crystals

Review
Morphology, Thermal Stability, and Flammability
Properties of Polymer-Layered Double Hydroxide
(LDH) Nanocomposites: A Review
Mokgaotsa Jonas Mochane 1, * , Sifiso Innocent Magagula 1 , Jeremia Shale Sefadi 2, *,
Emmanuel Rotimi Sadiku 3 and Teboho Clement Mokhena 3
1 Department of Life Sciences, Central University of Technology, Free State, Private Bag X20539,
Bloemfontein 9300, South Africa; [email protected]
2 Department of Physical and Earth Sciences (PES), Sol Plaatje University, Kimberley 8301, South Africa
3 Department of Chemical, Institute of NanoEngineering Research (INER),
Metallurgical and Materials Engineering, Tshwane University of Technology, RSA, Pretoria 0001,
South Africa; [email protected] (E.R.S.); [email protected] (T.C.M.)
* Correspondence: [email protected] or [email protected] (M.J.M.); [email protected] (J.S.S.)




Received: 15 May 2020; Accepted: 1 July 2020; Published: 14 July 2020


Abstract: The utilization of layered nanofillers in polymer matrix, as reinforcement, has attracted
great interest in the 21st century. This can be attributed to the high aspect ratios of the nanofillers and
the attendant substantial improvement in different properties (i.e., increased flammability resistance,
improved modulus and impact strength, as well as improved barrier properties) of the resultant
nanocomposite when compared to the neat polymer matrix. Amongst the well-known layered
nanofillers, layered inorganic materials, in the form of LDHs, have been given the most attention.
LDH nanofillers have been employed in different polymers due to their flexibility in chemical
composition as well as an adjustable charge density, which permits numerous interactions with
the host polymer matrices. One of the most important features of LDHs is their ability to act as
flame-retardant materials because of their endothermic decomposition. This review paper gives
detailed information on the: preparation methods, morphology, flammability, and barrier properties
as well as thermal stability of LDH/polymer nanocomposites.

Keywords: nanocomposites; nanofillers; thermal stability; flammability; polymer matrix

1. Introduction
Polymer matrices are normally reinforced with inorganic fillers in order to improve their properties
and widen their applications [1]. The well-known fillers include silicate, carbon based, calcium
carbonate, fibres, etc. It is apparent that the incorporation of filler requires high content in order to have
any significant influence of the properties of the polymer matrices. A higher composition of fillers,
in most cases, results in increased weight of the resultant composites, which limits the applications of
such systems. In order to solve the problem of weight, nanoparticles have recently emerged as the
filler of choice to enhance the properties of the resultant polymer matrix. This is due to the ability of
nanoparticles to influence the properties of a polymer matrix with considerably low contents, thereby
allowing the nanocomposites to maintain low density of the polymer matrix.
The incorporation of layered inorganic fillers into polymer matrices to form polymer/layered
inorganic nanocomposites has attracted a lot attention due to their distinctive properties [2]. Layered
double hydroxides/polymer nanocomposites belong to an important class of polymer/layered inorganic
nanocomposites because they have shown significant improvement in the composites’ thermal stability,
flame retardancy, and improvement in overall physical properties [3,4]. Due to high pressure that

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Crystals 2020, 10, 612 2 of 26

can limit or prohibit the use of halogen flame retardant materials because of environmental concerns,
LDHs have emerged as a suitable candidate for halogen-free flame-retardant material [5–8]. It is well
documented in the literature that the methods used for the synthesis of LDH include: urea hydrolysis,
hydrothermal synthesis, co-precipitation, and ion exchange [9,10].
From a chemistry point of view, the structure of LDH can be presented by the following formula:
[M 1−x Mx III (OH)2 ] intra [Ax/m m− ·nH2 O] inter .
II

In the formula, inter and intra are the intralayer crystalline domain and interlayer spaces,
respectively. The layers of the LDHs are positively charged edge-shared octahedral coordinated metal
hydroxide crystal structures, sandwiched by charge compensating interlayer anions with optional
solvation in water. Furthermore, MII (M2+ ) is the divalent cation, whereas MIII (M3+ ) is the trivalent
cation and A is described as an anion with the valency m. Nevertheless, it is apparent that LDHs
consist of high charge density in the interlayer and they seem to have an impenetrable action between
the hydroxides when compared with the well-known layered silicates, which makes exfoliation very
difficult [2]. Furthermore, the fact that polymers are hydrophobic results in further hindrance of the
polymer chains into the LDHs. It is very clear that there is the need to incorporate anionic materials in
order to improve the intercalation of polymers into the LDHs layers. The easiest and convenient route
for fabrication of polymer/LDHs with improved properties is to modify the clay with surfactant or
other materials with the aim of preparing a stable LDHs/polymer nanocomposite system. This review
paper discusses the different modifications of LHDs and the preparation of polymer nanocomposites
with enhanced properties, i.e., better dispersion, flammability resistance, and thermal stability.

2. History of Layered Double Hydroxides (LDHs)

The existence of LDHs dates back to 1842, where minerals consisting of LDHs were discovered in
Sweden. The laboratory synthesis of LDHs began in 1942 and was based on the reaction of dilute metal
solutions with bases. Due to their structural similarities to the hydrotalcites, LDHs were referred to as
hydrotalcite-like compounds (HTLCs). Hydrotalcites are compounds that exist as hydroxycarbonates
of magnesium and aluminium or magnesium and iron (pyroaurite). These hydroxycarbonates are
found in nature, in the form of foliated and twisted plates [11]. In the early 1970s, hydrotalcites
began to be used as catalysts and precursors of various catalysts. This triggered a lot of interest
towards the research of LDHs [11,12]. The first studies on the single crystal X-ray diffraction of
minerals revealed that LDHs possessed a layered structure. Each layer consists of two cations and
the interlayer space was filled with water and carbonate ions. However, at first, this was debated
by several researchers. The reason for this was that even though the main components of the LDH
structure had been identified, some researchers still felt that the intrinsic details associated with the
structural components of LDHs were not yet understood [13]. LDHs can be formed naturally through
natural processes and synthetically in the laboratory. In nature, LDHs are formed naturally by natural
processes, such as the weathering of basalt rocks [14,15] and the precipitation [16] of saline water.
As mentioned earlier, the structure of LDHs resembles that of naturally occurring hydrotalcites with
the formula, [Mg6 Al2 (OH)16 ]CO3 ·4H2 O and a general formula, [M(II)1−x M(III)x (OH)2 ](Yn− )x/n ·YH2 O,
where M(II) and M(III) are divalent and trivalent metals, respectively; 0.2 < x < 0.33 and Yn− are
exchangeable interlayer anions [17–19]. Synthetically formed LDHs have a highly hydrophilic nature
with an amorphous or semicrystalline hexagonal structure. The structure of the LDH layers is based
on the brucite compound [Mg(OH)2 ]. The layers that are adjacent to each other are usually tightly
bound together [11]. The structure of LDHs is shown in Figure 1.
Crystals 2020, 10, 612 3 of 26

