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hydroxide/polyacrylamide nanocomposite
Cite this: Soft Matter, 2015,
11, 9038 hydrogels with ultrahigh deformability†
Lianying Wu,ab Ziqiao Hu,a Guangming Chen*a and Zhibo Li*ac

A convenient green preparation method has been developed to achieve layered double hydroxide
(LDH)/polymer nanocomposite (NC) hydrogels. In contrast to previous publications using toxic organic
solvent of formamide or methanol in LDH exfoliation or anion exchange, the interlayer anion exchange
and exfoliation of LDH are completed in one step with the help of an amino acid (L-serine). The LDH/
polyacrylamide (PAM) NC hydrogels are achieved by a convenient exfoliation–adsorption in situ poly-
merization method. The exfoliation of LDH is characterized by dynamic light scattering and transmission
electron microscopy. Interestingly, the developed NC hydrogels reveal ultrahigh deformability and extra-
ordinary stretchability, confirmed by qualitative images and qualitative tensile and compression tests. The
Received 4th September 2015, molecular mechanism for the ultrahigh deformability and extraordinary stretchability is discussed by
Accepted 20th September 2015 crosslinking density, inter-crosslinking molecular weight and swelling tests. We believe that the findings
DOI: 10.1039/c5sm02232k reported herein will deepen our understanding towards the chemistry of network soft materials
including gels, and further widen the applications of polymer hydrogels in mechanical devices such as
www.rsc.org/softmatter artificial muscles, biomedical devices and drug delivery systems.

1. Introduction performance is still a major challenge. To this end, we have first


developed layered double hydroxide (LDH)/polymer NC hydro-
Polymer/inorganic nanocomposite (NC) hydrogels have gels with extraordinary stretchable properties.9
attracted much current interest due to their unique network LDHs consist of positively charged metal hydroxide nanosheets
microstructure and super mechanical properties.1–6 In these with a thickness of around 0.48 nm and exchangeable anions in
NC hydrogels, the homogeneously-dispersed inorganic nano- the interlayer.10,11 Compared with other common inorganic nano-
particles act as crosslinkers. A unique network microstructure particles, LDHs have a variety of intrinsic advantages: the consti-
consisting of a number of flexible polymer chains linked tuents can be conveniently changed; their layer sizes are highly
by inorganic nanoparticles contribute to their significantly tuneable; more importantly, they have the unique interlayer anion
enhanced mechanical and water-swelling properties.1–5 For exchangeability.12–14 Therefore, they have wide applications includ-
example, ultrahigh elongation at break was achieved, which ing catalysts,15 photoluminescence,16,17 UV-ray shielding,18
could reach 1000–3000%. However, only few types of inorganic thermal stabilizers,19 and flame retardancy.20 However, unlike
nanoparticles such as clay1,2 and graphene3–6 have been clay minerals (such as montmorillonite), the original LDHs
demonstrated to achieve polymer NC hydrogels with signifi- cannot be swollen automatically and dramatically delaminated
cantly improved mechanical properties. Common inorganic in water, due to their high surface charge density and strong
nanoparticles including nanoscale silica have been reported attractions between adjacent nanosheets. Generally, formamide
to be unable to fabricate polymer NC hydrogels.7,8 Therefore, is used as the dispersion medium to exfoliate or delaminate the
the fabrication of new types of polymer NC hydrogels with high inorganic LDH with nitrate as counter ions, and then LDH/PAM
nanocomposite dispersions can be obtained.21 Nevertheless,
a
Beijing National Laboratory for Molecular Sciences (BNLMS), Institute of formamide is an organic solvent with low volatility and high
Chemistry, Chinese Academy of Sciences, Beijing 100190, P. R. China. boiling temperature (B210 1C), having a strong toxicity to
E-mail: chengm@iccas.ac.cn human health and is poisonous to the environment.22
b
University of Chinese Academy of Science, Beijing 100049, P. R. China
c
Green and sustainable hydrogels have received increasing
School of Polymer Science and Engineering, Qingdao University of Science and
Technology, Qingdao 266042, P. R. China. E-mail: zbli@qust.edu.cn
attention in recent years.23,24 In terms of green and sustainable
† Electronic supplementary information (ESI) available: XRD patterns, TGA curve, chemistry, it is vital to achieve aqueous LDH dispersions directly
and FTIR spectra. See DOI: 10.1039/c5sm02232k in water to replace the toxic organic solvent of formamide.

