Review

Properties and Applications of Polyvinyl Alcohol,

Halloysite Nanotubes and Their Nanocomposites
Tayser Sumer Gaaz 1,2, *, Abu Bakar Sulong 1, *, Majid Niaz Akhtar 1,3 , Abdul Amir H. Kadhum 4 ,
Abu Bakar Mohamad 4,5 and Ahmed A. Al-Amiery 4
Received: 15 October 2015; Accepted: 11 December 2015; Published: 19 December 2015
Academic Editor: Derek J. McPhee
1 Department of Mechanical & Materials Engineering, Faculty of Engineering & Built Environment,
Universiti Kebangsaan Malaysia, Bangi, Selangor 43600, Malaysia; majidniazakhtar@ciitlahore.edu.pk
2 Department of Machinery Equipment Engineering Techniques, Technical College Al-Musaib,
Al-Furat Al-Awsat Technical University, Al-Musaib, Babil 51009, Iraq
3 Department of Physics, COMSATS Institute of Information Technology, Lahore 54000, Pakistan
4 Department of chemical & Process Engineering, Faculty of Engineering & Built Environment,
Universiti Kebangsaan Malaysia, Bangi, Selangor 43600, Malaysia; amir@eng.ukm.my (A.A.H.K.);
drab@eng.ukm.my (A.B.M.); dr.ahmed1975@gmail.com (A.A.A.A.)
5 Fuel Cell Institute, University Kebangsaan Malaysia (UKM), Bangi, Selangor 43000, Malaysia
* Correspondence: taysersumer@gmail.com (T.S.G.); abubakar@ukm.edu.my (A.B.S.);
Tel.: +60-11-210-60892 (T.S.G.); +60-38-921-6678 (A.B.S.); Fax: +60-38-925-9659 (A.B.S.)

Abstract: The aim of this review was to analyze/investigate the synthesis, properties, and applications
of polyvinyl alcohol–halloysite nanotubes (PVA–HNT), and their nanocomposites. Different polymers
with versatile properties are attractive because of their introduction and potential uses in many fields.
Synthetic polymers, such as PVA, natural polymers like alginate, starch, chitosan, or any material with
these components have prominent status as important and degradable materials with biocompatibility
properties. These materials have been developed in the 1980s and are remarkable because of
their recyclability and consideration of the natural continuation of their physical and chemical
properties. The fabrication of PVA–HNT nanocomposites can be a potential way to address some of
PVA’s limitations. Such nanocomposites have excellent mechanical properties and thermal stability.
PVA–HNT nanocomposites have been reported earlier, but without proper HNT individualization
and PVA modifications. The properties of PVA–HNT for medicinal and biomedical use are attracting
an increasing amount of attention for medical applications, such as wound dressings, drug delivery,
targeted-tissue transportation systems, and soft biomaterial implants. The demand for alternative
polymeric medical devices has also increased substantially around the world. This paper reviews
individualized HNT addition along with crosslinking of PVA for various biomedical applications
that have been previously reported in literature, thereby showing the attainability, modification of
characteristics, and goals underlying the blending process with PVA.

Keywords: polyvinyl alcohol; halloysite nanotubes; properties; biomedical application; biocompatibility

1. Introduction
Polyvinyl alcohol (PVA), which is essentially made from polyvinyl acetate through hydrolysis, is
easily degradable by biological organisms and in water is a solubilized crystalline structure polymer [1].
PVA is an artificial polymer that has been used during the first half of the 20th century worldwide.
It has been applied in the industrial, commercial, medical, and food sectors and has been used to
produce many end products, such as lacquers, resins, surgical threads, and food packaging materials
that are often in contact with food [2]. PVA is a biodegradable imitation of natural polymers used

Molecules 2015, 20, 22833–22847; doi:10.3390/molecules201219884 www.mdpi.com/journal/molecules

Molecules 2015, 20, 22833–22847

in paper coating and textile sizing [3]. This polymer is widely used by blending with other polymer
compounds, such as biopolymers and other polymers with hydrophilic properties; it is utilized
for various industrial applications to enhance the mechanical properties of films because of its
compatible structure and hydrophilic properties [4]. Some man-made polymers, which are made
from non-renewable and non-biodegradable sources, such as PVA, are available [5]. Polymers that
are biologically decomposable originate from petroleum-based synthetic materials, which decompose
naturally under aerobic (composting) or anaerobic (landfill) conditions [6,7]. PVA is a widely used
thermoplastic polymer that is benign to living tissues, harmless, and nontoxic. This polymer is widely
investigated because
Molecules ofpage–page
2015, 20, its use in cross-linked products and nanofillers [6,8,9]. PVA is a biodegradable
polymer, and its degradability is enhanced through hydrolysis because of the presence of hydroxyl
compounds, such as biopolymers and other polymers with hydrophilic properties; it is utilized for
groups on various
the carbon atoms.
industrial Moreover,
applications it is water-soluble
to enhance and has of
the mechanical properties a hydrophilic
films because ofnature [6,10–14]. Rates
its compatible
and environmental
structure and conditions
hydrophilic forproperties
degradation may man-made
[4]. Some vary for many polymers,polymers,
which are suchmade as PVA
from [6,15–18];
non-renewable
these conditions include andcomposting
non-biodegradable in the sources,
presencesuch ofas PVA,
oxygen, are available
underneath [5]. Polymers that are
soil layers, in aqueous
biologically decomposable originate from petroleum-based synthetic materials, which decompose
media, andnaturally
even inunder anaerobic circumstances. In the paper industry, several synthetic, copolymers, and
aerobic (composting) or anaerobic (landfill) conditions [6,7]. PVA is a widely used
conventional polymers, such
thermoplastic polymer that asispolyurethane (PU), harmless,
benign to living tissues, polystyrene, and maleic
and nontoxic. anhydride
This polymer is widelySBR, SMA,
polyacrylamide PAM, and PVA, are typically utilized to enhance the features and characteristics of
investigated because of its use in cross-linked products and nanofillers [6,8,9]. PVA is a biodegradable
polymer, a
paper by coating and its degradability
film layer onto the is enhanced
whole through hydrolysis
sheet [7,19]. PVA because of the presence
is a major artificial of polymer
hydroxyl that has
groups on the carbon atoms. Moreover, it is water-soluble and has a hydrophilic nature [6,10–14]. Rates
been available for more than nine decades. PVA is synthesized through the saponification process of
and environmental conditions for degradation may vary for many polymers, such as PVA [6,15–18];
poly(vinylthese
acetate) [20,21]
conditions and has
include long been
composting in theused by blending
presence of oxygen, with other soil
underneath natural
layers,polymers
in aqueousbecause of
its film-forming
media, and features
even in [22,23].
anaerobic The complete
circumstances. In dissolution of PVA
the paper industry, severalinsynthetic,
water iscopolymers,
bound byand its intrinsic
conventional polymers, such as polyurethane (PU), polystyrene, ˝and
properties, which require the water temperature to be at ~100 C with a holding time of 30 min [23]. maleic anhydride SBR, SMA,
polyacrylamide PAM, and PVA, are typically utilized to enhance the features and characteristics of
All PVA grades are hydrophilic and depend on certain factors, such as molecular weight, element
paper by coating a film layer onto the whole sheet [7,19]. PVA is a major artificial polymer that has
dimensions been available for moreand
of distribution, thanparticle crystal
nine decades. PVA structure
is synthesized[23,24].
throughThe resulting gel
the saponification properties
process of have
poly(vinyl acetate)
been reported in literature [25]. [20,21] and has long been used by blending with other natural polymers because
of itsdeposits
Natural film-forming features [22,23]. The(Al
of aluminosilicate complete dissolution of PVA in water is bound by its intrinsic
2 Si2 O5 (OH)4 ¨nH2 O) are chemically similar to kaolin, but
properties, which require the water temperature to be at ~100 °C with a holding time of 30 min [23].
with halloysite nanotubes (HNTs), i.e., hollow tube-shaped, micro- to submicrosized structures have
All PVA grades are hydrophilic and depend on certain factors, such as molecular weight, element
limited high aspectofratio.
dimensions HNTs
distribution, andare quarried
particle crystal naturally fromThe
structure [23,24]. many countries
resulting around
gel properties havethe world,
been reported
such as Japan, China, inAmerica,
literature [25].
South Korea, Brazil, France, and Turkey [26]. Composite films with
Natural deposits of aluminosilicate (Al2Si2O5(OH)4·nH2O) are chemically similar to kaolin, but
enhanced mechanical and thermal properties can be prepared by casting from a PVA–HNT solution.
with halloysite nanotubes (HNTs), i.e., hollow tube-shaped, micro- to submicrosized structures have
The enhancement of the polymer properties is accredited to the uniform dispersion of the nanotubes
limited high aspect ratio. HNTs are quarried naturally from many countries around the world, such as
within the Japan,
polymer matrix,
China, America, which
South results in enhanced
Korea, Brazil, France, andinterfacial
Turkey [26]. interactions
Composite films in thewithcomposite
enhanced systems.
mechanical and thermal properties can be prepared by casting
Recently, the role of HNTs as a viable and biocompatible candidate for biomaterial applications from a PVA–HNT solution. The has
enhancement of the polymer properties is accredited to the uniform dispersion of the nanotubes within
been verified [27]. HNT toxicity has been studied, where the course of cell absorbance of HNTs is
the polymer matrix, which results in enhanced interfacial interactions in the composite systems.
conceived Recently,
in various cellsof[28].
the role HNTsThe as a main
viable aim of this article
and biocompatible is to discuss
candidate the synthesis,
for biomaterial applications properties,
has and
applications
beenofverified
PVA, HNTs,
[27]. HNT and theirhas
toxicity PVA–HNT
been studied, nanocomposites.
where the course of The
cellindividualized
absorbance of HNTs HNTis addition
conceived
and crosslinking ofinPVA
variousforcells [28]. The
various main aim of applications
biomedical this article is to discuss
are also thereviewed,
synthesis, properties,
therebyand showing the
applications of PVA, HNTs, and their PVA–HNT nanocomposites. The individualized HNT addition
prospective accessibility, modification of characteristics, and goals underlying the blending process
and crosslinking of PVA for various biomedical applications are also reviewed, thereby showing the
with PVA.prospective accessibility, modification of characteristics, and goals underlying the blending process
with PVA.
2. Chemical Structure of PVA
2. Chemical Structure of PVA
The properties of polyvinyl acetate depend on the extent or degree of its hydrolysis, specifically
The properties of polyvinyl acetate depend on the extent or degree of its hydrolysis, specifically
whether it is full or partial (Figure 1), which in turn dictates its categorization into two groups, namely,
whether it is full or partial (Figure 1), which in turn dictates its categorization into two groups,
(a) partially hydrolyzed
namely, and
(a) partially (b) fullyand
hydrolyzed hydrolyzed.
(b) fully hydrolyzed.