Crystals 2020, 10, x FOR PEER REVIEW 3 of 31

Figure 1. General chemical

Figure 1. Generalstructure
chemicalofstructure
layered double hydroxides
of layered (LDHs). Adapted
double hydroxides (LDHs)from
[10].Scarpellini,
D., Falconi, C., Gaudio, P., Mattoccia, A., Medaglia, P.G., Orsini, A., Pizzoferrato, R., Richetta, M.,
During the synthesis
Morphology of Zn/Aloflayered
LDHs, many
doubledifferent combinations grown
hydroxidenanosheets of divalent
onto and trivalentthin
aluminum metal cations
films,
are used; these include: magnesium, aluminium, zinc, nickel, chromium, iron,
Microelectron. Eng. 2014, 126, 129–133. With the kind permission of Elsevier [10].copper, indium, gallium,
and calcium [17,20–22].
LDHs are
LDHs areusually
usuallypreferred
preferredoveroverclays
claysororother
other layered
layered materials.
materials. This
This is because
is because thethe synthesis
synthesis of
of LDHs
LDHs haspotential
has the the potential of forming
of forming LDHs with LDHs a widewith a wide
range range of compositions
of compositions and metal-ionand metal-ion
combinations.
combinations.
Their preferenceTheir
overpreference
clay is alsooverdueclay is also
to the factduethattoLDHs
the fact thathigh
have LDHs have density.
charge high chargeThedensity.
charge
The charge
density density
of the LDHs ofisthe LDHs is determined
determined by the ratio by of
thethe
ratio of the divalent
divalent and trivalent
and trivalent metal cations.
metal cations. If the
If the divalent/trivalent ratio is low, the charge density increases [11].
divalent/trivalent ratio is low, the charge density increases [11]. LDHs have unique physical andLDHs have unique physical
and chemical
chemical properties
properties that arethat are related
closely closely torelated
those of to clays.
those The of clays. The charged
positively positively charged
layered layered
structure of
structure
LDHs of LDHs
induces induces
properties, such asproperties,
anion mobility,suchsurface
as anion mobility,
basicity, and anionsurface basicity, and
exchangeability. anion
The water
exchangeability.
and the anions foundThe water
betweenandthe thelayers
anionsoffound
LDHsbetween
are labile. theTherefore,
layers of LDHs
exchangeare labile. Therefore,
reactions can be
exchange
used reactions
to replace these can be used anions
interlayer to replace withthese interlayer
various inorganicanions with various
or organic anions inorganic
[23]. Whenor organic
LDHs
anions
are [23]. When
calcinated, mixed LDHs
metalare calcinated,
oxides mixed metal
with properties, suchoxides
as large with properties,
surface area and such as large
surface surface
basicity are
area and surface
obtained. basicity
At elevated are obtained.
temperatures, theAt elevated
metal oxides temperatures,
formed also the formmetal oxides formed
a homogenous also with
mixture form
a homogenous
small crystallitemixture
sizes [11].with
Thesmall
LDHs crystallite
and metal sizes [11]. formed
oxides The LDHs and calcination
during metal oxides formed
also have during
a high
calcination
catalytic also have a high catalytic activity.
activity.
LDHs possess
LDHs possess a structural reconstruction
reconstruction or memory effect effect property
property that is only unique to them.
Structural reconstruction
Structural reconstruction is aa property
property that that is
is induced
induced by by the
the calcination
calcination ofof LDHs
LDHs and and the
the treatment
treatment
of metal oxides with a specific anionic solution [24]. These materials can
of metal oxides with a specific anionic solution [24]. These materials can easily adsorb anions and easily adsorb anions and
cations [25,26]. The
cations Themagnetic
magneticproperties
propertiesofofLDHs LDHs are usually
are usually regulated
regulated bybythethe
chemical
chemical nature of the
nature of
interlayer
the spaces
interlayer spacesin in
them.
them.TheThe chemical
chemical environment
environment in inthese
thesespaces
spacescan canbe be modified
modified by the the
intercalation with
intercalation with organic
organic anions
anions of of different
different chain
chain lengths.
lengths. This results in in hybrid
hybrid materials
materials with
with
tunable magnetic
tunable magnetic properties
properties[27].
[27]. The
The intercalation
intercalationof ofLDHs
LDHswith withlong-chain
long-chainsurfactants,
surfactants,e.g.,
e.g. dodecyl
dodecyl
sulphates,forms
sulphates, forms hybrid
hybrid materials
materialsthatthat swell
swell inin organic
organic solvents.
solvents. This swelling characteristic
characteristic isis usually
exploited in the
exploited thefabrication
fabricationofofmonolayers
monolayers used
used in in
nanohybrid
nanohybrid andand
nanocomposite
nanocomposite synthesis [28].[28].
synthesis The

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Crystals 2020, 10, 612 4 of 26

The chemical environment in between the layers of LDHs is usually altered by the exchange of anions.
The exchange of anions follows the following order of preference:

− − − −
NO−
3 < Br < Cl < F < OH < SO4
2−
< CO2−
3

Here, the NO− 3

anion can be easily replaced by the CO2−3
anion. Therefore, in the preparation
of a precursor for interaction, the NO− 3
anion is preferred over the CO2−
3
anion. This is because the
interaction has to happen in such a manner that the introduction of the guest molecule does not
change the structure of the host. During this interaction, the existing ion is replaced by the guest
molecule. The anions that are weakly bonded to the hydroxide layers are usually the most vulnerable
for replacement by other ions [29–31].
Many different methods are used for the synthesis of LDHs. The type of method used depends
on the required characteristics and applications of the resultant material. The most commonly used
methods/techniques are methods such asco-precipitation, hydrothermal synthesis, urea hydrolysis,
sol-gel, ion-exchange, and rehydration. There also are other methods often employed, such as self-oxide
method, template synthesis method, and surface synthesis method. The co-precipitation method is
one of the commonly used methods. In this method, the LDH structure is formed by the mixing of
aqueous solutions of M(II), M(III), and interlayer anions. This method gives the liberty to prepare
LDHs that consist of a wide range of anions and cations. The co-precipitation method is uniquely
used to prepare organic-anion LDHs [13]. The co-precipitation method can be further subdivided
into three other methods, viz co-precipitation by filtration, co-precipitation at lower supersaturation,
and co-precipitation at higher supersaturation methods.
The hydrothermal synthetic method is usually employed to regulate particle size and particle size
distribution. The hydrothermal synthesis method follows two synthesis routes. The first route is where
the materials are prepared at temperatures above 373 K in a pressured autoclave. Here, the LDHs are
synthesized from MgO and Al2 O3 precursors or from mixtures formed through the decomposition
of the precursor nitrate compounds [11,32,33]. In the other synthesis route, LDHs are prepared at
low temperatures and are also subjected to a process of aging. During the aging process, the LDH
precipitate is refluxed at a specific temperature for 18 h.
In the urea hydrolysis method, urea is used as a precipitation agent in the synthesis of LDHs,
at specific temperatures. The degree of crystallinity of LDHs depends on the synthesis temperature
and decomposition rate. At low temperatures, large particles are formed due to the slow nucleation
and slow decomposition rates of the urea [34,35]. The urea hydrolysis method is uniquely used in the
synthesis of LDHs with a high charge density [34].
In the sol-gel method, LDHs are produced by first forming a sol via the hydrolysis and partial
condensation of a metallic precursor, followed by the formation of a gel. Here, the hydrolysis and
condensation rates of the metallic precursors determine the properties of the resultant LDHs [36].
The condensation and hydrolysis rates of the metallic precursors are also susceptible to modification
by various reaction parameters, such as pH, type and concentration of the precursor, synthesis
temperature, and solvent used. The sol-gel method forms LDHs with a larger surface area than those
formed by the co-precipitation method [37–39]. However, properties such as basicity as well as the
divalent and trivalent metal ion molar ratios of LDHs synthesized with the sol-gel method are still not
understood [38–40].
The ion-exchange method involves the exchange of interlayer anions with other guest anions
introduced into the LDH structure in order to obtain the LDH-guest compound. Several factors, such as
affinity towards the guest anions, the medium of exchange, pH, and the chemical nature of the brucite
layers affect the ion-exchange in LDHs [41].
In the rehydration method, the mixed metal oxides formed after the calcination of LDHs at high
temperatures between 500–800 ◦ C are rehydrated and formed into an LDH structure in the presence of
the desired anions [42–47].
Crystals 2020, 10, 612 5 of 26

3. Selective Polymer Matrices for Fabrication LDHs

Polymer matrices are frequently reinforced by different nanofillers to reduce the limitations of
polymers and widen their applications. LDHs nanofillers have been incorporated into polymer matrices
to improve the mechanical properties, flammability resistance, and the overall physical properties of
polymers. Polymer matrices in nanofiller polymer nanocomposites are used to provide shape and
durability in the nanocomposites.
Different polymer matrices have been used for fabrication of polymer-LDHs nanocomposites.
The polymer matrices include polymethyl methacrylate (PMMA), epoxy, polylactic acid (PLA),
polyvinyl chloride (PVC), polypropylene (PP), poly(ethylene terephthalate)(PET), polystyrene (PS),
polyaniline, low-density polyethylene (LDPE), acrylonitrile-butadiene-styrene (ABS), ethylene vinyl
acetate (EVA), linear low density polyethylene (LLDPE), cellulose, and poly(caprolactone) [48–60].
Based on the polymer matrices mentioned above, it is clear that thermoplastic and thermosets
were used as host matrices for preparation of LDHs-nanocomposites. However, it is apparent
that thermoplastic matrices were preferred over the thermosets because the former are lightweight,
can be re-melted, and shaped. Due to an environmental protection, there is a slight shift towards
fabrication of biopolymer matrix/LDHs nanocomposites. The resultant nanocomposite is termed
“green nanocomposite”, and these nanocomposites are favourites to replace petroleum-based plastics.
Table 1 summarizes selective polymer matrices for preparation of LDHs nanocomposites.

Table 1. LDHs nanocomposites with selective polymer matrices.

Type of Polymer (Thermoset or

Nanocomposites Typical Example of Nanocomposite References
Thermoplastic)
Polyaniline (PANI)/LDHs Thermoset PANI/Mg– Al-LDH [48]
Polyaniline (PAn)/LDHs Thermoset PAn/(3:1; Zn/Al-LDHs) [49]
Polypropylene (PP)/LDHs Thermoplastic, polyolefin PP/MgAl-layered double hydroxides [50]
PLA/(Mg-Al-LDH-C12 ) and
PLA/LDHs Thermoplastic, polyester [51]
PLA/Mg- Al -LDH-CO3
EP/Zn-Al-CO3 -HA LDH and
Epoxy (EP)/LDHs Thermoset EP/Mg-Al-CO3 -HA LDH, [52]
HA = Hydroxyapatite
Ethylene propylene diene
Thermoplastic, elastomer EPDM/Cu–Al –LDHs [53]
(EPDM)/LDH
LLDPE/LDH Thermoplastic LLDPE/Zn Al-LDH [54]
LDPE with (i) Mn2 Al-LDH-stearate and (ii)
LDPE/LDHs Thermoplastic [55]
Co2 Al-LDH-stearate
poly(3-hydroxybutyrate-co-3
Thermoplastic, polyester PHBV/Mg- Al layered double hydroxide [56]
-hydroxyvalerate) (PHBV)
TPU/CoAl-LDH and TPU/APP@ Co Al –LDH
Thermoplastic Polyurethane Thermoplastic [57]
APP = ammonium polyphosphate
Poly(-caprolactone)
Thermoplastic, polyester PCL/Zn Al -LDH [58]
(PCL)/LDH
Highly amorphous vinyl HAVOH/Zn Al -LDH-CNTs
Thermoplastic [59]
alcOHol (HAVOH)/LDH CNTs = carbon nanotubes
Polybutylene succinate
Thermoplastic, polyester PBS/Mg Al-LDH [60]
(PBS)/LDH