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Recently, the LDH intercalated by isethionate (HO(CH2)2SO3, Ise) coupled plasma (ICP) atomic emission spectroscopy, X-ray
(LDH–Ise) was found to be easily exfoliated in water,25 and the diffraction (XRD) (Fig. S1, ESI†), thermogravimetric analysis
aqueous dispersion had high stability towards heating, shear force (TGA) (Fig. S2, ESI†) and Fourier transform infrared (FTIR)
and acid/alkali tolerance.26 In a subsequent study, with the use spectra (Fig. S3, ESI†), the chemical formula of ZnAl–LDH–NO3
of this water-delaminated LDH–Ise dispersion, we fabricated is Zn1.68Al(OH)5.36NO31.18H2O.
aqueous dispersion of LDH/polymer nanocomposites27 and The LDH/polyacrylamide (PAM) nanocomposite (NC) hydro-
LDH/polymer NC hydrogels with ultrahigh stretchability.9 gels (LmM) were prepared using an exfoliation–adsorption in situ
Unfortunately, the toxic organic solvent of methanol was employed free radical polymerization method. First, the ZnAl–LDH–NO3
as the medium of the anion exchange during the preparation of powder was directly dispersed in 1.5 M L-serine aqueous solution
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LDH–Ise. Considering the presence of methanol in its preparation, followed by agitation and ultrasonication treatments to obtain
the applications of LDH–Ise in the fabrication of novel materials a transparent aqueous dispersion. Next, after the monomer
such as polymer NC hydrogels are not totally green. Therefore, it is (AM, 20 wt%) was dissolved in the former LDH dispersion, the
still challenging to develop a new green preparation procedure to initiator (APS, 10 mg mL1 in water) and the accelerator
achieve LDH/PAM NC hydrogels. (TEMED) were added, and then stirred at 0 1C for 10 min to
The aim of the present work is to develop a new green procedure yield a homogeneous dispersion. Subsequently, free-radical poly-
to achieve LDH/polymer NC hydrogels with ultrahigh mechanical merization was carried out in a water bath at 10 1C for 72 h to
properties, using either formamide or LDH–Ise. Here, an amino afford the NC hydrogels. Oxygen was excluded in the whole
acid of L-serine (L-Ser) was used to intercalate the LDH with nitrate experimental procedure. The compositions of LmM hydrogels
as counter ions (LDH–NO3).28 The selection of L-Ser rather than are given in Table 1. The hydrogels were fabricated in cylind-
other amino acids and the concentration were decided by our rical glass vessels (12.5 mm in inner diameter and 145 mm in
experiments as well as the literature.28 Importantly, water was used length) or rod-like glass vessels (5 mm in inner diameter and
as the medium during both the anion exchange reaction and the 70 mm in length).
exfoliation of LDH accomplished in one step, which is distinctly
superior to the preparation of LDH–Ise using methanol9,27 and the 2.3. Characterization
