and 8B)
and a higher cell density (Figure 8C). And the interactions
among OH in PVA, water and Ca2+ in SP enhanced the
confinement of the system on water, making free water in
system reduced and bound water increased, avoiding the for-
mation of the uncontrollable cell caused by severe evapora-
tion of water, thus further improving the cell structure of the
porous composite.
However, with the increase of SP, the expansion ratio of
the porous composite gradually decreased (Figure 8A), due
to the steric hindrance effect of the layered SP on the
4664 PU ET AL.

FIGURE 7 SEM photos of PVA/SP porous composites (SP content of A-E: 0, 1, 5, 10, 15 wt%) and F, the appearance of the porous material.
PVA, poly(vinyl alcohol); SEM, scanning electron microscopy; SP, shell powder [Color figure can be viewed at wileyonlinelibrary.com]

F I G U R E 8 A, Expansion
ratio, B, cell size, C, cell density,
and D, specific surface area of
PVA/SP porous composites. PVA,
poly(vinyl alcohol); SP, shell powder
PU ET AL.
movement of PVA molecular chains, which enhanced the
melt strength of the system and made the cell growth more
difficult. The effect of SP on the melt strength of the system
could be indirectly identified from the increased melt viscos-
ity with the addition of SP, as shown in Figure 9.
It should be noticed that when SP content reached 10 wt%,
some large cells appeared (Figure 7D), possibly due to the
aggregation of some SP particles, which weakened their
nucleation efficiency. Further increasing SP content to 15 wt
%, quite irregular cells formed (Figure 7E) ascribing to the
further enhanced melt strength caused by SP, which limited
the cell growth to a deeper extent. The gradually enhanced
melt strength also meant that the cell wall was more and more
difficult to be broken through, so the porosity of the porous
material decreased with SP content increasing from 0 to 15 wt
FIGURE 9 Dependence of apparent viscosity on shear rate of
water-swelled PVA and PVA/SP. PVA, poly(vinyl alcohol); SP, shell
powder [Color figure can be viewed at wileyonlinelibrary.com]
FIGURE 10 A, Effect of pH value and B, SP content on adsorption capacity of PVA/SP porous composites. PVA, poly(vinyl alcohol);
SP, shell powder [Color figure can be viewed at wileyonlinelibrary.com]
4665
%, i.e. 80.2%, 73.9%, 69%, 67.4%, and 65.3%, respectively.
Under the comprehensive effects of cell size, cell density as
well as porosity, the specific surface area of PVA/SP porous
composite presented different changes with SP content, that
is, first increased, reached the maximum at 10 wt% SP con-
tent, then sharply decreased.
3.5 | Adsorption property on Pb2+
Among all heavy metal ions, the toxicity of Pb2+ might be
the most serious, because Pb2+ can act on all the systems
and organs of human body, especially the nerves. Accord-
ingly, here, the adsorption capacity of PVA/SP porous com-
posite on Pb2+ was studied, as shown in Figure 10.
During the adsorption process, the pH value of the solu-
tion, which can influence the charge distribution on the sur-
face of the adsorbent, the solubility and the existence form
of metal ion as well as the ionization degree of the adsor-
bent, plays important role in the adsorption capacity of a
material on heavy metal ions in water.[35,36] To find out the
best pH value, the adsorbed solution with pH value from
1 to 5 was obtained by using 0.1 M H3NO3 and 0.1 M
NaOH. As shown in Figure 10A, with the increase of pH
value, the adsorption capacity of PVA/SP porous composite
on Pb2+ first increased and then decreased, the maximum
adsorption capacity achieved at pH = 3. In the strong acid
solution (pH = 1), H+ would occupy more binding sites on
the surface of the adsorbent, leading to the low adsorption
on Pb2+, only 0.36 mg/g. When pH value increased, the
binding sites occupied by H+ gradually exposed, so the
adsorption on Pb2+ increased. However, at relatively high
pH value, Pb in solution mainly existed as Pb(OH)2, rather
than Pb2+, the adsorption on Pb2+ decreased again.
4666
Figure 10B showed the Pb2+ adsorption capacity of
PVA/SP porous composite at the pH value of 3. Apparently,
pure PVA porous material presented quite poor adsorption
FIGURE 11 Pb2+ adsorption mechanism diagram of A, SP
and B, PVA/SP porous composite. PVA, poly(vinyl alcohol); SP, shell
powder [Color figure can be viewed at wileyonlinelibrary.com]
FIGURE 12 A, Langmuir model and B, Freundlich model for the adsorption of Pb2+ onto PVA/SP porous composite. PVA, poly(vinyl
alcohol); SP, shell powder [Color figure can be viewed at wileyonlinelibrary.com]
PU ET AL.
capacity on Pb2+. While with the addition of SP, the adsorp-
tion capacity of porous material on Pb2+ greatly increased and
reached the maximum, that is, 31.1 mg/g, when SP content
was 10 wt%. This might be attributed to the ion exchange of
the main component of SP, that is, CaCO3, with Pb2+.[37] With
the increase of SP, CaCO3 content increased, that is, Ca2+ used
for ion exchange increased, leading to the increase of Pb2+
content adsorbed by porous composite. However, when SP
reached 15 wt%, the adsorption capacity of the porous com-
posite on Pb2+ decreased to 25.6 mg/g, due to the enhanced
interactions between PVA and SP, which increased the physi-
cal cross-linking points in the system, and the reduced porosity
as well as specific surface area of the porous composite. All
retarded the entering of Pb2+ solution into the interior of the
porous composite to a certain extent, and had greater effects
on the adsorption capacity on Pb2+. Compared with the
adsorption capacity on Pb2+ of other adsorbents, for example,
iron-coated sand (1.211 mg/g),[38] Al2O3-supported iron oxide
(28.98 mg/g), [39] diatomite (24.0 mg/g),[40] etc., the adsorp-
tion effect of our porous foam was good. However, the adsorp-
tion capacity of our material on Cd2+ (6.05 mg/g) was much
lower than that of Pb2+ due to the precipitation of three dimen-
sional prismatic crystals on the surface of material with the
proceeding of Cd2+ adsorption, which would cover the surface
of shell powder and reduce its adsorption effect on Cd2+.