4. Preparation and Morphology of Polymer-LDHs Nanocomposites

In most studies, it was explained that dispersion of the filler/nanofiller within a polymer matrix
plays a very important role in the properties of the fabricated polymer nanocomposite. In an
LDHs/polymer system, the LDHs are normally modified with organic anions in order to enhance
their interactions with polymer matrices. The main reason for improving the interaction between
the two components, i.e., polymer and LDHs, is because the polymer is hydrophobic and LDHs is
hydrophilic [61]. Furthermore, the method of preparation was also found to have a huge impact on
the dispersion of the LDHs within the polymer matrix. The literature has shown that in most cases,
LDHs are fabricated with different metals, depending on the desired applications. Leng and co-workers
Crystals 2020, 10, 612 6 of 26

investigated the structure-property relationship of composites formed from polylactic acid (PLA) and
layered double hydroxides and the comparison of MgAl and NiAl LDH as nanofillers [62]. The metal (s)
LDHs were organically modified with sodium dodecyl benzene sulfonate (SDBS). LDHs and PLA
were prepared by a melt mixing process at a temperature of 190 ◦ C (463 K). The morphological
comparison was based on a 3 wt.% content of LDH. Large particles with an estimated size of 100 nm
with less agglomerates were obtained for MgAl LDH/PLA (Figure 2A). According to the authors,
this arrangement will allow partial exfoliation of the metal Al/LDH layers. However, in the system
fabricated from NiAl/LDH-PLA, more aggregates were reported. The structures obtained are more
favourable to intercalation than exfoliation. With the findings obtained above, it can be summarized that
the system of NiAl/LDH-PLA favoured intercalation, whereas the MgAl/LDH-PLA nanocomposites is
aCrystals
typical exfoliated system.
2020, 10, x FOR PEER REVIEW 7 of 31

2. TEM
Figure 2. TEMpicture
picturefor
fornanocomposites
nanocomposites with anan
with LDHLDHconcentration of 3of
concentration wt.%. (A) MgAl/LDH–PLA
3 wt.%. (A) MgAl/LDH–
size
PLA bare 2 µm;
size bare (B)(B)
2 µm; MgAl/LDH–PLA
MgAl/LDH–PLAsize sizebare
bare 200 nm; (C)
200 nm; (C)NiAl/LDH–PLA
NiAl/LDH–PLA size
size bare
bare 1 µm;
1 µm; (D)
(D) NiAl/LDH–PLA size bare 200 nm [62].
NiAl/LDH–PLA size bare 200 nm [62]. Adapted from Leng, J.; Kang, N.; De-Yi, W.; Falkenhagen, J.;
Thünemann, A.F.; Schönhals, A. Structure-property relationship of nanocomposites based on
Quispe-Dominguez
polylactide and layered et al.double
[63] investigated two types of mixing
hydroxides-comparison of MgAlmethods
and NiAl in order
LDH toascompare which
nanofiller.
method provides
Macromol. better
Chem. dispersion
Phys. of MgAl-DBS
2017, 1700232, 1–12. WithLDH
the in a PLA
kind matrix.ofLDH
permission Johnwas
Wileymodified with sodium
and Sons.
dodecylbenzene sulfonate (DBS). The methods employed in this study include: (i) sonication-assisted
masterbatch melt mixing and
Quispe-Dominguez (ii)[63]
et al. direct melt mixing.
investigated twoSonication-assisted
types of mixing methodsmasterbatch melt mixing
in order was
to compare
undertaken
which method by dissolving PLA and
provides better MgAl-DBS
dispersion in methylene
of MgAl-DBS LDHchloride as a matrix.
in a PLA solvent.LDH
Afterwas
12 hmodified
and at a
temperature 80 ◦ C, the solvent
with sodiumofdodecylbenzene was evaporated,
sulfonate withmethods
(DBS). The the masterbatch
employed formed,
in thisprocessed at 170 ◦(i)
study include: C
in a twin-screw compounder
sonication-assisted masterbatchfor 10 min.mixing
melt However, andfor(ii)
direct mixing,
direct meltthere was no
mixing. need for solvent
Sonication-assisted
mixing; PLAmeltand mixing
MgAl-DBS ◦ C for 10 min. It was observed that
masterbatch was were melt-mixed
undertaken directly at
by dissolving PLA170and MgAl-DBS in methylene chloride
the
as asonication-assisted
solvent. After 12 masterbatch
h and at a melt mixing method
temperature of 80 °C, resulted in better
the solvent wasdispersion, intercalation,
evaporated, with the
and exfoliation
masterbatch of LDH
formed, when compared
processed at 170 °Ctoindirect mixing for
a twin-screw all investigated
compounder compositions.
for 10 min. However, Thefor
particle
direct
mixing, there was no need for solvent mixing; PLA and MgAl-DBS were melt-mixed directly at 170
°C for 10 min. It was observed that the sonication-assisted masterbatch melt mixing method resulted
in better dispersion, intercalation, and exfoliation of LDH when compared to direct mixing for all
investigated compositions. The particle size of the metal (s)-LDHs nanofiller has been proven to have
an influence on the dispersion of the nanofiller within a polymer matrix [64]. It was reported that the
 Crystals 2020, 10, 612 7 of 26

size of the metal (s)-LDHs nanofiller has been proven to have an influence on the dispersion of the
nanofiller within a polymer matrix [64]. It was reported that the fabrication of LDH with gel resulted
in large particle sizes (of between 3−4 µm), whereas the preparation of LDH nanoparticles through
sonication produced smaller nanoparticles (of between 50–200 nm) (Figure 3). The nanocomposites
with compositions of between 1–10 wt.% of Mg−Al LDH were prepared by the modified solution
mixing method. The authors reported better dispersion for smaller sonicated LDH nanoparticles
within isotactic polypropylene (iPP) matrix, as confirmed by wide angle x-ray diffraction (WAXD) and
atomic force microscopy. Table 2 illustrates the summary of some selective studies on the preparation
and2020,
Crystals morphology of polymer-LDHs
10, x FOR PEER REVIEW nanocomposites. 8 of 31

Figure
Figure 3. Graphic
3. Graphic representation
representation ofpreparation
of the the preparation of isotactic
of isotactic polypropylene/Mg–Al
polypropylene/ Mg−Al LDHLDH layered
layered
double
double hydroxide
hydroxide nanocompositesReprinted
nanocomposites. [64]. (adapted) with permission from Nagendra, B.;
MOHan, K.; Gowd, E.B. Polypropylene/layered double hydroxide (LDH) nanocomposites: Influence
of LDH particle size on the crystallization behaviour of polypropylene 2015 American Chemical
Society [64].
Crystals 2020, 10, 612 8 of 26

Table 2. Selective studies on preparation and morphology of polymer-LDHs nanocomposites.

Preparation Method of the

Polymer/LDHs System Synthesis of the Metal-LDH Nanofiller Summary of the Resultant Morphology References
Nanocomposites
Polyurethane (Pu)/CoAl-LDH Urea hydrolysis In-situ intercalation polymerization The exfoliation of the nanofiller within a matrix was reported. [65]
Four different nanocomposites were prepared depending on the chemical
functionalizing of PVC: (i) PVC/Mg-Al LDH (ii) (PVC+thiosulfate)/Mg-Al
Functionalized Poly (vinyl
Co-precipitation method Solution intercalation method LDH (iii) (PVC+sulfate)/Mg-Al LDH (iv) (PVC+thiourea)/Mg-Al LDH. [66]
chloride) (PVC)/Mg-Al LDH
Amongst all formed nanocomposites, more exfoliated structures were
observed for (PVC+thiourea)/Mg-Al.
Different LDH content (viz 2, 4, 6, 8%) were synthesized with PAN.
Polyacrylonitrile (PAN)/Zn-Al Transmission electron microscopy (TEM) showed disordered dispersion of
Co-precipitation In-situ polymerisation technique [67]
LDH nanofiller in the PAN matrix. However, at higher content of the nanofiller
(viz 8%), more agglomerates were obtained.
The PMMA nanocomposites consisting of 2, 4, 6, 8% composition of LDH
Poly(methyl was prepared by in situ polymerisation. The authors reported a random
methacrylate)/Mg–Al LDH Co-precipitation In-situ polymerisation dispersion of the nanofiller with a polymer matrix. There was an [68]
(PMMA/LDH) observation of exfoliation of the nanofiller with partial intercalation at
higher content of the nanofiller.
The urea-assisted hydrothermal method was
used for preparation of MgAl-LDH, while the
Poly (ethylene terephthalate)
co-precipitation method was used for Scanning electron microscopy (SEM) and TEM showed homogenous
(PET)/CaAl-LDH and Solution blending method [69]
fabrication of CaAl-LDH. The co-precipitation distribution of both CaAl-LDH and MgAl-LDH within a PET matrix.
MgAl-LDH
method was employed for MgAl-LDH with
stearic acid (MgAl-LDH-SA)
The nanofiller in this study were modified by Potassium dodecyl
Linear Low Density phosphate (PDP). SEM pictures showed uniform dispersion of the
High-energy ball milling Melt blending and blowing [70]
Polyethylene/ZnAl-PDP LDH nanofiller into the polymer matrix. The results were supported by XRD,
which indicated no diffraction peak for LDH.
The PMMA nanocomposites were prepared by the solvent blending
Poly(methyl
technique. The authors reported a wide dispersion of the nanofiller within
methacrylate)/Co–Al LDH Instinctive self-assembly approach Solvent blending technique [71]
the PMMA matrix. There was an observation of exfoliation of the
(PMMA/LDH)
nanofiller with partial intercalation at higher content of the nanofiller.
The nanofiller in this study was modified by dodecyl sulfate (DS). TEM
results showed uniform dispersion of the nanofiller into the polymer
Linear Low Density
Anion exchange method Solution intercalation method matrix. Moreover, XRD and TEM results showed the formation of a [72]
Polyethylene (LLDPE)/LDH
mixture of intercalated-exfoliated structures in the
LLDPE/LDH composites.
Crystals 2020, 10, 612 9 of 26