exfoliation of LDH–NO3 in formamide.21 Because polyacrylamide XRD measurements were conducted on a Rigaku D/max 2500
(PAM) is perhaps one of the most frequently-reported type of diffractometer with Cu Ka radiation (l = 0.15418 nm) at a scanning
polymer in polymer hydrogels, it was chosen in the present work. rate of 41 min1 over the range of rotating angle 2y = 51–401.
After LDH–L-Ser was exfoliated in water and the monomer FTIR spectra were collected using a Perkin-Elmer System
(acrylamide, AM) was adsorbed on LDH surfaces by hydrogen 2000 FTIR spectrometer for 64 scans with the range of 4000–
bonding, the LDH/PAM NC hydrogels were obtained by the in situ 400 cm1. The solid samples were ground with KBr (Aladdin)
free radical polymerization procedure. Subsequently, the LDH at a mass ratio of B1 : 100 and pressed into disks for FTIR
dispersion microstructure was characterized. The mechanical measurements.
properties including tensile and compression were measured. The contents of Zn and Al were obtained using a diluted
Finally, the molecular mechanism of the high deformability for nitric acid solution measured using a SPECTRO ARCOS EOP
the LDH/PAM NC hydrogels was discussed based on crosslinking Axial View Inductively Coupled Plasma Spectrometer (SPECTRO
density, inter-crosslinking molecular weight and swelling tests. Analytical Instruments GmbH).
Particle size distribution of aqueous LDH dispersion (2 wt%)
was measured by the dynamic light scattering (DLS) method
2. Experimental at 25 1C using a Malvern Nano-ZS Zetasizer Particle Analyser
2.1. Materials (Malvern Instruments, England).
Thermogravimetric analysis (TGA) was carried out on a TA
Acrylamide (AM, 99%) monomers and L-serine were purchased Instruments Q600 TGA/DSC simultaneous thermal analyser,
from J&K Technology Co. Ltd (Beijing) and GL Biochem (Shanghai) heating from 25 1C to 1000 1C at a heating rate of 10 1C min1.
Ltd, respectively. N,N,N0 ,N0 -Tetramethyl-ethylenediamine (TEMED)
Transmission electron microscopic (TEM) images were
(99%) was provided by Aladdin. All of the other chemical reagents,
taken using a JEOL-2200FS at 100 kV for dried gels (in an air-
including ammonium peroxydisulfate (APS), Zn(NO3)26H2O,
circulating oven at 80 1C for 2 days). Ultrathin films (ca. 80 nm
Al(NO3)39H2O, and NaNO3, are of analytical pure reagent
thick) were prepared for TEM observation by cutting dried gels
(A.R.) grade, purchased from Sinopharm Chemical Reagent
using a Leica Ultracut S microtome and collected on 300-mesh
Co., Ltd. Deionized water (18 MO cm) for all experiments was
copper grids.
obtained from a Millipore Milli-Q BiocelA10 purification unit.
For the preparation of hydrogels, nitrogen gas was bubbled
Table 1 The composition of reactants for the synthesis of LDH/PAM NC
through the deionized water for more than 3 h prior to use. hydrogels (LmM) with LDH–L-Ser as the crosslinker

