Wei Cui,
Zi-Jing Zhang,
Hang Li,
Le-Min Zhu,
Huan Liu and
Rong Ran*
College of Polymer Science and Engineering, State Key Laboratory of Polymer Materials Engineering, Sichuan University, Chengdu 610065, People's Republic of China. E-mail: ranrong@scu.edu.cn
First published on 9th June 2015
Dual physically cross-linked (DPC) hydrogels were facilely fabricated by introducing hectorite clay LAPONITE® XLG into a hydrophobically associated polyacrylamide (HAPAM) system via one-pot in situ polymerization. The DPC gels exhibited excellent mechanical strength and unique self-reinforcing behavior with the aid of an additional cross-linking effect provided by LAPONITE®. More impressively, the self-reinforcement of DPC gels could easily be achieved through any of the following three methods: self-healing, remolding or stretching, which was unrealizable for the reported hydrophobic association hydrogels. Compared with HAPAM gels, improved cationic dye adsorption capacity appeared in DPC gels owing to the existence of abundant negative charges on the surface of LAPONITE®. Our proposed methodology highlights the possibility of designing a new type of readily self-reinforced physically cross-linked hydrogels, which have great application potential in bioengineering and the treatment of organic dyes.
At present, enormous efforts have been devoted to developing tough hydrogels with favorable comprehensive properties, such as double network hydrogels,9–12 sliding-ring hydrogels,13 hydrophobically associated (HA) hydrogels,14 nanocomposite (NC) hydrogels,15 macromolecular microsphere composite hydrogels,16 and dipole–dipole or hydrogen bonding enhanced hydrogels.17,18 Among them, HA gels are proved to possess self-healing19,20 and reforming21 capacity without the introduction of extra cross-linking agent. The gelation results from the cross-linking effect supplied by hydrophobically associated micelles,22 whose role is similar to that of cross-linking agents in chemical cross-linked hydrogels. However, because of the single cross-linking pattern, HA gels usually exhibit weaker mechanical strength after loaded. In addition, the conventional amide monomers based HA gels have been considered feeble in dye adsorption on account of their non-ionic monomer composition. Another class of hydrogels physically cross-linked by nanoscopic inorganic materials such as clay is generally called NC gels. For these clay nanocomposite hydrogels, clay are uniformly dispersed and acted as 2-dimensional and multifunctional cross-linkers by adsorbing polymer chains through hydrogen bonding and electrostatic interaction to form a 3-dimensional network. However, NC gels of single cross-linked network usually perform poor mechanical strength23,24 and undesirable self-healing efficiency at low clay content.25,26 Consequently these inherent drawbacks of HA and NC gels have largely blocked their practical applications. In contrast to single cross-linked hydrogels, DN gels consist of two independently cross-linked networks demonstrate ultrahigh mechanical strength and remarkable toughness.27 Generally, DN gels exhibit the best mechanical properties when the first network is highly cross-linked and the second only lightly cross-linked.28 Nevertheless, the majority of DN gels are manufactured by a time consuming two-step approach, during the second step hydrogels with the first network are swelling in precursor solutions of the second network, resulting in an unmanageable total water content of DN gels. Extending this point of view, developing a class of hydrogel with similar network structure to DN gels through one step method seems an appealing alternative. Some approaches have been proposed in an endeavor to obtain this type of hydrogel, namely the dual cross-linked (DC) hydrogel. The existing knowledge of DC hydrogels mainly comes from hybrid physically–chemically cross-linked hydrogels, whose networks are synchronously cross-linked by covalent bonds and physical interactions.29,30 On account of the irreversible and permanent cross-linking pattern originated from covalent bonds, the self-healing property of hybrid DC hydrogel is usually suppressed seriously, which, however, proves to be a fantastic feature in applications.31,32 For HA and NC gels, though self-healing ability is endowed by reversible cross-linking patterns, the mechanical strength of them after repaired always decreases heavily due to low healing efficiency, resulting in their poor reusability. Reasonably, combining the hydrogel system of HA and NC gels to simultaneously ameliorate the mechanical strength and healing efficiency should be an imperative and instructive attempt.
Self-reinforcement is a desirable property for materials requiring recycle use,33 while it is not readily accessible for hydrogels because of their high water content. Tong et al. observed self-reinforcement from polymer–LAPONITE® NC gels by stretching and tearing.34 The orientation of LAPONITE® during elongation was responsible for the self-reinforcement of NC gels. Up to now, no self-reinforcing behavior has been discovered for HA and conventional DC gels, which seriously limited their other applications demanding repeated use such as cartilage, muscle, and adsorbing material for dye wastewater treatment.
In recent years dye contamination has become a serious environmental and social problem due to their environmental toxicity and public health damage. Polymeric hydrogels has been found to be severed as an optimum adsorbing material for dye wastewater treatment in terms of economic feasibility, adsorption-regeneration, simplicity of design, ease of operation and insensitivity to toxic substances.35 It is known that NC hydrogels can absorb and trap ionic dyes, in which LAPONITE® carrying strong negative charges on surface has been demonstrated powerful in dye adsorption because of their high specific surface area, chemical and mechanical stabilities, and a variety of surface and structural properties.36 However, limited recoverability and self-healing property of NC gels restricted their use for this application. Therefore, it naturally arouses our interest to explore a novel derivation of hydrogels, combining high mechanical strength, self-reinforcing behavior, dye adsorption capacity of HA, NC and DC gels.