5. Thermal Stability of Polymer/LDHs Nanocomposites

Different studies have investigated the thermal stability of LDH/polymer nanocomposites [63,65,73–84].
Various thermal stability results (decrease or increase in the thermal stability of the nanocomposites)
were recorded, depending on the LDH/polymer nanocomposites system. Lee et al. [84] reported an
increase in the thermal stability of a composite that had the addition of the nanofiller into an ethylene
vinyl acetate (EVA) matrix. In this study, an LDH nanofiller was modified with anionic surfactant,
such as sodium dodecyl sulfate (DS), sodium dodecylbenzene sulfonate (DBS), and stearate (SA).
When comparing the thermal stability (at 50% weight loss) of the three modifications, 6 phr of
DS-LDH/EVA nanocomposites showed 19 ◦ C increment, while both the 6 phr of DBS-LDH/EVA and
SA-LDH/EVA nanocomposites recorded 12 ◦ C increase from the pristine EVA (Figure 4). However,
Quispe-Dominguez et al. [63] reported a decrease in thermal stability with the incorporation of
magnesium-aluminium layered double hydroxides modified with dodecylbenzene sulfonate (DBS).
This was attributed to the catalytic effect of the modified nanofiller in the polymer matrix and as a
result, reducing the thermal stability of the overall nanocomposites. Due to the two different mixing
methods (viz: sonication-assisted masterbatch melt mixing and direct mixing) employed in this study
for preparation of the nanocomposites, differences in thermal stabilities were observed, depending on
the mixing method employed. It was reported that as much as the thermal stability decreases with
the addition and increases in nanofiller content, the nanocomposites prepared by masterbatch melt
mixing exhibited enhancement in thermal stability when compared with direct mixing, especially
when considering same nanofiller content. For example, at 1.25% of the nanofiller, masterbatch melt
mixing showed higher thermal stability than direct mixing at the same content. This behaviour was
ascribed to a finer dispersion and better intercalation of the nanofiller during masterbatch melt mixing.
Better dispersion and intercalation emphasize the fact that the PLA chains were more intercalated
in the LDHs layers, in case of the PLA nanocomposites prepared by the SMA melt mixing method,
resulting in an enhancement of thermal stability than the poorly dispersed and agglomerated nanofiller
in case of the direct mixing method. Zoromba et al. [83] modified both copper-aluminium LDH and
nickel-aluminium LDH with sodium stearate modifier and melt-mixed them with PP in an extruder.
The authors reported better improvements in the thermal stability of the modified nickel-aluminium
LDH when compared with neat PP, the unmodified nickel-aluminium LDH/PP, and copper-aluminium
LDH/PP nanocomposites. The improvement was attributed to better interfacial interaction between
the nanofiller and the polymer matrix.
In this study, PMMA nanocomposites were prepared by solution mixing by adding
flame resistant materials, such as intumescent flame retardant (IFR) (i) 1,2-Bis(5,5-dimethyl-1,3,2
-dioxyphospacyclOHexane phosphoryl amide) ethane (BPEA), (ii) graphene (reduced graphene oxide),
and (iii) magnesium aluminium-layered double hydroxide modified with sodium dodecyl sulfate.
It was reported that in the absence of IFR (BPEA), there was an increase in the thermal stability of
PMMA nanocomposites with reduced graphene oxide (rGO), LDH, and LDH+graphene as nanofillers
when compared with pure PMMA. The synergistic effect of LDH and LDH+graphene showed more
delay in the thermal decomposition of PMMA in comparison to PMMA/LDH and PMMA/graphene
alone. This is an indication that the synergistic effect of nanofillers can form a better protective
heat barrier and therefore delay the decomposition of the polymer, improving the thermal stability.
Interestingly, it became apparent from the same study that the synergy of LDH and graphene further
enhanced the thermal stability of PMMA/IFR composites. On the contrary, the synergistic effect of
two LDH nanofillers i.e., MgAl-layered double hydroxides (MgAl-LDH) and NiCo-layered double
hydroxides (NiCo-LDH) exhibited a decrease in the thermal decomposition of the nanocomposites,
in comparison to neat epoxy (EP) at the initial decomposition temperature (T5% ) [85]. This was ascribed
to the catalytic effect of the metals, which speed-up the polymer degradation. However, as much as the
onset of degradation temperature decreased with the addition of the nanolayers, a combination of 2.5%
of MgAl@NiCo exhibited a slightly higher thermal stability when compared with 2.5% of MgAl in the
Crystals 2020, 10, 612 10 of 26

epoxy matrix. Therefore, a general remark can be made such that the synergy of LDH and nanofillers
tend to produce a more compact char content than sole LDH in the polymer matrix.
Crystals 2020, 10, x FOR PEER REVIEW 12 of 31

Figure
Figure 4. Thermogravimetric
4. Thermogravimetric analysis
analysis curves
curves of (a)ofneat
(a) EVA,
neat EVA, (b) DS-LDH/EVA,
(b) 6-phr 6-phr DS-LDH/EVA, (c) DBS-
(c) DBS-LDH/EVA,
LDH/EVA, and (d) SA-LDH/EVA. The zoomed area corresponds to the TGA curves at temperatures
and (d) SA-LDH/EVA. The zoomed area corresponds to the TGA curves at temperatures from 420 to
from 420 to 470 oC. Adapted from Lee, J-H.; Zhang, W.; Ryu, H-J.; Choi, G.; Choi, J.Y.; Choy, J-H.
470 ◦ C [84].
Enhanced thermal stability and mechanical property of EVA nanocomposites upon addition of
6. organo-intercalated
Flammability PropertiesLDH nanoparticles. Polymer.
of Polymer/LDHs 2019, 177, 274-281. With the kind permission of
Nanocomposites
Elsevier [84].
Layered double hydroxide nanofillers have proven to be good flame-retardant materials for
protection Inofthis
polymers
study, PMMAagainstnanocomposites
heat [86]. A summarized
were prepared version of the flame-retardant
by solution mixing by adding mechanism
flame
of LDHresistant
occurs materials,
throughsuch as intumescent
the endothermic flame with
process retardant (IFR) (i) 1,2-Bis(5,5-dimethyl-1,3,2-
the generation of water and metal oxide
char.dioxyphospacyclOHexane
A number of authorsphosphoryl amide) ethane
have investigated the (BPEA), (ii) graphene
flammability (reduced
properties graphene
of LDH/polymer
oxide), and (iii) magnesium aluminium-layered double hydroxide
and/or polymer/LDHs+another nanofiller in order to enhance the flammability resistance modified with sodium dodecylof the
sulfate. It was reported that in the absence of IFR (BPEA), there was an increase in the thermal
nanocomposites [85–89]. In most of these studies, the flammability properties of the nanocomposites
stability of PMMA nanocomposites with reduced graphene oxide (rGO), LDH, and LDH+graphene
were investigated by cone calorimetry and limiting oxygen index methods. Cone calorimetry
as nanofillers when compared with pure PMMA. The synergistic effect of LDH and LDH+graphene
parameters include: heat release rate (HRR), total heat release (THR), time to ignition (TTI), mass loss
showed more delay in the thermal decomposition of PMMA in comparison to PMMA/LDH and
rate (MLR), and smoke
PMMA/graphene production
alone. This is anrate (SPR). Amongst
indication the coneeffect
that the synergistic calorimetry parameters,
of nanofillers can formthe HRR has
a better
emerged as anheat
protective important
barrier andparameter
thereforesince
delayitthe
measures the intensity
decomposition of fire. improving
of the polymer, A decrease inthermal
the HRR peak
symbolizes
stability.anInterestingly,
improvementitinbecame flammability resistance
apparent of the
from the samematerial
study under
that theinvestigation.
synergy of LDHFurthermore,
and
an increase
graphene in further
limiting oxygen the
enhanced index (LOI)stability
thermal values of is an indication
PMMA/IFR of improvement
composites. in flammability
On the contrary, the
of thesynergistic effect of two
nanocomposites. LDH
It was nanofillers
reported thati.e.theMgAl-layered doubleofhydroxides
synergistic effect LDHs with (MgAl-LDH) and
another nanofiller
and/orNiCo-layered
an intumescent doubleflame-retardant
hydroxides (NiCo-LDH)
materialexhibited a decrease
significantly in the thermal
improved decomposition
the flammability of
resistance
of theCrystals
polymer matrix
2020, 10, when
x; doi: FOR PEERcompared
REVIEW with LDH alone. Li et al. [87] investigated the flammability
www.mdpi.com/journal/crystals
Crystals 2020, 10, 612 11 of 26