2.2. Synthesis of LDH/PAM NC hydrogels Sample AM (g) APS (g) TEMED (mL) LDH (g) L-Ser (g) H2O (mL)
a
The inorganic constituent ZnAl–LDH–NO3 was synthesized using LmM 1.5 0.003 4.8 0.09–0.18 0.95 6
a typical coprecipitation method.19 Deduced by inductively a
m stands for the concentration 0.1  LDH/water (g L ). 1

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2.4. Mechanical property measurements the synthesis of LDH–Ise using methanol as the LDH exfoliation
Mechanical tensile tests were performed at 25 1C using an medium,9,25–27 the present method has obvious advantage in
Instron 3365 testing instrument. The specimens for tensile terms of the levels of green and sustainable materials. Subse-
tests were of rod-shape with 5 mm in diameter and 50 mm in quently, the monomer (AM), the accelerator (TEMED) and the
length. The distance between the two clamps was about 20 mm initiator (APS) were added. Due to the interfacial hydrogen bond-
and the crosshead speed was 100 mm min1. ing attractions, the AM monomer was adsorbed on the surfaces of
For the compressive stress–strain measurements, the cylindrical the organo-LDH (LDH–L-Ser). After the in situ free-radical polymer-
samples of the as-prepared hydrogels were used with dimensions of ization was completed on the LDH surfaces, LDH/PAM NC hydro-
12.5 mm in diameter and 10–12 mm in height. The crosshead gels (LmM, m stands for the concentration of 0.1  LDH/water
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speed was 10 mm min1. The compression strengths were (g L1)) were obtained.
obtained using the stress at a deformation of 85%.
For both tensile and compression measurements, the initial 3.2. Delamination and dispersion microstructure of LDH in
cross section was used to calculate the strengths and the moduli. water and NC hydrogels
The tensile or compression modulus was determined from the
The delamination and dispersion microstructures of the
linear increase in stress detected between the deformations of
LDH–L-Ser in water and the LDH/PAM NC hydrogels (L1M) are
10% and 20%.
investigated by DLS and TEM techniques, respectively. As
2.5. Swelling tests shown in Fig. 2a, in the glass vial, the aqueous dispersion of
LDH–L-Ser (2 wt%) is clear and transparent, without precipita-
Swelling experiments were conducted by immersing the
tion or aggregation, at the bottom. In addition, the appearance
as-prepared hydrogels (initial size of 5 mm in diameter and
of a Tyndall phenomenon, i.e. an obvious red light column
30 mm in length) in a large excess of water at room temperature
occurred after being irradiated by a laser light, also confirmed
for 3 days to reach swelling equilibrium. During this period,
the colloid system. Moreover, quantitative data of the exfolia-
water was changed several times. Swelling ratios (Q) are calcu-
tion and dispersion state were obtained by DLS measurements.
lated by the ratio of the weight of the swollen hydrogels (Wgel) to
The particle size distribution for the aqueous dispersion lay in
the corresponding lyophilized gels (Wdry).
the range between 20 and 70 nm with a particle dispersion
index (PDI) of 0.292. The maxima for the average hydrodynamic
3. Results and discussion diameters lie in ca. 22 nm and 24 nm. Therefore, it can be
concluded that the LDH–L-Ser was significantly delaminated
3.1. Preparation of LDH/PAM NC hydrogels using water as the and uniformly dispersed in water. The mechanism for the water
media for both anion exchange and exfoliation of LDH swelling and exfoliation of LDH–L-Ser may be ascribed to the
Fig. 1 shows the preparation procedure of LDH/PAM NC formation of hydrogen bonding as well as the improvement of
hydrogels. The amount of starting materials and the abbrevia- water permittivity by zwitterions.28
tions of NC hydrogels are illustrated in Table 1. In brief, first, Fig. 2b displays the TEM image of the LDH/PAM NC hydro-
ZnAl–LDH–NO3, synthesized by a typical coprecipitation method,19 gel (L1M). The dark areas stand for the individual platelets of
was mixed with L-Ser aqueous solution. The intercalation of L-Ser the irregular-shaped LDH–L-Ser dispersed in the L1M. The
via anion exchange reaction and the exfoliation of LDH were dimension of the platelets is obviously less than 100 nm, with
carried out simultaneously in one step. Compared with the two approximately 30 nm in diameter. In addition, in Fig. S4 (ESI†),
independent steps of anion exchange and exfoliation in previous the disappearance of the sharp peaks characteristic of the ordered
research,9 the fabrication procedure developed herein is obviously alignment of LDH nanosheets also confirms the significant
convenient. More importantly, water was used as the media to exfoliation in the NC hydrogel. The combination of TEM images
replace the toxic organic solvent of methanol. In contrast to the and XRD patterns demonstrate the dramatic exfoliation and the
previous research using formamide to exfoliate LDH–NO321 and homogeneous dispersion of LDH–L-Ser in the NC hydrogel, where

Fig. 1 Schematic illustration showing the preparation procedure of LDH/PAM NC hydrogels via exfoliation–adsorption in situ polymerization, where
water was used as the medium of anion exchange and exfoliation of the LDH.

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be compressed significantly and did not break at all, even at


an extremely high strain. Also note that after the compression
force was removed, the original cylinder shape could be
recovered automatically and rapidly. Therefore, we conclude
that unlike the brittle neat PAM and the conventional
chemically-crosslinked hydrogels, the present LDH/PAM NC
hydrogels possessed extraordinary mechanical toughness
and could withstand high degrees of various mechanical
deformations.
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Furthermore, quantitative studies of the tensile and com-