Figure 1.Figure 1. Structural

Structural formula
formula forfor PVA:(a)
PVA: (a)partially
partially hydrolyzed;
hydrolyzed;(b) fully
(b) hydrolyzed [2].
fully hydrolyzed [2].

2
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Molecules 2015, 20, page–page

The
Themolecular
molecularweights
weightsobtained
obtainedforfor
PVA PVA products
products may vary
may (20,000–400,000),
vary (20,000–400,000), depending
dependingon the
on
length of the
the length initial
of the vinyl
initial acetate
vinyl polymer,
acetate polymer, thethe
level ofofhydrolysis
level hydrolysistotoeliminate
eliminatethetheacetate
acetate groups
groups
and
and whether
whether itit occurs
occurs under
under alkaline
alkalineor or acidic
acidicconditions
conditions[2].
[2].Figure
Figure22shows
showsthe
thestructure
structureofofPVA.
PVA.
Hydrolysis
Hydrolysislevels
levelsvaryvaryfrom
fromwhat is considered
what is considered a typical valuevalue
a typical of 80%ofto80%
reach
to more
reachthanmore99%. Nearly
than 99%.
fully hydrolyzed
Nearly forms result
fully hydrolyzed in forming
forms result inPVA hydrogels
forming PVA with tuneable
hydrogels properties
with tuneablethrough crosslinking
properties through
of the linear polymers,
crosslinking which
of the linear subsequently
polymers, whichresult in polymerresult
subsequently (gel)-fluid (sol) species.
in polymer Polymer
(gel)-fluid (sol)contents
species.
affect the contents
Polymer physical affect
statustheof the resulting
physical statusmaterial: low polymer
of the resulting content
material: lowresults
polymerin acontent
soft materials
results
because the fluid moves freely through the matrix, whereas a higher polymer
in a soft materials because the fluid moves freely through the matrix, whereas a higher polymer content results in
considerable
content results stiffening and strengthening
in considerable stiffening and of strengthening
the material’sofmatrix [29]. Studies
the material’s matrixon[29].
theStudies
diffusive
on
permeability
the diffusiveof solutes in PVA
permeability gel membranes
of solutes in PVA gel and the application
membranes and for
the separation
applicationhave been delineated
for separation have
because of chemical
been delineated stability,
because particularly
of chemical on film-forming,
stability, particularly onand hydrophobicity
film-forming, and [30].
hydrophobicity [30].

Figure
Figure 2.
2. (a)
(a) The
The structure
structure of
of vinyl
vinyl alcohol;
alcohol; (b)
(b) PVA
PVA is
is synthesized
synthesized by
by the
the hydrolysis
hydrolysis of
of polyvinyl
polyvinyl
acetate
acetate [26].
[26].

3.
3. Chemical
Chemicaland
andPhysical
PhysicalProperties
PropertiesofofPVA
PVA
The
The chemical
chemical and and physical
physicalproperties
propertiesof ofPVA
PVA maymay vary
vary based
based on on the
the percentage
percentageof ofhydrolysis,
hydrolysis,
which
which determines
determines the the PVA
PVAgradegradeand andits
itsmolecular
molecularweight
weight [2].The
[2]. The surface
surface properties
properties of of
PVAPVA fillers
fillers are
are fundamentally significant in the selection criteria of PVA fillers [3]. PVA itself
fundamentally significant in the selection criteria of PVA fillers [3]. PVA itself has substantial tensile has substantial tensile
strength,
strength, moremore flexibility,
flexibility, and
and hardness
hardness and and gas
gas and
and aroma
aroma barrier
barrier characteristics.
characteristics. Compared
Compared with with anyany
other
otherknown
knownpolymer,
polymer, PVA PVA demonstrates
demonstrates remarkably
remarkably superior
superiorfeatures
featuresas asananoxygen
oxygenbarrier;
barrier;however,
however,
to
to avoid
avoidthe thedegradation
degradation of of
its its
permeability
permeabilitytoward gas,gas,
toward it must be protected
it must from moisture
be protected [4]. PVA,
from moisture [4].
like proteins, is a water-soluble polymer. The water solubility and physical properties
PVA, like proteins, is a water-soluble polymer. The water solubility and physical properties of PVA, of PVA, including
its film form,
including areform,
its film highly
are affected by thebydegree
highly affected of hydrolysis,
the degree of hydrolysis, molecular
molecular weight,
weight, and
anditsits crystal
crystal
precipitation [5]. PVA is partially crystalline upon formation and is characterized
precipitation [5]. PVA is partially crystalline upon formation and is characterized by properties such by properties suchas
as chemical
chemical resistance,
resistance, waterwater solubility,
solubility, and and biodegradability.
biodegradability. The similarity
The similarity in physical
in physical properties
properties makes
makes it compatible
it compatible with humanwith human
tissues. tissues. Biocompatible
Biocompatible PVA hasPVA has a structure
a structure that can
that can absorb absorb
protein protein
molecules
molecules and engage with minimal cell adhesion and has no toxic effects,
and engage with minimal cell adhesion and has no toxic effects, therefore, PVA membranes have therefore, PVA membranes
have been widely
been widely developeddeveloped for biomedical
for biomedical applications
applications [30]. PVA [30].
canPVA can chemically
chemically bound to bound to or
or physically
physically entangled with a nanoparticle surface [31]. PVAs are very common
entangled with a nanoparticle surface [31]. PVAs are very common polymers, widely used as surface polymers, widely used
as surface materials, which should be retained on water surface [32–34], in
materials, which should be retained on water surface [32–34], in a huge range of fields as films [35,36]a huge range of fields as
films [35,36]
and glues [37]and gluesof
because [37] because
their of their
exceptional exceptional
chemical chemical
and physical and physical
properties properties
[38–40], [38–40],
biocompatibility,
biocompatibility, stability to temperature variation,
stability to temperature variation, and non-toxicity [41,42]. and non-toxicity [41,42].

22835
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Molecules 2015, 20, 22833–22847
Molecules 2015, 20, page–page
Molecules 2015, 20, page–page

4. ChemicalStructure
4. Chemical StructureofofHNTs
HNTs
4. Chemical Structure of HNTs
Micrographs
Micrographs of of HNTs
HNTs can
can be
be seen
seen in
in Figure
Figure 3.
3. A
A predominant
predominant percentage
percentage of
of the
the halloysites
halloysites are
are
Micrographs of HNTs can be seen in Figure 3. A predominant percentage of the halloysites are
of tube-shaped structures have the following measurements: the length varies from 150
of tube-shaped structures have the following measurements: the length varies from 150 nm to 2 μm, nm to 2 µm,
of tube-shaped structures have the following measurements: the length varies from 150 nm to 2 μm,
the
the outer
outer diameter ranges from
diameter ranges from 20
20 nm
nm to
to 100
100 nm;
nm; and
and the
the lumen
lumen diameter
diameter ranges
ranges from
from 55 nm
nm to
to 30
30 nm.
nm.
the outer diameter ranges from 20 nm to 100 nm; and the lumen diameter ranges from 5 nm to 30 nm.
Given
Given the distinctive and
the distinctive and differential
differential morphological
morphological aspects
aspects of
of HNTs,
HNTs, uncommon
uncommon charge
charge distributions,
distributions,
Given the distinctive and differential morphological aspects of HNTs, uncommon charge distributions,
surfaces with lower
surfaces with lower hydroxyl
hydroxyl density,
density, and
and crystals
crystals with
with an
an unequalled
unequalled structure
structure are
are observed
observed [7].
[7].
surfaces with lower hydroxyl density, and crystals with an unequalled structure are observed [7].
The
The featured
featuredcharacteristics
characteristicsofof
PVA–HNTs
PVA–HNTs films werewere
films determined through
determined the tensile
through strength,
the tensile optical
strength,
The featured characteristics of PVA–HNTs films were determined through the tensile strength,
transmittance, and scanning electron microscopy [43].
optical transmittance, and scanning electron microscopy [43].
optical transmittance, and scanning electron microscopy [43].

Figure 3.
Figure 3. TEM micrograph
TEM micrograph
3. TEM of
micrograph of HNTs
of HNTs [44].
HNTs [44].
Figure [44].

Figure 4 illustrates a crystalline-shaped typical unit of HNTs, which comprises a bilayer formation
Figure
Figure 44 illustrates
illustrates aa crystalline-shaped
crystalline-shaped typical
typical unit
unit of
of HNTs,
HNTs, which
which comprises
comprises aa bilayer
bilayer formation
formation
and two kinds of –OH groups, as follows: (a) the outer –OH groups located in the unshared plane of
and two kinds of –OH groups, as follows: (a) the outer –OH groups located
and two kinds of –OH groups, as follows: (a) the outer –OH groups located in the unshared in the unshared plane of
plane
the tetrahedral (silicon and oxygen) sheet and b) the inner hydroxyl groups located in the shared
the tetrahedral
of the tetrahedral (silicon
(siliconand
andoxygen)
oxygen)sheet
sheetand
andb)(b)the
theinner
innerhydroxyl
hydroxylgroups
groupslocated
locatedin in the
the shared
shared
octahedral (aluminum and oxygen) sheet. Consequently, siloxanes form the outer side of HNTs, with
octahedral (aluminum and oxygen) sheet. Consequently, siloxanes form the
octahedral (aluminum and oxygen) sheet. Consequently, siloxanes form the outer side of HNTs, outer side of HNTs, with
a small amount of silicon hydroxyl groups positioned in the HNTs’ endings and surface defects.
a small
with amount
a small amountof silicon hydroxyl
of silicon hydroxylgroups
groups positioned
positioned in in
thetheHNTs’
HNTs’endings
endingsandandsurface
surface defects.
defects.
However, most of the aluminum hydroxide groups are located on the inner side. The development of
However, most of
However, most of the
the aluminum
aluminum hydroxide
hydroxide groups
groups areare located
located on on the
the inner
inner side.
side. The
The development
development of of
H-bonding affects the blue shift of the Fourier transform infrared (FTIR) absorption of Si-O stretching
H-bonding affects the blue shift of the Fourier transform infrared (FTIR) absorption
H-bonding affects the blue shift of the Fourier transform infrared (FTIR) absorption of Si-O stretching of Si-O stretching
because most of the aluminum hydroxide pairs are placed on the inner side of the crystalline
because mostofofthethe
because most aluminum
aluminum hydroxide
hydroxide pairspairs are placed
are placed on the on theside
inner inner side
of the of the crystalline
crystalline formation,
formation, and the blue shift of luminol is far less than that for the Si-O group [45].
formation, and the blue shift of luminol is far less than that for
and the blue shift of luminol is far less than that for the Si-O group [45]. the Si-O group [45].