properties of the three LDHs (viz: MgFe-LDHs, MgAl-LDHs and MgAlFe-LDHs) incorporated into an
EVA matrix. In this study, the LDHs nanofillers were produced from bittern by the co-precipitation
method. Generally, there was a decrease in the heat release rate (HRR) of the EVA matrix with the
addition of the LDHs nanofillers. The HRR peak of pristine EVA was recorded as 1645.8 kW/m2 .
It became apparent that with the addition of the three LDHs, the HRR peaks were found to have
reduced, i.e., EVA 1 (MgAl-LDHs) recorded a value of 222.65 kW/m2 , while EVA 2 (MgFe-LDHs) and
EVA 3 (MgAlFe-LDHs) showed values of 311.87 and 286.96 kW/m2 , respectively. It can be concluded
that the reduction in HRR is attributed to the formation of char residues in the presence of nanofillers,
which acted as a protective barrier against heat. Since ≥90% of the layered double hydroxides must
be modified in order to improve the dispersion of the nanoplatelets within the polymer matrix,
it became apparent that the surfactants played a key role in the flammability properties of the resultant
nanocomposite. Qiu et al. reported on the effect of surfactant (viz: sodium dodecyl sulfate (DDS)
and stearic) on the flammability of PP and Mg3 Al LDHs nanocomposites [88]. Mg3 AlLDHs were
prepared with surfactants i.e., sodium dodecyl sulfate (DBS) and stearic by employing the aqueous
miscible organic solvent modification technique, whereas the nanocomposites were prepared by the
solvent mixing technique. The addition of both sodium dodecyl sulfate and stearic modified-LDH
resulted in a decrease in the peak heat release rate (PHRR), with the stearic-based LDH nanofiller
showing moderate improvement in the flame resistance of PP than the sodium dodecyl sulfate (DDS)
modified-LDH. At both 20 wt.% of stearic modified-LDH and sodium dodecyl sulfate modified-LDH,
the pHRR decreased by 61% and 58%, respectively, in comparison to the neat PP. However, as much as
there is an improvement in the flammability resistance of the LDHs/nanocomposites, there is a need for
the formation of strong char layers during the process of burning. This can be achieved by combining
two or more nanofillers with LDHs. Another study [85] reported on the flammability properties of
the synergistic effect between NiCo-LDH and MgAl-LDH incorporated in an epoxy matrix. ZIF-67,
a type of metal organic framework (MOF), was used as a precursor to tie up the Co2+ on the layered
double hydroxide in order to convert more of it into NiCo-LDH platelets. Various weight percentages
(wt.%) of MgAl@NiCO (viz 2, 2.5 and 3) as well as MgAl-LDH (2.5 and 3 wt.%.) were mixed with
the epoxy matrix. MgAl@ZIF-67 was used as the benchmark to compare its flammability with neat
EP, EP/2.5% MgAl, and EP/2.5% MgAl@NiCo. The addition of 2.5% MgAl reduced the PHRR when
compared to neat EP, with the peak decreasing further with the addition of EP/2.5% MgAl@NiCo
(Figure 5). The reduction of PHRR in the presence of 2.5% MgAl@NiCo was attributed to the formation
of more compact char than the MgAl, which can delay the entrance of heat and oxygen into the system
and as a result, enhance the flammability resistance.
It was further proven that the addition of three metal LDHs improved the flammability resistance
of the polymer matrix more than two metal LDHs [89]. The authors investigated the flammability
properties of neat iPP, 6% Co-Al LDH, 6% Zn-AlLDH, 6% Co-Zn-AlLDH, and 10% Co-Zn-Al LDH
polypropylene nanocomposites. The three metal LDH nanocomposites showed better reduction in
flammability than the two metal LDH nanocomposites, at the same content. The behaviour was
attributed to the effective char formation for the 6% Co-Zn-Al LDH when compared with 6% Co-Al
LDH and 6% Zn-Al LDH. This thermally stable char can prevent volatile gases/products from escaping
out of the system and acting as a protective heat barrier, thereby preventing heat from entering the
system, as a result improving the flammability resistance of the overall system. It is well known that a
protective char will become fragile when more gaseous volatile products escape the system, which
will provide easier passage of oxygen and heat into the material. Hence, it is important for flame
retardant materials to form a stable and compact char in order to prevent the escape of volatiles gases
and entering of heat into the system. Table 3 summarizes selective studies on the flammability of the
polymer/LDH system.
Crystals 2020, 10, 612 12 of 26

Table 3. Selective studies on the flammability properties of a polymer/LDHs system.

Preparation Method of the

Polymer/LDHs System Synthesis of the Metal-LDH Nanofiller Summary of the Flammability Results References
Nanocomposites
It was reported that the hybrid mixture of AMO-LDH-OCNT improved the
Polypropylene (PP)/(AMO-LDHs)
flammability resistance of PP better than AMO-LDHs alone. A synergy
and (O-CNT),
Hydrothermal method Solution mixing fabricated from 10 wt.% AMo-LDH+1 wt.% oCNT showed 40% reduction in [90]
AMO = Aqueous miscible organic
peak heat release rate (pHRR) when compared with 20 wt.% AMO-LDH
o = oxidized
(31% reduction in pHRR).
An ion exchange method was used for The addition of LDH (Mg-Al- CO3 −2 LDH) reduced the pHRR from
Polypropylene (PP)/LDHs and PP/M-LDHs,
fabrication of dihydrogen phosphate Melt mixing by using an extruder 1032 kW/m2 (pristine PP) to 837 kW/m2 with the pHRR decreasing [81]
M-LDHs = Mg-Al-H2 PO− LDHs
4 intercalation (Mg-Al- H2 PO−
4
) (534 kW/m2 ) further with the addition M- LDHs (Mg-Al-H2 PO−
4
LDHs).
Solvent treatment (Aqueous miscible
The addition of 10 and 20 wt.% of APP-LDH resulted in an improvement in
Polypropylene (PP)/APP-LDHs and ZB, organic) was used for treatment of LDHs.
flammability resistance in comparison to carbonate LDH (Mg3 Al-CO3 LDH).
APP = Ammonium polyphosphate, Mg3 Al-APP LDH and Mg3 Al-CO3 LDH Solvent mixing [91]
The synergistic effect of ZB and APP-LDH improved the flammability
ZB = Zinc borate were synthesized by the
resistance further in comparison to APP-LDH alone.
hydrothermal method
The investigated samples include: TPU (100%), TPU/NO− 3
-LDHs-GO (80/20
mass %), TPU/SDS-LDHs (80/20 mass %), TPU/SDS-LDHs-1%GO (80/20
mass %), TPU/SDS-LDHs-3%GO (80/20 mass %) and TPU/SDS-LDHs-5%GO
(80/20 mass %). The addition of the nanofillers into the TPU matrix reduced
the peak heat release rate (PHRR), which is an indication of flammability
Thermoplastic resistance. The LDHs nanofiller modified with sodium dodecyl sulfate (SD)
NO−3
-LDHs-GO was fabricated by the
polyurethane/LDHs-graphene oxide Melt mixing method showed better flammability resistance properties when compared with [92]
co-precipitation method
(TPU/LDHs-GOs) NO− 3
-LDHs. This was attributed to a better exfoliation of the SDS-modified
nanofiller, which provided a better chance of a char formation. The synergy
between GO and LDHs improved the flammability resistance more than
NO− 3
-LDHs-Go and SDS-LDHs samples, with TPU/SDS-LDHs-5%GO (80/20
mass %) showing more reduction in PHRR. This is due to the ability of Go to
be an effective flame-retardant material.
CaMgAl-LDHs was fabricated by
Co-precipitation method. Borated
The addition of 10, 20, 30 and 40% of O-CaMgAl-LDHs increased with the
Acrylonitrile-Butadiene-Styrene/(CaMgAl CaMgAl-LDHs was prepared by
addition and increasing in o-CaMgAl-LDHs content. The synergistic of
-Layered Double Hydroxides) dissolving CaMgAl-LDHs into boric acid Melt blending by two-roll mix [93]
O-CaMgAl-LDHs, ammonium polyphosphate (APP) and graphite (EG)
(CaMgAl-LDHs) solution. In order to form
showed higher values than O-CaMgAl-LDHs.
O-CaMgAl-LDHs, B-CaMgAl-LDHs was
dissolved in sodium oleate solution.
used as the benchmark to compare its flammability with neat EP, EP/2.5% MgAl, and EP/2.5%
MgAl@NiCo. The addition of 2.5% MgAl reduced the PHRR when compared to neat EP, with the
peak decreasing further with the addition of EP/2.5% MgAl@NiCo (Figure 5). The reduction of PHRR
in the presence of 2.5% MgAl@NiCo was attributed to the formation of more compact char than the
MgAl,2020,
Crystals which can delay the entrance of heat and oxygen into the system and as a result, enhance
10, 612 13 ofthe
26
flammability resistance.