pression properties of the LDH/PAM NC hydrogels have been
conducted. As shown in Fig. 4a and Table 2, the as-prepared
LDH/PAM NC hydrogels (LmM) displayed excellent tensile pro-
perties. The tensile yield strengths and fracture strengths
increased with increasing loadings of LDH–L-Ser. More impor-
tantly, all of these as-prepared NC hydrogels were extraordinary
stretchable. The elongation at break for L1M was 3800%, and
the fracture strains for L2M or L3M were higher than 3950%
and 4936%, respectively. Note that the LDH contents in these
NC hydrogels were very low. Indeed, the ultrahigh elongations
at break for LDH/PAM NC hydrogels reported herein are
comparable to the highest values of the reported polymer NC
hydrogels such as clay/PAM,1,2 graphene/PAM3–6 and LDH–Ise/
PAM9 NC hydrogels. Interestingly, a distinct yielding phenom-
enon occurred in LmM, which has been observed in our
Fig. 2 Delamination and dispersion of LDH–L-Ser in (a) water and (b) LDH/ previous research of the LDH–Ise/PAM NC hydrogels9 but was
PAM NC (L1M) hydrogels. The inset image shows the glass vial containing different from other polymer NC gels.1–6 Therefore, the whole
aqueous LDH–L-Ser dispersion with a distinct Tyndall phenomenon. stretching process can be divided into three major stages. In
the first stage (I), an initial elastic deformation with high
modulus occurred, and the stress increased linearly with the
the dispersed inorganic nanoparticles of LDH–L-Ser might act as strain. In the subsequent stage (II), the yielding phenomenon
crosslinkers to greatly enhance the mechanical properties. happened, accompanied by the decrease of the stress, in which
a transiently unstable necking phenomenon could be clearly
3.3. Mechanical properties observed. In the final stage (III), a stable necking process took
Fig. 3 reveals that all of the as-prepared LDH/PAM NC hydrogels place with an extremely large deformation until the damage of the
display a high transparency and uniformity with the naked eye. sample. In addition, the work of rupture (or called fracture energy)
Neither distinct large aggregates of inorganic particles nor was employed to evaluate the toughness of the NC hydrogels. The
obvious heterogeneous macroscopic phase separation could NC hydrogels reported herein had similar toughness to our
be observed, indicating that the obtained NC hydrogels contained previously-published LDH–Ise/PAM NC hydrogels,9 and enhanced
no frozen structural inhomogeneity. Additionally, LDH/PAM NC with the increase of LDH–L-Ser loadings as well.
hydrogels did not dissolve in excess water; indeed, they displayed Besides tensile measurements, the compression tests of the
equilibrium swelling behaviour. These results suggest that a as-prepared LDH/PAM NC hydrogels were conducted as well.
stable network structure composed of polymer chains and In Fig. 4b, the NC hydrogels of LmM displayed greatly
LDH–L-Ser nanoparticles occurred. In sharp contrast to con- enhanced compression properties, when compared with neat
ventional chemically crosslinked hydrogels, the present NC PAM and chemically crosslinked hydrogels.9 The compression
hydrogels showed extraordinary mechanical toughness, and stress–strain curves revealed that all of the NC hydrogels were
could bear high degrees of versatile mechanical deformations not damaged even under a high strain up to 85%, and could
such as (a) elongation, (b) bending, (c) knotting, (d) knotting recover to its original shape after relaxation. This also suggests
and subsequent elongation, and (e) compression without dis- that the LDH/PAM NC hydrogels had excellent elasticity. In
tinct breakage or damage. Furthermore, these deformations addition, Table 2 shows that both the compression strengths
were reversible. In Fig. 3a, the rod-like sample of the NC and moduli for the LmM hydrogels increased with the content
hydrogel could be easily stretched to dozens of times in length. of LDH–L-Ser.
The NC hydrogel could also withstand high levels of torsion
(Fig. 3b), be knotted (Fig. 3c), or even knotted and subsequently 3.4. Mechanism discussion
stretched greatly (Fig. 3d) without any damage. Additionally, as To shed light on the mechanism of the ultrahigh deform-
shown in Fig. 3e, the NC hydrogel with cylindrical shape could ability of LDH/PAM NC hydrogels, the crosslinked network

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Fig. 3 All of the as-prepared LDH/PAM NC hydrogels exhibited ultrahigh toughness, and could bear high degree of various mechanical deformations
including (a) elongation, (b) bending, (c) knotting, (d) knotting and subsequent elongation, and (e) compression.