Figure 4. Crystalline structure of HNTs [46].

Figure
Figure 4.
4. Crystalline
Crystalline structure
structure of
of HNTs [46].
HNTs [46].
5. Advantages and Disadvantages of PVA and HNTs
5.
5. Advantages
Advantagesand andDisadvantages
Disadvantagesof ofPVA
PVA and
and HNTs
HNTs
PVA has been the subject of intensive research because it has many applications in industry. Under
PVA has been
PVA has been the
the subject
subject of
of intensive
intensive research
research because
because it
it has
has many
many applications
applications in industry. Under
wet conditions, its properties are diminished because of the plasticizing action ofinwater
industry. Under
molecules
wet
wet conditions, its properties are diminished because of the plasticizing action of water molecules
[47]. HNTs more likely reduce the PVA decomposition to a considerable extent, but they are [47].
conditions, its properties are diminished because of the plasticizing action of water molecules not
[47].
HNTs HNTs
moreinmore reduce
likely likely reduce
the PVA the PVA decomposition
decomposition to a considerable
to a considerable butextent, butnot
they are not
efficacious ameliorating the abstraction of the linked groups. Theextent,
combinationtheyprocedure
are efficacious
at lower
efficacious
in in ameliorating
ameliorating the abstraction
the abstraction of the in of thegroups.
linked linked groups. The combination
The combination procedure
procedure at lower
at lower HNT
HNT concentrations is more effective the thermal decomposition of composite films compared
HNT concentrations is more effective in the thermal decomposition of composite films compared
with the higher HNT concentration cases. Its abundance as a low-cost polymer is rendering it more
with the higher HNT concentration cases. Its abundance as a low-cost polymer is rendering it more
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Molecules 2015, 20, 22833–22847

concentrations is more effective in the thermal decomposition of composite films compared with the
higher HNT concentration cases. Its abundance as a low-cost polymer is rendering it more attractive
than other polymers [48,49]. Physical blending and chemical modification by grafting, interpenetrating
polymer networks (Table 1), and crosslinking method greatly contribute to the alleviation of
such disadvantages [50].

Table 1. Summary of main properties.

No. HNTs PVA

1 Natural, nontoxic [51,52] Non-toxic [48,49]
Hydrogels exhibit swelling feature in water with the
2 Non-swelling [51,52] peculiar characteristics of retaining water within its matrix
without dissolving [50].
Compatibility polymers oriented, such as
3 PVA is more biologically compatible [48,49]
polypropylene and polyethylene [51,52]
PVA has relatively low strength and thermal stability for
Excellent mechanical properties such as tensile
some applications, excellent mechanical properties such
strength with 5 wt % HNTs increase 300% and
4 as: strength (1.6 ˘ 0.1 GPa), elastic modulus (48 ˘ 3 GPa),
thermal stability because HNTs are stable even at
strain (6.5% ˘ 1.4%), and toughness (40 ˘ 6 J¨ g´1 ) [54]
very high temperatures [3,53] in PVA film.
and flexibility in dry state [47]
5 Formula [Al2 Si2 O5 (OH)4¨nH2 O] [55] Formula [-CH2 CHOH-]n
HNT is naturally occurring, will also have the benefit
To overcome the limited biological performance and to
to reinforce PVA and impart other biological
enhance the mechanical properties of PVA, a new class of
6 properties to the bionanocomposites, such as
engineering designed PVA bionanocomposites has been
drug/gene delivery capacity without fear of being
introduced recently [53]
carcinogenic [53]

6. Applications of PVA and HNTs

For over 50 years, hydrogels have been invented and applied in numerous biomedical disciplines,
such as production of contact lenses and absorbable sutures, osteoporosis, asthma treatment, and
neoplasms. Thus, much attention has been given to the use or modification of different polymeric
materials that can be currently used for biomedical devices to fulfill the increased need for those
materials in medical applications.

6.1. Biomedical Applications of PVA and HNTs

PVA is already used in biomedical applications for its compatibility [25]. PVA composites, such
as PVA gels, are used in different biomedical fields, such as in the manufacturing of contact lenses,
artificial heart surgery, drug delivery systems, and wound dressings. In medical devices, PVA is
used as a biomaterial because of its highly favorable properties, such as biocompatibility, nontoxicity,
non-carcinogenic, swelling properties, and bioadhesive characteristics. This material is very useful
and desirable for biomedical application and uses. Table 2 identifies some non-implant and implant
devices that are currently made of different PVA forms and HNTs [26].

Table 2. Uses of PVA and HNTs in non-implant and implantable devices [26,52].

Device Type Product PVA Product HNTs

Surgical sponges and packing Diuretic drug transportation to remove hazardous species
Non-implant
Eye wetting drops Sustained release of drugs, food additives, and fragrances
devices
Contact lenses Antimicrobial agents
Hydrophilic coatings (Catheters, leads, etc.) Human breast cells
Vascular embolic agents Fibroblasts
Implantable
Tissue adhesion barriers Corrosion protection implant alloys
devices
Nerve guides Biosensors
Used in advanced ceramic materials, especially
Cartilage replacements
biocompatible implants

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Molecules 2015, 20, 22833–22847

Crystalline structures can be controlled by modifying the chemical composition of OH groups [32].
Bio-inertness and compatibility are other PVA properties that have implications in advanced medical
fields, hemodialysis, drug delivery system, and implantable medical devices [38,56]. PVA-based
materials are used in pharmaceutical and in biomedical fields as drug carriers and are also applied
in tissue engineering science [56–63]. Additionally, PVAs with their crystalline structure consist of
H-atoms interlinked between the hydroxyl group, and these hydrogen atoms could be interlinked [64].
The application of transdermal patches is being used as a component of the biomedical system because
of the desirable PVA properties, such as water solubility and biodegradability. PVA cross-linked
microspheres are used in oral precision relief systems [42,65].
Hydrophilicity and processing characteristics allow this polymer to be mixed with other natural and
artificial polymers [38,66]. PVA composites in hydrogel form have been used extensively in the medical
field because of their biocompatibility, and are a well-known polymer gel with several applications,
such as in organ replacement, drug delivery devices, and wound management [52,53,67–70]. From this
point of view, encapsulating measurement nanoparticle (MNP) in PVA is a challenging and promising
topic. PVA’s good structure and biocompatibility with MNP, along with the cost of material, allow
its biomedical and pharmaceutical applications [71,72]. PVA is a polymer that acts as a protective
agent with formations in water solution and abundant OH groups; it also tends to absorb metal ions
and form complex products [71,73]. Several research groups have investigated the application of
nanotechnology in PVA, and they have reported their hydrogel preparation based on organically
modified montmorillonite and studied their potential use as the main wound dressing devices
in vitro [52,74] and in vivo [75] environments.
Biocompatibility of HNTs was improved by wrapping amylase on the surface. Basically, the
utilization of the amylase-HNTs for applications in absorbing metal ions or dyes can be regarded as
absorbents in biomedical aspects and also as biological nanoreactors and nanofillers in biopolymer
matrix. In addition, in hydrocarbon processing and catalytic conversions, HNTs were used for storing
molecular hydrogen. In the environmental sector, HNTs present several biological and non-biological
uses, such as a diuretic drug transportation to remove hazardous species [76].

6.2. General Applications of PVA and HNTs

Addition of HNTs was intended to make PVA water-insoluble and hence more useful in
commercial applications. Examination of the composites indicated that HNTs were uniformly
dispersed in both PVA as well as crosslinked PVA. Excellent mechanical properties of the PVA–HNT
nanocomposites were achieved. These nanocomposites are intended to be composted at the end of
their life rather than end up in landfills like most traditional petroleum-based non-biodegradable
plastics [9]. PVA is used in many industries, such as textile, paper industry, and food packaging
industry [29,54] because of its high chemical and thermal stability, and low manufacturing cost [77].
It is also a popular water-soluble polymer and has high strength and high optical transparency in
water. Because of these desirable properties, PVA is used in packaging and as optical polarizer [43].
This polymer is also applicable in other industries, including polymer recycling, food packaging,
binding and coating, and adhesives. PVA is a type of biodegradable resin even if it is an artificial
polymer derived from petroleum [78]. The extensive use of PVA is observed in different fields of
science and technology, such as coating and finishing agents, emulsifiers, wood, and leather [79].
PVA is an excellent source for fiber, polymer, textile, surface, organic [80].

7. Fabrication Approaches for PVA-HNTs Composites

HNTs can be mixed with most plastics using traditional equipment, such as the twin screw
extruder and the two roll mill. The selection of fabrication methods has mainly focused on
improvement of nanotube dispersion in the polymer matrix and on the enhancement of interfacial
interactions. The common processing methods used for PVA-HNTs composites are presented in the
following sections.