To intuitively identify the combination effect of PVA and
SP on Pb2+ adsorption, the Pb2+ adsorption mechanism dia-
gram of SP and PVA/SP porous composite was given, as
shown in Figure 11. And the Pb2+ adsorption capacity of SP
at pH = 3 was tested, that is, 23.4 mg/g, lower than the porous
composite with 10 wt% SP, that is, 31.1 mg/g. Ascribing to
the main component (CaCO3) and rich irregular porous surface
of SP, SP is considered as an effective adsorption material on
PU ET AL.
T A B L E 2 Parameters and regression
Langmuir model
coefficients (R2) for the two equilibrium
models C0 (mg/L) qm (mg/g)
100–500 70.92
heavy metal ions. However, when singly using SP powders,
the calcium ions were liable to stack together (Figure 11A),
thus retarding the full exchange of Pb2+ and Ca2+ and
resulting in the relatively low Pb2+ adsorption capacity. While
in PVA matrix, the good dispersion of SP and the good hydro-
philicity of PVA dramatically increased the contact opportu-
nity of Ca2+ and Pb2+, ultimately increasing the Pb2+
adsorption of the porous composite (Figure 11B).
The adsorption isotherm was then used to study the
adsorption mechanism between the porous composite and Pb2
+
. And two models, for example, Langmuir and Freundlich,
were adopted. Langmuir model (Equation (8)) is based on a
homogeneous mono layer adsorption that all active sites have
the same affinity to adsorbate, whereas Freundlich model
(Equation (9)) is based on a heterogeneous multilayer adsorp-
tion owning to the variety of the binding sites. [41]
1 1 1 1
= • + ð8Þ
qe K L qm C e qm
1
lgqe = lgK F + lgC e ð9Þ
n
where qe is the equilibrium adsorption capacity (mg/g), Ce
is the equilibrium concentration (mg/L), qm is the maximum
adsorption capacity (mg/g), and KL is the Langmuir equilib-
rium constant (L/mg). KF and n are Freundlich constants
related to the adsorption capacity and the adsorption inten-
sity, respectively. The larger the value of KF is, the higher
the degree of heterogeneity is; n > 1 means that the adsorp-
tion process is spontaneous, and the larger the value of n is,
the higher the degree of spontaneousness is.
Figure 12 showed the curves fitted to the Langmuir model
(A) and Freundlich model (B) in an initial concentration range
of 100 to 500 mg/L, and the adsorption isotherm data were
summarized in Table 2. Apparently, the Pb2+ adsorption pro-
cess for the porous composite was more suitable to be
described by Freundlich isotherm attributing to its relatively
higher (R2 = .964) than Langmuir isotherm (R2 = .956),
i.e. the adsorption process inclined more to the heterogeneous
adsorption, and this process was spontaneous (n = 1.342).
4 | CONCLUSION
By using water as both plasticizer and physical blowing
agent, PVA/SP porous composite with potential use in the
4667
Freundlich model
KL (L/mg) R2 n KF (L/mg) R2
0.067 .956 1.342 4.864 .964
removal of heavy metal ions from waste water was prepared.
The effects of SP content on the foaming mechanism as well
as the adsorption capacity of PVA/SP porous composite on
Pb2+ were studied. The results showed that SP particles
could form hydrogen bonding and coordination interactions
with both PVA and water, thus altering the proportion of
three kinds of water in system and realizing the controllable
evaporation of water in system. SP particles could also act
as heterogeneous nucleation agent in system, making the
system change from homogeneous nucleation to heteroge-
neous nucleation, so effectively increased the number of
nucleation sites and improved the cell structure of the mate-
rial. However, too high SP content restricted the movement
of PVA molecular chains to a greater extent, contrarily
increasing the melt strength of the system and decreasing the
cell numbers. With the increase of SP content, the adsorption
capacity of PVA/SP porous composite on Pb2+ increased,
and reached the highest at 10 wt% SP content, that is,
31.1 mg/g. The material developed in this paper would be a
good candidate for wastewater treatment caused by heavy
metal ions.
A C KN O W L E D G M E N T
This work was financially supported by National Natural
Science Foundation of China (51720105012), Program of
Innovative Research Team for Young Scientists of Sichuan
Province (2016TD0010), and State Key Laboratory of Poly-
mer Materials Engineering (Grant No. sklpme 2014-1-04).
OR CI D
Li Li https://orcid.org/0000-0002-3576-4372
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How to cite this article: Pu L, Xie Y, Qiu W, Li L.
Thermoplastic foaming mechanism and Pb2+
adsorption of poly(vinyl alcohol)/shell powder porous
composite. Polymer Composites. 2019;40:4658–4668.
https://doi.org/10.1002/pc.25333