The classic kinetic theory of rubber elasticity29 has been


always applied to investigate the crosslinking structure and the
density of polymer based hydrogels,
F = fN*kT (a  a2) (1)
where F, f, k, T and a are the force per unit original cross-
sectional area of the hydrogels, a front factor, Boltzmann’s
constant, the absolute temperature and the extension ratio,
respectively. Here, a equals 2 and the corresponding stress at
100% elongation were adopted. f and T were 1 and 298.15 K,
respectively. As illustrated in Table 2, the N* values calculated
based on eqn (1) for all of the NC hydrogels are low (L1M:
10.7 mol m3, L2M: 9.99 mol m3, and L3M: 11.2 mol m3),
confirming a low degree of crosslinking network structure
occurring in the LmM hydrogels reported herein. As a result,
the inter-crosslinking distances were long. Furthermore, Mc
could be calculated according to eqn (2), assuming the low
crosslinking density in NC hydrogels,30
N* = rNAV/Mc (2)
where r and NAV is the density of the polymer hydrogel and the
Avogadro’s number, respectively. Table 2 reveals that the Mc for
all of the NC hydrogels are high, thus various deformation
stresses could be successfully relaxed to avoid break or damage.
The crosslinked network microstructure composed of long and
flexible polymer molecular chains among the LDH nano-
Fig. 4 Stress–strain curves of (a) tensile and (b) compression measure-
particles led to extremely high deformability under elongation,
ments for the as-prepared LDH/PAM NC hydrogels (LmM).
bending, knotting, knotting and subsequent elongation, and
compression (Fig. 3), and further rendered the NC hydrogels
microstructure and the polymer molecular mobility were with excellent mechanical properties, especially the ultrahigh
studied by means of crosslinking density (number of crosslinked tensibility and elongation at break. Indeed, water molecules
chains per unit volume, N*), the inter-crosslinking molecular might also act as a lubricant for the hydrophilic polymer
weight (the chain lengths between crosslinking points, Mc) and network, and distinctly reduced the friction forces among the
swelling tests. polymers.31

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Table 2 Tensile and compression mechanical properties of LDH/PAM NC hydrogels (LmM)

Yield Fracture Elongation Tensile Toughnessa 104 Mc Compressive Compressive


Sample strength (kPa) strength (kPa) at break (%) modulus (kPa) (MJ m3) N* (mol m3) (g mol1) strength (MPa) modulus (kPa)
L1 M 20.9 21.0 3800 36.4 0.64 10.7 9.38 0.43 53.7
L2M 21.7 433.4 43950 32.1 0.83 9.99 10.0 0.69 66.9
L3M 26.6 467.0 44936 39.5 1.70 11.2 8.96 1.02 78.3
a
Toughness was calculated from the areas under the tensile stress–strain curves.
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compression tests showed that the NC hydrogels exhibited extra-


ordinary stretchability and compressibility. Finally, based on
calculations of N*, Mc as well as swelling tests, the molecular
mechanism of the ultrahigh deformability of LDH/PAM NC hydro-
gels were discussed. The present research opens up a new avenue
to develop green preparation of novel polymer NC hydrogels with
ultrahigh mechanical deformability, which will deepen the under-
standing towards the chemistry of network polymers including
gels, and further widen the applications of polymer hydrogels in
mechanical devices such as artificial muscles, biomedical devices
and drug delivery systems.

Fig. 5 Swelling ratios of the LDH/PAM NC hydrogels (LmM) at different


contents of LDH.
Acknowledgements
G. Chen is thankful for the financial support from Youth Innova-
In addition, the low actual crosslinking density and high
tion Promotion Association, Chinese Academy of Sciences.
water absorption capacity were demonstrated by swelling tests.
All of the LmM hydrogels were highly swelled retaining their
original shape rather than obviously dissolved. This further Notes and references
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9044 | Soft Matter, 2015, 11, 9038--9044 This journal is © The Royal Society of Chemistry 2015