22838
Molecules 2015, 20, 22833–22847

7.1. Dispersion Processing

Dispersion mixing is the most commonly used method for fabricating PVA-HNT composites
because it is easily performed and suitable for a small sample size. This process is realized by dispersing
Molecules 2015, 20, and
the nanotubes page–page
PVA in a suitable solvent (i.e., water and organic solvent) with vigorous stirring
followed by ultrasonic treatment. Finally, the PVA-HNTs composites are obtained as film or hydrogels
after
after casting
casting [74].
[74]. The
The incorporation
incorporation of of HNTs
HNTs significantly
significantly reduces
reduces thethe level
level of
of decomposition
decomposition activity
activity
of
of the PVA backbone, thereby increasing its efficiency. The effect of low concentration of HNTs shows
the PVA backbone, thereby increasing its efficiency. The effect of low concentration of HNTs shows
more significant effect
more significant effectcompared
comparedwithwiththetheeffect
effectofofhigh
highconcentration
concentration onon the
the thermal
thermal decomposition
decomposition of
of
thethe composite
composite films
films when
when the
the aggregationprocess
aggregation processisisinvolved
involvedininhigh
highHNT
HNTconcentration.
concentration. Surface
Surface
properties
properties of of the
the fillers
fillers determine
determine thethe interaction
interaction between
between thethe fillers
fillers and
and PVA,
PVA, which
which are
are of primary
of primary
importance in filler selection criteria. Figure 5, adapted from [3], shows the particle size and
importance in filler selection criteria. Figure 5, adapted from [3], shows the particle size and distribution distribution
of
of HNTs
HNTs in in different
different PVA–HNT
PVA–HNTmixtures
mixtures

Figure
Figure5.
5.The
Theparticle
particlesize
sizeand
anddistribution
distributionof
ofHNTs
HNTs in
in mixture
mixture of PVA-HNTs [3].
PVA-HNTs [3].

Considering
Considering the
thedesirable
desirablefeatures
featuresandandsolubility
solubilityininwater,
water,HNTs
HNTsare used
are asas
used thethe
carrier agent
carrier of
agent
aofmixture in ainmixture
a mixture containing
a mixture polymers
containing polymersfor nanoparticles. As anAs
for nanoparticles. example, PVA–HNT
an example, PVA–HNTfilms films
have
considerable mechanical
have considerable and physical
mechanical properties
and physical and canand
properties be processed throughthrough
can be processed the selection of suitable
the selection of
PVA–HNT mixturesmixtures
suitable PVA–HNT [81]. PVA–HNT films can
[81]. PVA–HNT be can
films made be by crosslinking
made with glutaraldehyde
by crosslinking in an
with glutaraldehyde
aqueous mixture
in an aqueous and and
mixture casting on glass
casting substrates.
on glass PVA
substrates. PVAhas remarkably
has remarkablyhigh
hightransparency,
transparency, which
indicates the homogenous distribution of HNT within the composite films [82].

7.2. Electrospinning
Electrospinning
Electrospinning is
Electrospinning is aa simple
simple and versatile fiber synthesis technique
technique in which a high-voltage
high-voltage
electric field is applied to a stream of polymer solution, thereby forming continuous micro/nanofibers.
micro/nanofibers.
Electrospun fibers
Electrospun fibers create a fabric network
network with
with high
high porosity,
porosity, very small pore size, and very large
surface-to-volume ratio.
surface-to-volume ratio. Therefore,
Therefore, these
these materials
materials could
could be
be used
used for
for many
many biomedical
biomedical applications,
applications,
such as drug delivery, artificial organs, wound dressing, and medical prostheses. The polymers used
for electrospinning
electrospinning withwith HNTs
HNTs range from polylactide
polylactide (PLA)
(PLA) toto PVA.
PVA. Biodegradable
Biodegradable PLA
PLA and
and PVA
PVA
have good electrospinning properties, leading to their application in many areas. Dichloromethane
or chloroform was employed to dissolve the PLA with dimethyl formamide to enhance the electric
Water was
conductivity. Water was used
used as
as aa solvent
solvent for
for PVA.
PVA. Mixing the HNTs with the polymer solution
before spinning could generate composite nanofibers [74]. Non-woven mats containing electrospun
fibers with high porosity and large specific surface area provide a potential way of manufacturing
high-performance fiber-reinforced
high-performance fiber-reinforced polymer
polymer composites
composites through
through polymer
polymer solution
solution impregnation.
impregnation.
experiments have
Recent experiments have demonstrated
demonstrated that
that electrospun
electrospun fibers
fibers are
are effective in reinforcing rubber
films and enhancing the strength and stiffness of the epoxy matrix. The mechanical performance of
the electrospun fiber reinforced polymer composites is known to critically depend on the interface
adhesion between the fibers and the matrix [83].
22839
8. Characterization of PVA–HNT Composites
In this section we discuss the preparation, characterization, water absorption capacity, thermal
Molecules 2015, 20, 22833–22847

the electrospun fiber reinforced polymer composites is known to critically depend on the interface
adhesion between the fibers and the matrix [83].

8. Characterization of PVA–HNT Composites

In this section we discuss the preparation, characterization, water absorption capacity, thermal
stability and flame retardant behavior of PVA-HNTs nanocomposites with special reference to
filler loading.
Molecules 2015, 20, page–page
Molecules 2015, 20, page–page

8.1. Morphological Studies

8.1. Morphological
Morphological Studies of
of PVA–HNT
PVA–HNT Nanocomposites
Nanocomposites
8.1. Studies of PVA–HNT Nanocomposites
Figure 66shows
showsthe
thephysical aspect
physical of nanocomposite
aspect of nanocomposite
nanocompositefilmsfilms
of PVA-HNT with 2 with
of PVA-HNT
PVA-HNT wt % HNT loading.
Figure 6 shows the physical aspect of films of with 22 wt
wt %% HNT
HNT
Two methods
loading. Two were used
methods to prepare
were used tothe nanocomposite
prepare the films. Moreover,
nanocomposite films. the well dispersed
Moreover, the well HNTs in
dispersed
loading. Two methods were used to prepare the nanocomposite films. Moreover, the well dispersed
the
HNTs mixture
theprepared
in the mixture by coagulation
prepared method separate
by coagulation
coagulation methodfrom the solidified
separate from thePVA
the during the
solidified PVA precipitation
during the
the
HNTs in mixture prepared by method separate from solidified PVA during
process and cannot
precipitation reaggregate
process and cannot[3].
reaggregate [3].
precipitation process and cannot reaggregate [3].

Figure6.6.
Figure
Figure 6.TEM
TEMphotos
TEM photosof
photos of PVA-HNT
of PVA-HNT nanocomposite
PVA-HNT nanocomposite films
nanocomposite films (2
(2 wt
(2 wt
wt%% HNTs)
%HNTs) prepared
HNTs)prepared by:
preparedby: (a)
by:(a) coagulation
(a)coagulation
coagulation
(b)
(b) casting
casting [3].
[3].
(b) casting [3].

Sulfuric acid
Sulfuric acid treatment
acid treatment was
treatment wasperformed
was performedfor
performed foronly
for only111h,h,
only h,particularly
particularlywhen
particularly whena aahigh
when highYoung’s
high Young’s
Young’s modulus
modulus
modulus is
is desired.
desired.
is desired. Longer
Longer sulfuric
Longersulfuric acid
sulfuricacid treatment
acidtreatment
treatmentwouldwould decrease
woulddecrease
decreaseitsits tensile
itstensile strength.
tensilestrength. Sulfuric
strength. Sulfuric acid
Sulfuric acid dissolves
acid dissolves
Al3+
Al
3+ ions, thereby resulting in HNTs that consist of amorphous silica. Thus, the reduction in the
ions, thereby
3+ ions, thereby resulting
resulting inin HNTs that consist of amorphous silica.
amorphous silica. Thus,Thus, the reduction in the
crystalline structure of HNTs was first considered. Figure 7 shows TEM images
crystalline structure of HNTs was first considered. Figure 7 shows TEM images of untreated HNTs of untreated HNTs
(Figure 7a)
(Figure 7a) and
and 88 h-treated
h-treated HNTs
HNTs (Figure
(Figure 7b).
7b). Untreated
Untreated HNTs
HNTs havehave aa clear
clear hollow
hollow tubular
tubular structure,
tubular structure,
structure,
whereas the
whereas the tubular
tubular profile
profile is
is difficult
difficult to
to identify
identify for
for sulfuric
sulfuric acid-treated
acid-treated HNTs
HNTs
tubular profile is difficult to identify for sulfuric acid-treated HNTs [43]. [43].
[43].

Figure 7.
Figure 7. TEM images
images of HNTs:
HNTs: (a) untreated
untreated and
and (b)
(b) after
after acid
acid treatment
treatment [7].
[7].
Figure 7. TEM
TEM images of
of HNTs: (a)
(a) untreated and (b) after acid treatment [7].
The fractured
The fractured surfaces
surfaces ofof untreated,
untreated, H
H2SOSO44 treated
treated for
for 11 h,
h, and
and HH22SO
SO44 treated
treated for
for 88 h
h PVA-HNT
PVA-HNT
The fractured surfaces of untreated, H22SO 4 treated for 1 h, and H2 SO4 treated for 8 h PVA-HNT
films are
films are shown
are shown
shownin in Figure
inFigure 8. Figure
Figure8.8.Figure
Figure8a8a shows
8ashows traces
showstraces of resin
tracesofofresin
resin elongation
elongation originating
originating from
from a slip
a slip caused
caused
films elongation originating from a slip caused by
by poor
by poor adhesion
adhesion of of PVA
PVA andand HNTs,
HNTs, but
but Figure
Figure 8b8b exhibits
exhibits nono slippage,
slippage, and
and the
the HNTs
HNTs are are well
well
poor adhesion of PVA and HNTs, but Figure 8b exhibits no slippage, and the HNTs are well distributed
distributed in
distributed in PVA.
PVA. Nonetheless,
Nonetheless, traces
traces of
of resin
resin elongation,
elongation, as as well
well as
as untreated
untreated HNTs, are are shown
shown inin
in PVA. Nonetheless, traces of resin elongation, as well as untreated HNTs, areHNTs,shown in Figure 8c.
Figure 8c.
Figure 8c. Thus, long
long treatment
treatment times
times with H H22SO
SO44 may
may negatively
negatively affect
affect the
the interfacial
interfacial adhesion
adhesion
Thus, long Thus,
treatment times with H2 SO4 with
may negatively affect the interfacial adhesion between PVA
between
between PVA
PVA and
and HNTs
HNTs [43].
[43].
and HNTs [43].