Figure
Figure 5. Heatrelease
5. Heat releaserate
rate(HRR)
(HRR)ofofneat
neat,
(a)EP,
EP EP/2.5% MgAl,
(b) EP/2.5% EP/2.5%
MgAl MgAl@NiCo,
(c) EP/2.5% MgAl@NiCo EP/2.5%
(d)
MgAl@ZIF-67 [85].
EP/2.5% MgAl@ZIF-67. Adapted from Zhang, Z.; Qin, J.; Zhang, W.; Pan, Y.-T.; Wang, D.-Y.; Yang, R.
Synthesis
7. Barrier of a novel
Properties ofdual layered
Layered doubleHydroxides
Double hydroxide hybrid
(LDH)nanomaterial and its application in epoxy
nanocomposites. Chem. Eng. J. 2020, 381, 122777. With the kind permission of Elsevier [85].
Layered double hydroxides (LDHs) are usually combined with polymer matrices to form films
with good
It wasgas barrierproven
further properties,
that for
theapplications
addition ofinthreefood packaging
metal LDHs andimproved
encapsulation of electronic
the flammability
devices
resistance[94,95].
of the LDHs consistmatrix
polymer of crystalline layered
more than twostructures
metal LDHs[96–99] thatThe
[89]. induce gas barrier
authors properties
investigated the
by increasing the
flammability diffusionoflength
properties of gases,
neat iPP, therefore
6% Co-Al LDH, resisting permeating
6% Zn-AlLDH, 6%gases in the resultant
Co-Zn-AlLDH, and polymer
10% Co-
film.
Zn-AlThe LDH development
polypropylene of organic-inorganic
nanocomposites. composite
The three metalmaterials
LDHwith gas barrier properties,
nanocomposites showed bettere.g.,
LDH/polymer films, still faces
reduction in flammability thana few
thechallenges.
two metalOne LDH of them is that the diffusion
nanocomposites, of gas content.
at the same molecules is
The
only suppressed
behaviour in the direction
was attributed of the film,
to the effective i.e.,
char the gas molecules
formation for the 6%flowing
Co-Zn-Al parallel to the compared
LDH when inorganic
structural
with 6% layersCo-Al are LDH not and
resisted
6% [100–102].
Zn-Al LDH. In suchThisa case, the gasstable
thermally barrierchar
properties of the film
can prevent are
volatile
usually improvedfrom
gases/products by increasing
escaping theoutcontent
of the of the crystalline
system and actinglayered
as a structures.
protective However, the loading
heat barrier, thereby
with these inorganic
preventing heat from crystalline
enteringstructures
the system, reduces the flexibility
as a result improvingandthe
toughness of the barrier
flammability materials.
resistance of the
Another challenge
overall system. iswell
It is that known
the incorporation of highly
that a protective charoriented inorganic
will become structural
fragile when morelayers into polymer
gaseous volatile
matrices
productsalso causes
escape thepolymer
system, aggregation. This aggregation
which will provide creates
easier passage of voids
oxygen through which
and heat intogas
themolecules
material.
permeate
Hence, it easily. This results
is important in a retardant
for flame film with materials
compromised gas abarrier
to form stable properties
and compact [103].
charInina quest
order to
to
curb the challenges
prevent the escapefaced by the development
of volatiles of LDH-based
gases and entering of heatgasinto
barrier
the materials, considerable
system. Table efforts
3 summarizes
have beenstudies
selective directed on towards developing
the flammability thepolymer/LDH
of the structure of LDHs.system. Dou et al. [104] discovered that the
incorporation of plate-like LDH (P-LDH) into a polymer matrix, e.g., chitosan (CTS), improved the
oxygen barrier properties of the resultant films. However, the challenge was that the oxygen barrier
properties were not that good for very thin films. Hence, in another study [95], the authors converted the
LDH with a plate-like structure to one with a hierarchical structure (H-LDH). The oxygen transmission
rate of the resultant H-LDH/CTS films was reduced by almost 37% when compared to that of the
original P-LDH/CTS films, indicating that the structural conversion of the LDHs improved their gas
barrier properties. The synthesis of H-LDH was performed via the continuous calcination-rehydration
treatment of P-LDH. The resultant H-LDH was then used as a scaffolding material for the fabrication
of chitosan multi-layered films via an alternate spin-coating process. This process led to the formation
of (H-LDH/CTS)n films with excellent oxygen barrier properties. The (H-LDH/CTS)n films exhibited
Crystals
an oxygen2020, transmission
10, x; doi: FOR PEER
rateREVIEW
(OTR) that was below the detection limit ofwww.mdpi.com/journal/crystals
commercial instruments
(<0.005 cm /m day atm).This was attributed to the capabilities of H-LDH to resist the migration of
3 2

oxygen molecules from multiple directions by creating a longer diffusion pathway. Large amounts
of oxygen molecules were also absorbed by the large surface area of the H-LDH. The large surface
area of the H-LDH filled-in all the gaps between H-LDH and the polymer matrix, thus closing-up
the space for oxygen permeation [95]. During the development of LDH/polymer gas barrier films,
improving the durability of the films is quite important, especially for applications such as food
packaging and encapsulation of electronic devices. In order to achieve this, LDH/polymer films with
Crystals 2020, 10, 612 14 of 26

self-healing properties are designed and fabricated. This results not only in a film with excellent gas
barrier properties, but also one with the ability to repair itself after damage by external stimuli. In a
study by Dou et al. [94], (LDH/PSS)n -PVA films with self-healing properties triggered by humidity
were fabricated via the layer-by-layer assembling of layered double hydroxide nanoplatelets and
poly(sodium styrene-4-sulfonate) (PSS), followed by the subsequent incorporation of poly(vinyl alcohol)
(PVA). The even distribution of the highly oriented LDH nanoplatelets in the film was responsible for
the resistance of permeating gases by creating a long diffusion pathway. The PVA was responsible for
the humidity-stimulated self-healing properties of the films. When the films were exposed to humidity
after the development of the stimuli crack, the water molecules triggered the formation of hydrogen
bonds among the hydroxyl groups of PVA, thus causing the stimuli crack to close. Hydrogen is usually
used as an alternate fuel to fossil fuels because its combustion only produces water, which implies
less air pollution. However, amongst many other methods of storing hydrogen, LDHs have been
considered as the best substances for the storage of hydrogen gas. This is achieved through the
conversion of LDHs into microporous materials through intercalation with other anionic substances.
Huang and Cheng [105] intercalated Li-Al layered double hydroxides with various organic anions
via a co-precipitation method. The maximum hydrogen absorption per micropore surface area of the
LDHs prepared in this study was higher than that of metal organic frameworks (MOFs) reported in
the literature, hence confirming the microporous nature of the prepared LDHs. Table 4 summarizes
selective studies on the barrier properties of polymer-LDHs nanocomposites.
Crystals 2020, 10, 612 15 of 26

Table 4. Selective studies for the preparation and barrier properties of polymer-LDHs nanocomposites.

Synthesis of the Metal-LDH Preparation Method of the

Polymer/LDHs System Summary of the Resultant Barrier Properties References
Nanofillers Nanocomposites
The resultant composite films exhibited improved gas-barrier properties.
The water vapour penetration of the films decreased significantly at low
CNFs/MgAl-CO3 -LDHs with different LDH
MgAl-CO3 -LDHs concentrations of: 5 wt.% and 10 wt.%. At 5 wt.%
ratios were prepared by a
Cellulose nanofibrils LDHs were synthesized via the MgAl-CO3 -LDHs, the water vapour penetration was reduced by 50 % as
filtering/evaporation process that induced [106]
(CNFs)/MgAl-CO3 -LDHs hydrothermal method compared to the pure CNFs film. When the concentration was increased to
barrier and strengthening properties in the
10 wt.%, the water vapour penetration decreased further, reaching a low of
composite films.
1927 g/m2 ·24 h, which was the lowest content of penetrated water vapour
compared to all the MgAl-Co3 -LDHs loadings.
The oxygen transmission rate (OTR) of the films with a higher aspect ratio,
Nitrile butadiene rubber (U-mLDH/NBR)30 , was reduced by 92.2% compared with the pure NBR film.
The U-mLDHs nanoplatelets were The NBR/U-mLDH composites were
(NBR)/polyvinyl pyrrolidone The improved gas barrier properties were due to the decreased diffusion
prepared by a slightly improved prepared by a layer-by-layer spin-coating [107]
modified ultrathin LDH pathway of the oxygen molecules. The free space between the U-mLDH and
co-precipitation method. assembly technique.
nanoplatelets (U-mLDHs). NBR was due to the large aspect ratio of the U-mLDH and the improved
interfacial adhesion at the LDH-polymer interface.
LDH intercalated with an aliphatic
The water vapour barrier properties of the LLDPE composite films with 1%
Linear low density polyethylene long-chain anion was prepared by a The films were prepared by melt blending
LDH were enhanced by 60.36%. This was attributed to the LDH inducing a [70]
(LLDPE)/LDH composite films. single pot high-energy balling and blow processing.
longer diffusion pathway for the water molecules.
method.
Poly(vinyl alcohol)(PVA)/hydrid
MgAl-LDH-rGO hybrids were The oxygen transmission rate (OTR) of PVA/LDH-rGO films was decreased
layered double hydroxides The PVA/LDH-rGO hybrid films were
prepared by the co-precipitation by 86% at 1% LDH-rGO loading. The improved barrier properties were [108]
(LDHs)-reduced grapheme oxide prepared by the solution casting method.
method. attributed to the uniformly dispersed LDH-rGO hybrids in PVA.
(rGO) (LDH-rGO).
Crystals 2020, 10, 612 16 of 26