22840
 The fractured surfaces of untreated, H2SO4 treated for 1 h, and H2SO4 treated for 8 h PVA-HNT
films are shown in Figure 8. Figure 8a shows traces of resin elongation originating from a slip caused
by poor adhesion of PVA and HNTs, but Figure 8b exhibits no slippage, and the HNTs are well
distributed in PVA. Nonetheless, traces of resin elongation, as well as untreated HNTs, are shown in
Figure 8c.
Molecules 2015,Thus, long treatment times with H2SO4 may negatively affect the interfacial adhesion
20, 22833–22847
between PVA and HNTs [43].

Figure 8. SEM images of fractured surfaces of PVA-HNT films after different H2SO4 treatment times
Figure 8. SEM images of fractured surfaces of PVA-HNT films after different H2 SO4 treatment times
(8 wt % HNT
Molecules 20,loading);
page–page(a) untreated; (b) H2SO4 treatment for 1 h and (c) H2SO4 treatment for 8 h [66].
(8 wt %2015,
HNT loading); (a) untreated; (b) H2 SO4 treatment for 1 h and (c) H2 SO4 treatment for 8 h [66].
Molecules 2015, 20, page–page 8
8.2. Thermal Properties of PVA-HNT Nanocomposites
8.2. Thermal Properties of PVA-HNT Nanocomposites
8.2. Thermal Properties of PVA-HNT Nanocomposites
PVA is a partially crystalline-structured polymer with physical and chemical properties, such as
PVA PVAis ais partially
a partiallycrystalline-structured
crystalline-structured polymerwith
polymer with physical and chemical properties, suchsuch
interchain and intrachain polymer interactions, becausephysical and chemical
of the H-bonding inproperties,
between hydroxyl as
as interchain
interchain and and intrachain
intrachain polymer
polymerinteractions,
interactions,because
becauseofofthe the H-bondingininbetween
betweenhydroxyl
hydroxyl
groups. The introduction of nanosized HNTs particles with –OH H-bonding
groups changes the intermolecular
groups.
groups. TheThe introduction
introduction ofofnanosized
nanosized HNTs
HNTs particles with
particleschains, –OH groups
with –OH groupschanges
changesthetheintermolecular
intermolecular
and intramolecular interaction between the polymer which in turn changes the composition
andandintramolecular
intramolecular interaction
interaction between
between the
thepolymer
polymer chains,
chains, whichin
which inturn
turnchanges
changesthethe composition
of the physical structure and the crystallization behavior. Thus, the properties of PVA composition
films change.
of the
of physical
the
Figure physical
9 shows structure
structure
a DSC curveand the
andof thecrystallization
neatcrystallization
PVA and PVA-HNTbehavior.
behavior. Thus,the
Thus,
composites the properties
inproperties
cooling ofof
mode,PVAPVA films
films
thereby change.
change.
illustrating
Figure
Figure 9
that the shows
9 shows a DSC
DSC
crystalline curve
curve
PVA of
of neat
peak neat PVA
PVA and
structure and
PVA-HNT
shifts PVA-HNT composites
composites inwith
to high temperature cooling in cooling mode,
mode, thereby
increasing thereby
illustrating
HNT contents and
illustrating
that the that the
crystalline crystalline
PVA peak PVA peak
structure structure
shifts
the crystallization of neat PVA is more persistent [3]. to highshifts to high
temperature temperature
with with
increasing HNT increasing
contents HNT
and
the crystallization
contents of neat PVAof
and the crystallization is neat
morePVApersistent
is more[3].persistent [3].

Figure 9. DSC cooling thermograms of neat PVA and PVA-HNT composite films with different HNT
Figure 9. DSC
Figure 9. DSC cooling
coolingthermograms
thermogramsof ofneat
neat PVA
PVA and PVA-HNT composite
and PVA-HNT compositefilms
filmswith
withdifferent
different HNT
HNT
contents: (a) 0 wt % (neat PVA); (b) 2 wt %; (c) 10 wt %; (d) 40 wt %; (e) 53 wt % [3].
contents: (a)(a)
contents: 0 wt %%
0 wt (neat
(neatPVA);
PVA);(b)
(b)2 2wt
wt%;
%;(c)
(c)10
10wt
wt%;
%; (d)
(d) 40
40 wt %; (e)
(e) 53
53 wt
wt%%[3].
[3].

Figure
Figure 10
1010 shows
shows thethe glass transition temperature(T(T)g)ofofdifferent
different composites.
composites. A gradual decrease
Figure shows theglass
glasstransition
transitiontemperature
temperature (Tgg) of different composites. AAgradual
gradual decrease
decrease
in Tg with increased HNT contents in the polymer composition is observed, and the preparation
in T
ing Twith
g withincreased
increasedHNTHNTcontents
contentsin inthe
the polymer
polymer composition
composition isis observed,
observed,and
andthethepreparation
preparation
method has no effect on the Tg of the resulting PVA-HNT composite film. The effect of measurements
method
method hashas
nono
effect ononthe
effect theTT
g gof
of the
the resulting
resulting PVA-HNT composite
composite film.
film. The
The effect
effect ofof measurements
measurements
of nanoparticles on Tg of PVA composites is the opposite [3].
of nanoparticles
of nanoparticlesononTgTof PVA
g of PVAcomposites
compositesisisthetheopposite
opposite [3].

Figure
Figure 10.10.
T Tcurves
g curves
ofofPVA-HNT
PVA-HNTcomposites
compositeswith
withdifferent
different HNT
HNT contents [3].
[3].
Figure 10. gTg curves of PVA-HNT composites with different HNT contents [3].

The TGA curves of PVA, HNTs, and PVA-HNT composites are shown in Figure 11. The neat PVA
The TGA curves of PVA, HNTs, and PVA-HNT composites are shown in Figure 11. The neat PVA
curve is represented
representedby
bytwo
twoweight
weightloss
losssteps. 22841
steps.The
The weightloss
lossofofcomposites
compositesnear
near350
350°C
°Cand
and450
450°C°Cisis
curve is weight
due to the decomposition process of crosslinked chains and the basic units of PVA, respectively
due to the decomposition process of crosslinked chains and the basic units of PVA, respectively [3]. [3].
Molecules 2015, 20, 22833–22847

The TGA curves of PVA, HNTs, and PVA-HNT composites are shown in Figure 11. The neat PVA
curve is represented by two weight loss steps. The weight loss of composites near 350 ˝ C and 450 ˝ C is
due to the
Molecules decomposition
2015, 20, page–page process of crosslinked chains and the basic units of PVA, respectively [3].

Figure
Figure 11.
11. TGA
TGA curves
curves of
of PVA,
PVA, HNTs and PVA-HNT
PVA-HNT composites
composites [3].
[3].

small difference
The small differencebetween
betweenTTmm and andthethedecomposition
decompositiontemperature
temperatureofofPVAPVA causes
causes difficulty
difficulty in
in production
production of of
thethe film.
film. TheThe polymer’suse
polymer’s useininthe
thefood
foodindustry
industryisislimited
limitedtotopackaging
packaging applications
because of
because of the
therising
risingcost
costofofthe
theproduction
production process.
process.ToToimprove
improve simple packaging
simple filmfilm
packaging formation, the
formation,
PVAPVA
the thermal properties
thermal are enhanced
properties [79]. The
are enhanced versatility
[79]. of HNTsofinHNTs
The versatility producing varieties of
in producing enhanced
varieties of
PVA composites
enhanced and the simple
PVA composites and the production of PVA-HNT
simple production composites
of PVA-HNT and the and
composites enhanced thermal
the enhanced
properties
thermal consolidate
properties its novelty.
consolidate itsTable 3 presents
novelty. Table 3apresents
list of HNT-based PVA composites
a list of HNT-based with the ranges
PVA composites with
of HNT
the loading
ranges of HNT and the intended/achieved
loading target thermal
and the intended/achieved targetproperties for each composition.
thermal properties for each composition.

Table
Table 3.3. HNT-based PVA
PVA composites
composites with
with the
the range
range of
of HNTs
HNTsloading
loadingand
andthe
theintended/achieved
intended/achieved
target thermal properties for
for each
each composition.
composition.

Property Improvements
Property Improvements (Percentage
(Percentage %) %)
HNTs
HNTs (wt %)
(wt %) Form Form Ref. Ref.
Tc (°C) Tg (°C) Tm (°C)˝ TGA (°C)˝
Tc (˝ C) Tg (˝ C) Tm ( C) TGA ( C)
0, 2, 10, 40 & 53 Film - 12.3 - 28.6 [3]
0, 2, 10, 40 & 53 Film - 12.3 - 28.6 [3]
0 & 10 Film 12 - 1.8 - [6,7]
0 & 10 Film 12 - 1.8 - [6,7]
0, 3.75,
0, 3.75, 7.5 &7.5
15 & 15 Modification
Modification - - - - - - 14.314.3 [7,19][7,19]
0, 5,0,105,&1020 & 20 Reinforce
Reinforce - - 12.8
12.8 5.25.2 30 30 [9] [9]
0, 1,0,2.51,&2.5
5 &5 Reinforce
Reinforce 2.6 2.6 3.9
3.9 0.50.5 8.8 8.8 [47] [47]
0, 2,0,5,2,
7.55,&7.5
10 & 10 Film Film - - - - 0.20.2 - - [53] [53]
0, 0.25, 0.5, 1, 3 & 5 Film - - - 14.5 [72]
0, 0.25, 0.5, 1, 3 & 5 Film - - - 14.5 [72]

8.3. Mechanical Properties

8.3. Mechanical Properties of
of PVA-HNT Nanocomposites
PVA-HNT Nanocomposites
The
The tensile strength of
tensile strength of PVA-untreated
PVA-untreated halloysites
halloysites filmfilm was
was reduced, but the
reduced, but the Young’s
Young’s modulus
modulus
increased
increased compared with neat PVA film. Sulfuric acid treatment was conducted on PVA to
compared with neat PVA film. Sulfuric acid treatment was conducted on PVA to improve
improve its
its
tendency and to create film composites. This treatment is applied on the HNTs for
tendency and to create film composites. This treatment is applied on the HNTs for the improvement of the improvement
of interfacial
interfacial adhesion.
adhesion. Treated
Treated HNTs
HNTs improved
improved thetensile
the tensilestrength
strengthofofPVA-HNTs
PVA-HNTs filmsfilms when
when the
the
nanotubes were subjected to sulfuric acid treatment for a short time, less than 2 h. Polymer
nanotubes were subjected to sulfuric acid treatment for a short time, less than 2 h. Polymer composites composites
and
and nanoclay
nanoclay particles
particles are
are usually
usually called
called polymer
polymer or or clay
clay nanocomposites.
nanocomposites. TheseThese small
small amounts
amounts of
of
filler greatly increased the strength because of the magnitude of the specific area [20,43] of
filler greatly increased the strength because of the magnitude of the specific area [20,43] of the nanoclay the nanoclay
particles
particles or
or composites. Blending with
composites. Blending with HNTs
HNTs induces
induces changes
changes in in the
the nano-physiology
nano-physiology and and causes
causes
changes in the chemical structure of PVA films. The incorporation of HNTs enhances
changes in the chemical structure of PVA films. The incorporation of HNTs enhances the mechanical the mechanical
properties
properties ofof PVA
PVA [82].
[82].
PVA has high tensile strength and is soluble in water. Figure 12 describes the relationship between
tensile strength and Young’s modulus of PVA–untreated HNT films, with various HNT loadings. As
the contents of HNTs increase, the tensile strength decreases with less ratio, and the Young’s modulus
22842
is greater. Only the lack of adhesion capacity between the polymer matrix and fillers reduced the
strength [66]. The versatility of HNTs for producing varieties of enhanced PVA composites, and the
production of PVA-HNTs nanocomposites and the enhanced mechanical properties consolidating
Molecules 2015, 20, 22833–22847

PVA has high tensile strength and is soluble in water. Figure 12 describes the relationship between
tensile strength and Young’s modulus of PVA–untreated HNT films, with various HNT loadings.
As the contents of HNTs increase, the tensile strength decreases with less ratio, and the Young’s
modulus is greater. Only the lack of adhesion capacity between the polymer matrix and fillers reduced
Molecules
the 2015, 20,
strength page–page
[66]. The versatility of HNTs for producing varieties of enhanced PVA composites, and
the production of PVA-HNTs nanocomposites and the enhanced mechanical properties consolidating
their novelty.
their novelty. Table
Table 44 presents
presents aa list
list of
of HNT-based
HNT-based PVA
PVAcomposites
compositeswith
withthe
therange
range of
of HNT
HNT loadings
loadings
and the
and the intended/achieved
intended/achieved target
target mechanical
mechanical properties
properties for
for each
each composition.
composition.

Figure
Figure 12. Tensile
12. Tensile strength
strength andand Young’s
Young’s modulus
modulus of of PVA-HNTfilms
PVA-HNT filmswith
withdifferent
different amounts
amounts of
of HNTs
HNTs[66].
[66].

Table4.4 HNT-based PVA

Table PVA composites
composites with
with the
the range
range of
ofHNTs
HNTsloading
loadingand
andthe
theintended/achieved
intended/achieved
target mechanical properties for each composition.
target mechanical properties for each composition.

Property
Property Improvements
Improvements (Percentage
(Percentage %) %)
HNTs (wt %) Form Tensile Young’s Elong. at Break Ref.
HNTs (wt %) Form Tensile Young’s Elong. at Break Ref.
Strength
Strength Modulus (mm/mm)
Modulus (mm/mm)
0, 3.75, 7.5 & 15 Modification 13.6 - - [7,19]
0, 3.75, 7.5 & 15 Modification 13.6 - - [7,19]
0, 5,0,10 & 20
5, 10 & 20 Reinforce
Reinforce 22.7
22.7 407.1
407.1 - - [9] [9]
0, 2,0,5,2,7.5 &&
5, 7.5 1010 Film
Film 81.8
81.8 - - - - [53] [53]
0, 2,0,4,2,6,4,8,
6, 10
8, 10
&&1212 Film
Film 6.46.4 80.280.2 - - [66] [66]
0, 0.25, 0.5, 1, 3 & 5 Film 20 94.9 82.9 [72]
0, 0.25, 0.5, 1, 3 & 5 Film 20 94.9 82.9 [72]

9. Conclusions
9. Conclusions
PVA
PVA is anan artificial
artificialpolymer
polymerthat thathashas
beenbeen
usedused in medical
in the the medical and other
and other fields fields
for thefor
lastthe
30
last 30 This
years. years. This polymer
polymer has beenhas beenwidely
studied studied widely
based based on
on clinical andclinical and nonclinical
nonclinical research.
research. PVA-HNT
PVA-HNT nanocomposites
nanocomposites can be usedcan be used clinical
in general in general clinical operations
operations such as
such as cartilage cartilage replacement
replacement or cartilage
or cartilage transplantation
transplantation because theybecause
have thethey have the
advantage ofadvantage of being
being readily readily
available available
compared withcompared
cartilage
with cartilage transplantation.
transplantation. Disease transmission
Disease transmission concerns and concerns
limitedand limited availability
availability characterize
characterize cartilage
cartilage transplantation. Moreover, PVA-HNT nanocomposites can be used in eye
transplantation. Moreover, PVA-HNT nanocomposites can be used in eye contact lenses, eye drops, contact lenses, eye
drops,
and druganddelivery
drug delivery
systemssystems
to targettotissue
targetwith
tissue with abnormal
abnormal growth
growth rates. rates. In summary,
In summary, we have
we have reviewed
reviewed PVA and PVA–HNT nanocomposite applications due to their biocompatibility,
PVA and PVA–HNT nanocomposite applications due to their biocompatibility, non-toxicity, non-toxicity,
noncarcinogenicity,
noncarcinogenicity, smoothness,
smoothness, and
and flexibility
flexibility in
in potential
potential applications
applications inin bone
bone tissue
tissue engineering
engineering
and
and drug
drug delivery
delivery systems.
systems.

Acknowledgments: The
Acknowledgments: The authors
authors thank
thank Universiti
Universiti Kebangsaan
Kebangsaan Malaysia
Malaysia and
and the
the Ministry
Ministry of
of Higher
Higher Education
Education
for the grants and financial support AP-2013-10 and FRGS/2/2013/TK01/UKM/02/3 to support this work.
for the grants and financial support AP-2013-10 and FRGS/2/2013/TK01/UKM/02/3 to support this work.
Author Contributions: T.S.G. was wrote the manuscript. A.B.S. was supervised the whole work. M.N.A. was
Author Contributions:
provided T.S.G. wasthe
good advice throughout wrote the A.A.H.K.
paper. manuscript.
wasA.B.S. was supervised
supervised the wholethe whole
work. work.
A.B.M. wasM.N.A. was
provided
provided
good good
advice andadvice
editedthroughout the paper.
the paper. A.A.A.A. wasA.A.H.K. was supervised
the principle the
investigator whole
and work.
wrote A.B.M. was provided
the manuscript.
good advice and edited the paper. A.A.A.A. was the principle investigator and wrote the manuscript.

Conflicts of Interest: The authors declare no conflict of interest.

22843
References
1. Razzak, M.T.; Darwis, D.; Zainuddin; Sukirno. Irradiation of polyvinyl alcohol and polyvinyl pyrrolidone
Molecules 2015, 20, 22833–22847

Conflicts of Interest: The authors declare no conflict of interest.

References
1. Razzak, M.T.; Darwis, D.; Zainuddin; Sukirno. Irradiation of polyvinyl alcohol and polyvinyl pyrrolidone
blended hydrogel for wound dressing. Radiat. Phys. Chem. 2001, 62, 107–113. [CrossRef]
2. Demerlis, C.C.; Schoneker, D.R. Review of the oral toxicity of polyvinyl alcohol (PVA). Food Chem. Toxicol.
2003, 41, 319–326. [CrossRef]
3. Liu, M.; Guo, B.; Du, M.; Jia, D. Drying induced aggregation of halloysite nanotubes in polyvinyl
alcohol/halloysite nanotubes solution and its effect on properties of composite film. Appl. Phys. A Mater.
Sci. Process. 2007, 88, 391–395. [CrossRef]
4. Limpan, N.; Prodpran, T.; Benjakul, S.; Prasarpran, S. Influences of degree of hydrolysis and molecular weight
of poly (vinyl alcohol)(PVA) on properties of fish myofibrillar protein/PVA blend films. Food Hydrocoll. 2012,
29, 226–233. [CrossRef]
5. Maria, T.M.; Carvalho, R.A.; Sobral, P.J.; Habitantea, A.M.; Solorza-Feriab, J. The effect of the degree of
hydrolysis of the PVA and the plasticizer concentration on the color, opacity, and thermal and mechanical
properties of films based on PVA and gelatin blends. J. Food Eng. 2008, 87, 191–199. [CrossRef]
6. Qiu, K.; Netravali, A.N. A Composting Study of Membrane-Like Polyvinyl Alcohol Based Resins and
Nanocomposites. J. Polym. Environ. 2013, 21, 658–674. [CrossRef]
7. Tang, Y.; Zhou, D.; Zhang, J. Novel polyvinyl alcohol/styrene butadiene rubber latex/carboxymethyl
cellulose nanocomposites reinforced with modified halloysite nanotubes. J. Nanomater. 2013, 2013, 128.
[CrossRef]
8. Qiu, K.; Netravali, A.N. Fabrication and characterization of biodegradable composites based on
microfibrillated cellulose and polyvinyl alcohol. Compos. Sci. Technol. 2012, 72, 1588–1594. [CrossRef]
9. Qiu, K.; Netravali, A.N. Halloysite nanotube reinforced biodegradable nanocomposites using noncrosslinked
and malonic acid crosslinked polyvinyl alcohol. Polym. Compos. 2013, 34, 799–809. [CrossRef]
10. Cho, D.; Netravali, A.N.; Joo, Y.L. Mechanical properties and biodegradability of electrospun soy protein
Isolate/PVA hybrid nanofibers. Polym. Degrad. Stab. 2012, 97, 747–754. [CrossRef]
11. Luo, S.; Netravali, A.N. A study of physical and mechanical properties of poly (hydroxybutyrate-co-
hydroxyvalerate) during composting. Polym. Degrad. Stab. 2003, 80, 59–66. [CrossRef]
12. Chiellini, E.; Corti, A.; D’Antone, S.; Solaro, R. Biodegradation of poly (vinyl alcohol) based materials.
Prog. Polym. Sci. 2003, 28, 963–1014. [CrossRef]
13. Solaro, R.; Corti, A.; Chiellini, E. Biodegradation of poly (vinyl alcohol) with different molecular weights
and degree of hydrolysis. Polym Adv. Technol. 2000, 11, 873–878. [CrossRef]
14. Vijayalakshmi, S.P.; Madras, G. Effects of the pH, concentration, and solvents on the ultrasonic degradation
of poly (vinyl alcohol). J. Appl. Polym. Sci. 2006, 100, 4888–4892. [CrossRef]
15. Corti, A.; Solaro, R.; Chiellini, E. Biodegradation of poly (vinyl alcohol) in selected mixed microbial culture
and relevant culture filtrate. Polym. Degrad. Stab. 2002, 75, 447–458. [CrossRef]
16. Chiellini, E.; Corti, A.; Solaro, R. Biodegradation of poly (vinyl alcohol) based blown films under different
environmental conditions. Polym. Degrad. Stab. 1999, 64, 305–312. [CrossRef]
17. Jayasekara, R.; Harding, I.; Bowater, I.; Christie, G.B.; Lonergan, G.T. Biodegradation by composting of
surface modified starch and PVA blended films. J. Polym. Environ. 2003, 11, 49–56. [CrossRef]
18. Matsumura, S.; Tanaka, T. Novel malonate-type copolymers containing vinyl alcohol blocks as biodegradable
segments and their builder performance in detergent formulations. J. Environ. Polym. Degrad. 1994, 2, 89–97.
[CrossRef]
19. Ashori, A.; Raverty, W.D.; Harun, J. Effect of chitosan addition on the surface properties of kenaf
(Hibiscus cannabinus) paper. Fibers Polym. 2005, 6, 174–179. [CrossRef]
20. Zainuddin; Hill, D.J.; Le, T.T. An ESR study on γ-irradiated poly (vinyl alcohol). Rad. Phys. Chem. 2001, 62,
283–291. [CrossRef]
21. Pal, K.; Banthia, A.K.; Majumdar, D.K. Preparation and characterization of polyvinyl alcohol-gelatin hydrogel
membranes for biomedical applications. Am. Assoc. Pharm. Sci. PharmSciTech 2007, 8, E142–E146. [CrossRef]
[PubMed]