8. Mechanical Properties of Polymer-LDHs Systems

Mechanical properties are used to determine the strength and ductility of polymer nanocomposites.
The mechanical properties of LDH-based polymer nanocomposites were investigated by different
studies [109–114]. Numerous factors were found to affect the mechanical properties of LDHs
nanocomposites, including the content of LDHs, the type of LDHs, polymer matrix, dispersion of LDH
in polymer matrix, and the preparation method. Botan et al. investigated the mechanical properties
of polyamide 6 incorporated with two types of LDHs (viz Zn/Cr-L and Zn/Cr-P, with Zn = Zinc,
Cr = Chromium, L = lauric acid and P = palmitic acid) [109]. The LDHs nanocomposites were
fabricated by in situ polymerization with various composition of the filler (viz 1, 2, and 3 wt.%).
Mechanical properties of nanocomposites were investigated with tensile tester. The modulus of
elasticity (E) decreased at lower content of Zn/Cr-L i.e., 1 wt.%, with the E values increasing at
higher compositions of Zn/Cr-L (viz 2, and 3 wt.%). The decrease in E values at lower content was
attributed to the plasticizing effect due to the absorption of the water at lower content. Similarly,
the addition of Zn/Cr-P increased the E values of the polyamide 6 nanocomposites in all investigated
filler composition. The optimum composition for both fillers was obtained at 2 wt.%, with the
Zn/Cr-P nanofiller showing higher E values when compared with Zn/Cr-L counterpart. This was
attributed to the bilayer structures, which allowed an efficient stress-transfer. The effect of stearate
intercalated LDH on the properties of PU was investigated in the literature [110]. The polyurethane
(PU)/Stearate-intercalated LDH was fabricated by solution intercalation. There was an enhancement in
tensile strength (TS) with the incorporation of stearate-LDH (viz 1, 3, 5, and 8 wt.%) into PU matrix,
when compared with the neat PU. The tensile strength was observed to increase with decreasing
in stearate-LDH nanoparticles content. A higher tensile strength (TS) at 1 wt.% of stearate-LDH
was ascribed to a better exfoliation at this content. There was a reported increase in elongation at
break with addition of stearate-LDH nanoparticles into the PU. The behaviour was ascribed to the
plasticization of the alkyl chain intercalated into the LDH in the PU/stearate-LDH system. Feng and
co-workers investigated the properties of the LDHs reinforced peroxide-cured acrylonitrile butadiene
rubber [111]. The LDHs were organically modified with sodium dodecylbenzene (SDBS) and sodium
styrene sulfonate (SSS). The LDH modified with sodium styrene sulfonate (SSS) composites showed
better mechanical properties than neat acrylonitrile butadiene rubber (NBR) and LDH modified with
sodium dodecylbenzene composites. This behaviour was attributed to a better chemical bond between
the organically modified LDHs sodium styrene sulfonate (SSS) and NBR. Based on the above study,
it became apparent that the type of organic modifier may influence the overall properties of the
LDHs-polymer nanocomposites. Suresh and co-workers [112] investigated the Co-Al layered double
hydroxide reinforced polystyrene nanocomposites. In this study, Co-Al layered double hydroxide was
organically modified with sodium dodecyl sulfate (SDS) and the composites were prepared by melt
compounding. It was observed that at 1 wt.% of Co-Al LDH nanocomposite, there is an enhancement
in both tensile and tensile modulus when compared with neat PS and 3, 5 as well as 7 wt.% Co- Al LDH
nanocomposites, respectively (Figure 6). At lower content, i.e., 1 wt.%, there is a better exfoliation of
the nanoparticles in the PS matrix as well as enhanced interfacial interaction between the two phases,
which resulted in better mechanical properties. At higher content of the nanofiller, there is a probability
of agglomerated Co-Al LDH, which formed defects, and as a result lowering the mechanical properties.
Table 5 summarizes selective studies on the mechanical properties of LDH-polymer nanocomposites.
Crystals 2020, 10, 612 17 of 26
Crystals 2020, 10, x FOR PEER REVIEW 21 of 31

Figure 6. Tensile strength and tensile modulus of polystyrene and its Co-Al layered double hydroxide
Figure 6. Tensile strength and tensile modulus of polystyrene and its Co-Al layered double hydroxide
nanocomposites [112].
nanocomposites. Adapted from Suresh, K., Pugazhenthi, G., and Uppaluri, R. Properties of
polystyrene (PS)/Co-Alstudies
Table 5. Selective LDH nanocomposites
on mechanical prepared by melt
properties intercalation. Mater.
of LDH-polymer Today. 2019. 9:
nanocomposites.
333-350. With the kind permission of Elsevier [112].
Preparation of Polymer-LDHs
Polymer-LDHs Nanocomposites Summary of the Mechanical Properties References
Nanocomposites
Table 5. Selective studies on mechanical properties of LDH-polymer nanocomposites.
Epoxy (EP)/Mg-Al LDH
intercalated with ammonium Preparation of The addition of 10 and 20 mass% of intercalated LDHs
Polymer-LDHs
alcOHol polyvinyl
Solution intercalation
into EPof
showed higher tensile strength than neatReferences.
EP.
[113]
Polymer-LDHs Summary the Mechanical Properties
Nanocomposites
phosphate (AAPP)
Nanocomposites
Poly(ε-caprolactone)
Epoxy (EP)/Mg-Al
(PCL)/Silver-LDH (Ag-LDH).
LDH LDH = Mg-Al LDH
intercalated with TheIt was reportedof
addition that
10when
and the
20 composition
mass% of of Ag-LDHs
Type of silver-LDHs used are: was 0.5 wt.%, the tensile strength of the
ammonium
Ag-LDHs@PDA alcOHol Solution intercalation intercalated LDHs into EP
Ag-LDHs@TA-Fe(III)/PCL system showed
decreased by 11%, [113]
PDA = polydopamine
polyvinyl phosphate Solution casting method higher
while tensile strength than
the LDHs@PDA/PCL neat EP. reduced by
nanocomposite [114]
Ag-LDHs@TA-Fe (III) 4% when compared with neat PCL. The 0.5 wt.% of
(AAPP)
TA = tannic acid Ag-LDHs(PVP) showed 26% reduction in
Poly(ɛ-caprolactone)
Fe (III) = Iron (III) tensile strength.
Ag-LDHs (PVP)
(PCL)/Silver-LDH
PVP = pyrrolidone It was reported that when the
(Ag-LDH).
composition of Ag-LDHs
The study investigated was
1, 2, and 4%0.5 wt%,
of LDH incorporated
LDH= Mg-Al LDH into PI. The 2% of LDH showed higher tensile strength
the tensile strength of the Ag-LDHs@TA-
Type of silver-LDHs
Aromatic Polyimide
value when compared with neat PI, 1% LDH/PI and 4%
Fe(III)/PCL system decreased
LDH/PI nanocomposites. This wasby 11%, to a better
attributed
used are:
(PI)/Zn/Cr-LDH Solution casting
In situ polymerization
dispersion
[6]
Zn = Zinc, Cr = Chromium while theLDH in a polymer matrix at low content. [114]
LDHs@PDA/PCL
Ag-LDHs@PDA method However, at higher content, i.e., 4 wt.%, there was
nanocomposite
formation of an reduced by 4%resulted
aggregate, which whenin defect in
PDA= polydopamine
compared with neat thePCL. The 0.5 wt% of
nanocomposite.
Ag-LDHs@TA-Fe (III)
Ag-LDHs(PVP)
According toshowed
the study,26%5 wt.%reduction
of the LDHin showed
TA= tannic acid higher tensile strength in comparison to neat CNF, 10, 15
Cellulose nanofibrils (CNF)/Mg
Filtering/evaporation method
tensile strength.
and 25% of LDHs. Higher tensile strength at low content [106]
Fe (III)
Al-CO =3Iron
-LDHs(III)
was ascribed to a better dispersion of the nanofiller in
Ag-LDHs (PVP) a matrix.
Mechanical properties of EVAL/LDH composites were
Crystals 2020, 10, x; doi: FOR PEER REVIEW compared with neat EVAL. The www.mdpi.com/journal/crystals
authors reported that the
Poly(ethylene-co-vinyl alcOHol) charpy notched impact strength of the composites was
(EVAL)/LDHs, twice that of the neat EVAL polymer. This was attributed
LDH was organically Melt compounding to the extensive internal micro-cavitation of the highly [115]
modified with: Stearate (SA), dispersed and randomly dispersed LDH platelets during
to form SA-LDH impact loading. The large surface area created by the
micro-cavitation enhanced the requisite energy
dissipation mechanism.
Crystals 2020, 10, 612 18 of 26