22844
Molecules 2015, 20, 22833–22847

22. Horii, F.; Hu, S.; Ito, T.; Odani, H.; Kitamaru, R.; Matsuzawa, S.; Yamaura, K. Cross polarization/magic
angle spinning 13 C-NMR study of solid structure and hydrogen bonding of poly (vinyl alcohol) films with
different tacticities. Polymer 1992, 33, 2299–2306. [CrossRef]
23. Albdiry, M.T.; Yousif, B.F. Morphological structures and tribological performance of unsaturated polyester
based untreated/silane-treated halloysite nanotubes. Mater. Des. 2013, 48, 68–76. [CrossRef]
24. Peppas, N.A.; Merrill, E.W. Development of semicrystalline poly (vinyl alcohol) hydrogels for biomedical
applications. J. Biomed. Mater. Res. 1977, 11, 423–434. [CrossRef] [PubMed]
25. Paradossi, G.; Cavalieri, F.; Chiessi, E.; Spagnoli, C.; Cowman, M.K. Poly (vinyl alcohol) as versatile
biomaterial for potential biomedical applications. J. Mater. Sci. Mater. Med. 2003, 14, 687–691. [CrossRef]
[PubMed]
26. Baker, M.I.; Walsh, S.P.; Schwartz, Z.; Boyan, B.D. A review of polyvinyl alcohol and its uses in cartilage and
orthopedic applications. J. Biomed. Mater. Res. B Appl. Biomater. 2012, 100, 1451–1457. [CrossRef] [PubMed]
27. Vergaro, V.; Abdullayev, E.; Lvov, Y.M.; Zeitoun, A.; Cingolani, R.; Rinaldi, R.; Leporatti, S. Cytocompatibility
and uptake of halloysite clay nanotubes. Biomacromolecules 2010, 11, 820–826. [CrossRef] [PubMed]
28. Lee, A.; Tsai, H.Y.; Yates, M.Z. Steric stabilization of thermally responsive N-isopropylacrylamide particles
by poly (vinyl alcohol). Langmuir 2010, 26, 18055–18060. [CrossRef] [PubMed]
29. Tan, C.J.; Tong, Y.W. The effect of protein structural conformation on nanoparticle molecular imprinting of
ribonuclease a using miniemulsion polymerization. Langmuir 2007, 23, 2722–2730. [CrossRef] [PubMed]
30. Yang, J.M.; Su, W.Y.; Leu, T.L.; Yang, M.C. Evaluation of chitosan/PVA blended hydrogel membranes.
J. Membr. Sci. 2004, 236, 39–51. [CrossRef]
31. Guo, Z.; Zhang, D.; Wei, S.; Wang, Z.; Karki, A.B.; Li, Y.; Bernazzani, P.; Young, D.P.; Gomes, J.A.;
Cocke, D.L.; et al. Effects of iron oxide nanoparticles on polyvinyl alcohol: Interfacial layer and bulk
nanocomposites thin film. J. Nanopart. Res. 2010, 12, 2415–2426. [CrossRef]
32. Kenawy, E.R.; Kamoun, E.A.; Eldin, M.S.; El-Meligya, M.A. Physically crosslinked poly
(vinyl alcohol)-hydroxyethyl starch blend hydrogel membranes: Synthesis and characterization for
biomedical applications. Arab. J. Chem. 2014, 7, 372–380. [CrossRef]
33. Kamoun, E.A.; Chen, X.; Eldin, M.S.; Kenawy, E.R. Crosslinked poly (vinyl alcohol) hydrogels for wound
dressing applications: A review of remarkably blended polymers. Arab. J. Chem. 2015, 8, 1–14. [CrossRef]
34. Zhao, L.; Mitomo, H.; Zhai, M.; Yoshii, F.; Nagasawa, N.; Kume, T. Synthesis of antibacterial
PVA/CM-chitosan blend hydrogels with electron beam irradiation. Carbohydr. Polym. 2003, 53, 439–446.
[CrossRef]
35. Muggli, D.S.; Burkoth, A.K.; Anseth, K.S. Crosslinked polyanhydrides for use in orthopedic applications:
Degradation behavior and mechanics. J. Biomed. Mater. Res. 1999, 46, 271–278. [CrossRef]
36. Hyon, S.H.; Cha, W.I.; Ikada, Y.; Kita, M.; Ogura, Y.; Honda, Y. Poly (vinyl alcohol) hydrogels as soft contact
lens material. J. Biomater. Sci. Polym. Ed. 1994, 5, 397–406. [CrossRef] [PubMed]
37. Kaity, S.; Isaac, J.; Ghosh, A. Interpenetrating polymer network of locust bean gum-poly (vinyl alcohol) for
controlled release drug delivery. Carbohydr. Polym. 2013, 94, 456–467. [CrossRef] [PubMed]
38. Lee, H.; Mensire, R.; Cohen, R.E.; Rubner, M.F. Strategies for hydrogen bonding based layer-by-layer
assembly of poly (vinyl alcohol) with weak polyacids. Macromolecules 2011, 45, 347–355. [CrossRef]
39. Ghebaur, A.; Garea, S.A.; Iovu, H. New polymer–halloysite hybrid materials—potential controlled drug
release system. Int. J. Pharm. 2012, 436, 568–573. [CrossRef] [PubMed]
40. Han, D.; Yan, L.; Chen, W.; Li, W. Preparation of chitosan/graphene oxide composite film with enhanced
mechanical strength in the wet state. Carbohydr. Polym. 2011, 83, 653–658. [CrossRef]
41. Mutsuo, S.; Yamamoto, K.; Furuzono, T.; Kimura, T.; Ono, T.; Kishida, A. Release behavior from
hydrogen-bonded polymer gels prepared by pressurization. J. Appl. Polym. Sci. 2011, 119, 2725–2729.
[CrossRef]
42. Shuai, C.; Mao, Z.; Lu, H.; Nie, Y.; Hu, H.; Peng, S. Fabrication of porous polyvinyl alcohol scaffold for bone
tissue engineering via selective laser sintering. Biofabrication 2013, 5, 015014. [CrossRef] [PubMed]
43. Ng, K.W.; Wanivenhaus, F.; Chen, T.; Hsu, H.C.; Allon, A.A.; Abrams, V.D.; Torzilli, P.A.; Warren, R.F.;
Maher, S.A. A novel macroporous polyvinyl alcohol scaffold promotes chondrocyte migration and interface
formation in an in vitro cartilage defect model. Tissue Eng. A 2012, 18, 1273–1281. [CrossRef] [PubMed]

22845
Molecules 2015, 20, 22833–22847

44. Lin, Y.; Ng, K.M.; Chan, C.M.; Sun, G.; Wu, J. High-impact polystyrene/halloysite nanocomposites prepared
by emulsion polymerization using sodium dodecyl sulfate as surfactant. J. Coll. Interface Sci. 2011, 358,
423–429. [CrossRef] [PubMed]
45. Stasio, F.D.; Korniychuk, P.; Brovelli, S.; Uznanski, P.; McDonnell, S.O.; Winroth, G.; Anderson, H.L.;
Tracz, A.; Cacialli, F. Highly Polarized Emission from Oriented Films Incorporating Water-Soluble Conjugated
Polymers in a Polyvinyl Alcohol Matrix. Adv. Mater. 2011, 23, 1855–1859. [CrossRef] [PubMed]
46. Du, M.; Guo, B.; Lei, Y.; Liu, M.; Jia, D. Carboxylated butadiene–styrene rubber/halloysite nanotube
nanocomposites: Interfacial interaction and performance. Polymer 2008, 49, 4871–4876. [CrossRef]
47. Swapna, V.P.; Selvin, T.P.; Suresh, K.I.; Saranya, V.; Rahana, M.P.; Ranimol, S. Thermal properties of poly
(vinyl alcohol)(PVA)/halloysite nanotubes reinforced nanocomposites. Int. J. Plast. Technol. 2015. [CrossRef]
48. Silva, E.D.; Lebrun, L.; Metayer, M. Elaboration of a membrane with bipolar behaviour using the
semi-interpenetrating polymer networks technique. Polymer 2002, 43, 5311–5320. [CrossRef]
49. Wang, J.; Wang, X.; Xu, C.; Zhang, M.; Zhang, X. Preparation of graphene/poly (vinyl alcohol)
nanocomposites with enhanced mechanical properties and water resistance. Polym. Int. 2011, 60, 816–822.
[CrossRef]
50. Gopishetty, V.; Tokarev, I.; Minko, S. Biocompatible stimuli-responsive hydrogel porous membranes via
phase separation of a polyvinyl alcohol and Na-alginate intermolecular complex. J. Mater. Chem. 2012, 22,
19482–19487. [CrossRef]
51. Ravindra, K.; Manasi, G.; Sheetal, G.; Kumar, P.B. Halloysite Nanotubes and Applications: A Review.
J. Adv. Sci. Res. 2012, 3, 25–29.
52. Lvov, Y.; Abdullayev, E. Functional polymer-clay nanotube composites with sustained release of chemical
agents. Prog. Polym. Sci. 2013, 38, 1690–1719. [CrossRef]
53. Zhou, W.Y.; Guo, B.; Liu, M.; Liao, R.; Rabie, A.B.; Jia, D. Poly (vinyl alcohol)/halloysite nanotubes
bionanocomposite films: Properties and in vitro osteoblasts and fibroblasts response. J. Biomed. Mater.
Res. A 2010, 93, 1574–1587. [CrossRef] [PubMed]
54. Song, K.; Zhang, Y.; Meng, J.; Green, E.C.; Tajaddod, N.; Li, H.; Minus, M.L. Structural polymer-based carbon
nanotube composite fibers: Understanding the processing–structure–performance relationship. Materials
2013, 6, 2543–2577. [CrossRef]
55. Joussein, E.; Petit, S.; Churchman, J.; Theng, B.; Righi, D.; Delvaux, B. Halloysite clay minerals—A review.
Clay Miner. 2005, 40, 383–426. [CrossRef]
56. Chen, D.H.; Leu, J.C.; Huang, T.C. Transport and hydrolysis of urea in a reactor–separator combining
an anion-exchange membrane and immobilized urease. J. Chem. Technol. Biotechnol. 1994, 61, 351–357.
[CrossRef] [PubMed]
57. Li, J.K.; Wang, N.; Wu, X.S. Poly (vinyl alcohol) nanoparticles prepared by freezing-thawing process for
protein/peptide drug delivery. J. Controll. Release 1998, 56, 117–126. [CrossRef]
58. Yoshii, F.; Zhanshan, Y.; Isobe, K.; Shinozaki, K.; Makuuchi, K. Electron beam crosslinked PEO and PEO/PVA
hydrogels for wound dressing. Radiat. Phys. Chem. 1999, 55, 133–138. [CrossRef]
59. Yoshii, F.; Makuuchi, K.; Darwis, D.; Iriawan, T.; Razzak, M.T.; Rosiak, J.M. Heat resistance poly
(vinyl alcohol) hydrogel. Radiat. Phys. Chem. 1995, 46, 169–174. [CrossRef]
60. Salunkhe, A.B.; Khot, V.M.; Thorat, N.D.; Phadatare, M.R.; Sathish, C.I.; Dhawale, D.S.; Pawar, S.H. Polyvinyl
alcohol functionalized cobalt ferrite nanoparticles for biomedical applications. Appl. Surface Sci. 2013, 264,
598–604. [CrossRef]
61. Lee, J.; Isobe, T.; Senna, M. Preparation of ultrafine Fe3 O4 particles by precipitation in the presence of PVA
at high pH. J. Coll. Interface Sci. 1996, 177, 490–494. [CrossRef]
62. Kayal, S.; Ramanujan, R.V. Doxorubicin loaded PVA coated iron oxide nanoparticles for targeted drug
delivery. Mater. Sci. Eng. C 2010, 30, 484–490. [CrossRef]
63. Chu, W.B.; Yang, J.W.; Liu, T.J.; Tiu, C.; Guo, J. The effects of pH, molecular weight and degree of hydrolysis
of poly (vinyl alcohol) on slot die coating of PVA suspensions of TiO2 and SiO2 . Coll. Surfaces A Physicochem.
Eng. Asp. 2007, 302, 1–10. [CrossRef]
64. Sirousazar, M.; Kokabi, M.; Hassan, Z.M.; Bahramian, A.R. Dehydration kinetics of polyvinyl alcohol
nanocomposite hydrogels containing Na-montmorillonite nanoclay. Sci. Iran. 2011, 18, 780–784. [CrossRef]

22846
Molecules 2015, 20, 22833–22847

65. Sirousazar, M.; Kokabi, M.; Hassan, Z.M. In vivo and cytotoxic assays of a poly (vinyl alcohol)/clay
nanocomposite hydrogel wound dressing. J. Biomater. Sci. Polym. Ed. 2011, 22, 1023–1033. [CrossRef]
[PubMed]
66. Fujii, K.; Nakagaito, A.N.; Takagi, H.; Yonekura, D. Sulfuric acid treatment of halloysite nanoclay to improve
the mechanical properties of PVA/halloysite transparent composite films. Compos. Interfaces 2014, 21,
319–327. [CrossRef]
67. Jang, J.; Lee, D.K. Plasticizer effect on the melting and crystallization behavior of polyvinyl alcohol.
Polymer 2003, 44, 8139–8146. [CrossRef]
68. Fernandes, E.M.; Pires, R.A.; Mano, J.F.; Reis, R.L. Bionanocomposites from lignocellulosic resources:
Properties, applications and future trends for their use in the biomedical field. Prog. Polym. Sci. 2013,
38, 1415–1441. [CrossRef]
69. Jayasekara, R.; Harding, I.; Bowater, I.; Christie, G.B.; Lonergan, G.T. Preparation, surface modification and
characterisation of solution cast starch PVA blended films. Polym. Test. 2004, 23, 17–27. [CrossRef]
70. Heuschmid, F.F.; Schuster, P.; Lauer, B.; Fabian, E.; Leibold, E.; Ravenzwaay, B.V. Polyethylene
glycol-polyvinyl alcohol grafted copolymer: Study of the bioavailability after oral administration to rats.
Food Chem. Toxicol. 2013, 51, S3–S6. [CrossRef] [PubMed]
71. Ghaffari-Moghaddam, M.; Eslahi, H. Synthesis, characterization and antibacterial properties of a novel
nanocomposite based on polyaniline/polyvinyl alcohol/Ag. Arab. J. Chem. 2014, 7, 846–855. [CrossRef]
72. He, Y.; Kong, W.; Wang, W.; Liu, T.; Liu, Y.; Gong, Q.; Gao, J. Modified natural halloysite/potato starch
composite films. Carbohydr. Polym. 2012, 87, 2706–2711. [CrossRef]
73. Spiridon, I.; Popescu, M.C.; Bodârlău, R.; Vasile, C. Enzymatic degradation of some nanocomposites of poly
(vinyl alcohol) with starch. Polym. Degrad. Stab. 2008, 93, 1884–1890. [CrossRef]
74. Liu, M.; Jia, Z.; Jia, D.; Zhou, C. Recent advance in research on halloysite nanotubes-polymer nanocomposite.
Prog. Polym. Sci. 2014, 39, 1498–1525. [CrossRef]
75. Dong, Y.; Chaudhary, D.; Haroosh, H.; Bickford, T. Development and characterisation of novel electrospun
polylactic acid/tubular clay nanocomposites. J. Mater. Sci. 2011, 46, 6148–6153. [CrossRef]
76. Chang, P.R.; Xie, Y.; Wu, D.; Ma, X. Amylose wrapped halloysite nanotubes. Carbohydr. Polym. 2011, 84,
1426–1429. [CrossRef]
77. Atabey, E.; Wei, S.; Zhang, X.; Gu, H.; Yan, X.; Huang, Y.; Shao, L.; He, Q.; Zhu, J.; Sun, L.; et al. Fluorescent
electrospun polyvinyl alcohol/CdSe@ZnS nanocomposite fibers. J. Compos. Mater. 2013, 47, 3175–3185.
[CrossRef]
78. Pandele, A.M.; Ionita, M.; Crica, L.; Dinescu, S.; Costache, M.; Iovu, H. Synthesis, characterization, and
in vitro studies of graphene oxide/chitosan–polyvinyl alcohol films. Carbohydr. Polym. 2014, 102, 813–820.
[CrossRef] [PubMed]
79. Zhao, Y.; Wang, S.; Guo, Q.; Shen, M.; Shi, X. Hemocompatibility of electrospun halloysite nanotube-and
carbon nanotube-doped composite poly (lactic-co-glycolic acid) nanofibers. J. Appl. Polym. Sci. 2013, 127,
4825–4832. [CrossRef]
80. Sakurada, I. Polyvinyl Alcohol Fiber; Marcel Dekker, Inc.: New York, NY, USA, 1985.
81. Dong, Y.; Bickford, T.; Haroosh, H.J.; Lau, K.T.; Takagi, H. Multi-response analysis in the material
characterisation of electrospun poly (lactic acid)/halloysite nanotube composite fibres based on Taguchi
design of experiments: Fibre diameter, non-intercalation and nucleation effects. Appl. Phys. A 2013, 112,
747–757. [CrossRef]
82. Qi, R.; Cao, X.; Shen, M.; Guo, R.; Yu, J.; Shi, X. Biocompatibility of electrospun halloysite nanotube-doped
poly (lactic-co-glycolic acid) composite nanofibers. J. Biomater. Sci. Polym. Ed. 2012, 23, 299–313. [CrossRef]
[PubMed]
83. Wu, S.; Zheng, G.; Guan, X.; Yan, X.; Guo, J.; Dai, K.; Liu, C.; Shen, C.; Guo, Z. Mechanically Strengthened
Polyamide 66 Nanofibers Bundles via Compositing With Polyvinyl Alcohol. Macromol. Mater. Eng. 2015.
[CrossRef]

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