9. Selective Applications of Different Polymer-LDHs Systems

Layered double hydroxides nanocomposites have been prepared for various applications including
energy, food packaging, water purification, gas sensing, biomedical, flame retardant, and agricultural
applications [68,116–119]. Qin and co-workers investigated the LDHs nanocomposites based on
PANI/ZnTI-LDHs for sensing ammonia gas (NH3 ) [116]. The LDHs (ZnTi-LDHs) nanofiller was
prepared by hydrothermal method and the nanocomposites were fabricated by in situ chemical
oxidative polymerization. The ability of the LDH nanocomposites in sensing NH3 was compared
with neat PANI and ZnTi-LDHs. The LDHs nanocomposites were found to exhibit a significant
NH3 sensing ability with good lengthy stability when compared with neat polymer and LDHs,
respectively. The results were ascribed to a more-loose architecture structure of the nanocomposite,
which improves the adsorption site as well as facilitation of the gas adsorption. The system consisting
of sulfonated polyaniline (SPAN) reinforced with graphene oxide (GO)-LDHs was investigated for
extraction phthalates in drinking water and distilled herbal beverages [117]. The study compared the
extraction efficiency of GO-LDH@SPAN nanocomposite with LDH and GO-LDH for extraction of
phthalates from aqueous solution. The extraction efficiency of the LDH@SPAN nanocomposite for
phthalate was higher than neat LDH and GO-LDH, with LDH showing lower extraction than GO-LDH.
The reason LDH showed lower extraction for phthalates was due to a possible weak hydrogen bond
between LDH and phthalates. The higher extraction efficiency of phthalates by GO-LDH was attributed
to a π-π bond between GO and aromatic ring of phthalates. The GO-LDH@SPAN nanocomposite
showed higher extraction of the analyte because SPAN can promote more π-π interaction with the
phthalate. Furthermore, as SPAN has O=S=O in the matrix, it presents more active sites for extraction
of the analytes. PMMA/Mg- Al LDH nanocomposites was fabricated by in situ polymerization for
a possible packaging application [68]. Two key results were significant in determining a possible
packaging application, i.e., thermal stability and gas permeability. The fabricated nanocomposites
were reinforced with 2, 4, and 8% of Mg-Al LDH. There was a decrease in the oxygen flow rate of
the nanocomposites in comparison to neat PMMA. This behavior was attributed to a dispersion of
LDH in a polymer matrix, which acts as protective barrier for oxygen permeability; as for neat PMMA,
the presence of voids resulted in oxygen penetration within the matrix. The addition of the LDH
into the PMMA enhanced the thermal stability of PMMA matrix when compared with neat PMMA.
The reduction in oxygen permeability and the enhancement in thermal stability of the PMMA/Mg-Al
LDH system suggest that the nanocomposite may be suitable for packaging application.
In recent times, the demand for highly flexible, durable, and lightweight piezoelectric
nanogenerators has led to the fabrication of piezoelectric and dielectric electrospun nanofabrics
of poly (vinylidene fluoride) (PVDF)/Ca-Al LDH composites. During the fabrication of the PVDF/Ca-Al
LDH composite nanofabrics, the Ca Al- LDH nanosheets were first synthesized via a modified
coprecipitation method before they were incorporated as filler into the PVDF matrix. The composite
nanofabrics of PVDF/Ca-Al LDH were finally obtained via the electrospinning of the composite solutions.
The synergy between the PVDF-LDH interaction and the in situ stretching, which was attributed
to the electrospinning, enhanced the nucleation of the electroactive β phase up to 82.79%. This was
an indication that these composite nanofabrics are suitable for piezoelectric-based nanogenerators.
The hand slapping and frequency-dependent mechanical vibration mode methods showed that the
piezoelectric performance of the PVDF/Ca-Al LDH composite nanofabrics can reach a maximum open
circuit output voltage of 4.1 and 5.72 V. The composite nanofabrics also had a high dielectric constant
and a low dielectric loss, which were attributed to high interfacial polarization at low frequencies with
increasing LDH loading. This showed that these materials have the potential to be used in electronic
devices [118].
Wang et al. [119] prepared Zn Al -LDH/polycaprolactone (PCL) nanocomposites for use in drug
delivery systems. The Zn Al-LDH was synthesized via the co-precipitation method while the ZnAl
-LDH/PCL nanocomposites were prepared by the solution intercalation method. The ZnAl-LDH/PCL
composite nanofabrics exhibited a higher weight loss and drug release amount when compared to neat
Crystals 2020, 10, 612 19 of 26

PCL. The drug release kinetics followed the first-order kinetic model for the Zn Al-LDH/PCL composites,
indicating that the drug release was content-dependent. However, for the neat PCL, the drug release
kinetics followed the Ritger-Peppas kinetic model, indicating that the release followed the Fikian
mechanism. Table 6 summarizes selective studies on the applications of LDH-polymer nanocomposites.

Table 6. Summary of selective studies on the application of LDH-polymer nanocomposites.

Preparation Method for the

Polymer-LDH System Intended Application References
Nanocomposites
Poly(lactide-co-glycolic acid) Solution mixing and casting into
Drug delivery applications [120]
(PLGA)/Mg Al-LDH thin films
Polypropylene-grafted maleic
anhydride (PP-g-MA)/Dye
co-precipitation Flame retardant applications [121]
structure-intercalated layered double
hydroxide (d-LDH)
Waterborne polyurethane (WPU)/LDH
Solution mixing and casting into
LDH = (Mx Al/CO3 2− , M = Mg and/or Coatings applications [122]
thin films
Zn, and x = 2, 3 and 4)
Low-saturation
Chitosan (CS)/NiFe-LDH Catalytic applications [123]
co-precipitation method.
Polylactic acid (PLA)/Intumiscent flame
Melt blending and hot pressing
retardant (IFR)/Phosphotungstic acid Flame retardant applications [124]
into films
intercalated Mg Al-LDH (PWA-LDH)
One-step route in which the
co-precipitation reaction of metal ions
(Co2+ , Ni2+ and Mn2+ ) was used to
CoNiMn-LDH/Polypyrrole
prepare LDH and the polymerization Electrocatalytic applications [125]
(PPy)/Reduced graphene oxide (RGo)
of pyrrole (Py) was used to prepare
PPy. Modified Hummer’s method
was used to prepare graphene oxide
Isotactic polypropylene
Solvent mixing method Flame retardant applications [89]
(iPP)/ZnAl-LDH
Removal of Cd2+ ions from
Polystyrene (PS)/MgAl -LDH Solution mixing [126]
aqueous media
Poly(vinyl chloride) (PVC)/MgAl LDH Solution intercalation method Biomedical applications [127]

10. Conclusions and Future Recommendations

Layered double hydroxides (LDHs) have been the nanofiller of choice in terms of improving the
flame retardancy and barrier properties of polymer matrices. However, the improvement in properties
of the LDHs/polymer systems depended on the dispersion of the nanofiller within the polymer matrices.
It is apparent that LDHs nanofillers in most cases has been organically modified in order to improve
the exfoliation of the nanofillers in polymer matrices. The dispersion of LDHs/polymer system varied
depending on the method of preparation, type of modifier, and the type of LDHs/polymer system.
Generally, there was an improvement in the flammability resistance of polymer matrices with the
addition of LDHs with different compositions. The flammability resistance improved more in the
presence of LDHs and other flame-retardant fillers. The synergy of LDHs and nanofillers improved
the flame retardancy more because it is able to form a strong and compact char layer, which can
inhibit the entry of heat into the system, thereby improving the overall flammability resistance of the
system. The gas barrier properties of LDH/polymer films were dependent on the orientation and
distribution of the LDH nanoplatelets. Highly oriented and evenly distributed LDH nanoplatelets
created a resistance for the migration of gas molecules from multiple directions by increasing the
diffusion pathway of the permeating gases. The intercalation of LDHs with organic anions altered their
gas barrier properties by converting the LDHs into microporous materials. However, although LDH
improved the properties of various polymer matrices, there is still a huge gap in terms of the thermal
conductivity of the LDHs-polymer nanocomposites. In the past, LDHs nanofillers were fabricated
with conductivity polymers such as polyaniline and polypyrrole; however, there are a few studies
investigating the thermal conductivity of LDHs in combination with well-known conductive fillers
such as expanded graphite, carbon nanotubes, carbon black, and carbon fiber to widen the applications
Crystals 2020, 10, 612 20 of 26

of LDHs nanocomposites. The fabricated hybrid LDH/conductive filler/polymer nanocomposite

may be used in applications such as flame retardant, supercapacitors, and batteries. Furthermore,
there is also less investigation on the effect of LDHs in natural fiber reinforced biopolymer composite
to form a “green” LDH/natural fiber/biopolymer hybrid composite. The resultant hybrid material
(viz LDH/natural fiber/biopolymer hybrid composite) may exhibit enhanced mechanical properties,
thermal stability, and flammability resistance and can be used in applications such as environmental
protection and flame retardancy.

Author Contributions: M.J.M. and S.I.M. co-designed and guided the review as well as co-writing
Sections 1–3, 6 and 7 of the article; J.S.S. and E.R.S. co-wrote Sections 4, 5 and 8; T.C.M. and M.J.M. co-wrote
Sections 9 and 10; while M.J.M. and S.I.M. compiled the article together. All authors have read and agreed to the
published version of the manuscript.
Funding: This research was funded by the National Research Foundation (NRF) of South Africa, grant number (s)
127278 and 114270.
Acknowledgments: The National Research Foundation (NRF) of South Africa is acknowledged for
financial support.
Conflicts of Interest: The authors declare no conflict of interest.

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