The existing literatures lead us to consider that it is supposed not difficult to combine the cross-linking networks of HA and NC gels simultaneously to obtain a type of dual physically cross-linked hydrogels since these two hydrogel systems are quite compatible. As far as we know, although a range of HA hydrogels and NC hydrogels have been reported, in the case of influences controlled by LAPONITE® and hydrophobic/hydrophilic monomers on the mechanical properties, there have been little progress in self-reinforcement of NC or HA gels. To the best of our knowledge, no self-reinforced hydrogel has been reported with the combination of HA and NC hydrogel systems so far.
In this work, we report the successful preparation of novel dual physically cross-linked (DPC) gels with unique self-reinforcing behavior and improved dye adsorption capacity by a simple one-pot polymerization method. The self-reinforcement of DPC gels could be achieved through three methods: self-healing, remolding and stretching, which was totally inaccessible for chemically cross-linked or hybrid DC gels. We have explored a strategy to improve the mechanical properties and self-healing efficiency of hydrogels by combining synergistic cross-linking effect provided by hydrophobically associated micelles and LAPONITE® nanosheets. The LAPONITE® added acts as cooperative cross-linking agent and improves the dye adsorption ability. The results show us an efficient way to synthesize self-reinforced dual physically cross-linked hydrogels for practical application as tough materials in tissue scaffolds and wastewater treatment.
In this work, DPC gels were designated as DPCn, where n stood for the mass fraction of LAPONITE® (varying from 0.5 to 1.5) relative to the total mass of initial reaction solution. For comparison, HA and NC gels under the same experimental conditions were also prepared. Nomenclature and composition contents of all gels are listed in Table 1.
Samples | LAPONITE® [g] | H2Oa [g] | AM [g] | SMA [g] | SDBS [g] | KPS [g] | H2Ob [g] |
---|---|---|---|---|---|---|---|
a Mass of water used to disperse LAPONITE® and dissolve monomers.b Mass of water used to dissolve initiator KPS. | |||||||
NC1 | 0.15 | 12.59 | 1.50 | 0 | 0 | 0.0075 | 0.75 |
NC1.5 | 0.225 | 12.515 | 1.50 | 0 | 0 | 0.0075 | 0.75 |
HA | 0 | 12.08 | 1.50 | 0.14 | 0.45 | 0.0082 | 0.82 |
DPC0.5 | 0.075 | 12.005 | 1.50 | 0.14 | 0.45 | 0.0082 | 0.82 |
DPC1 | 0.15 | 11.93 | 1.50 | 0.14 | 0.45 | 0.0082 | 0.82 |
DPC1.5 | 0.225 | 11.855 | 1.50 | 0.14 | 0.45 | 0.0082 | 0.82 |
Rheology measurements of DPC, HA gels were conducted with Bohlin Gemini 200 rheometer using a parallel plate of diameter 20 mm at 25 °C. First, the dynamic strain sweep from 0.1% to 10% was carried out at angular frequency of 1 rad s−1 to determine the linear viscoelasticity region. Then, the frequency sweep was performed over the frequency range of 0.1–100 rad s−1 at a fixed strain of 1%.
Qe = (C0 − Ce) × V/m | (1) |
We compared tensile mechanical properties among HA, NC gels and DPC gels. As shown in Fig. 1a, HA gels with single cross-linking network was very ductile and weak (tensile stress of 31.96 kPa). For NC gels with low content of LAPONITE® less than 1 wt%, single cross-linking network could not even support their own weight. When it came to 1 wt% (NC1) or 1.5 wt% (NC1.5), though bulk hydrogels were obtained, their mechanical strength was no more than 7 kPa (inset in Fig. 1a), which was merely 1/18 that of DPC1.5 gel. Therefore, NC gels were eliminated to test for comparison in subsequent measurements since they were too weak to even bear the test conditions. However, when LAPONITE® is introduced into the HA network to form DPC gels, additional cross-linking effect tends to enhance mechanical extensibility, strength, and toughness of the gels. It could also be seen in Fig. 1a that DPC gels exhibited outstanding mechanical properties compared to either HA or NC gel, and when the concentration of LAPONITE® increased from 0.5 to 1.5 wt%, the tensile strength of DPC gels increased obviously. For example, the tensile stress of DPC1 was 87.19 kPa, which was more than twice the total tensile stress of HA and NC1 gel. Therefore, we could conclude from these results that dual cross-linking effects provided by both hydrophobically associated domains and LAPONITE® played the synergistic effect, allowing DPC gels to survive much higher strength than that of single cross-linked hydrogel. The detailed values of tensile parameters were summarized in Table 2.
Samples | Tensile strength (kPa) | Elongation (%) | Tensile modulus (kPa) | The maximum load (N) |
---|---|---|---|---|
NC1 | 5.71 | 2270 | 0.12 | 0.25 |
NC1.5 | 6.96 | 2235 | 0.44 | 0.39 |
HA | 31.96 | 2136 | 0.99 | 2.19 |
DPC0.5 | 75.17 | 2821 | 1.81 | 5.32 |
DPC1 | 87.19 | 1633 | 2.91 | 6.33 |
DPC1.5 | 107.11 | 1605 | 3.06 | 6.96 |
In Fig. 1b we compared the tensile hysteresis curves of DPC and HA gels during a loading–unloading cycle to reveal their energy dissipation capacity, which was another indicator to assess the mechanical property of hydrogels. Hysteresis loops were observed when DPC and HA gels were stretched to 1500% and reverted at the same speed of 100 mm min−1. At strain of 1500%, all DPC gels exhibited similar large hysteresis loops, which extended a little with increasing LAPONITE® content. While single cross-linked HA gel only showed a very small hysteresis loop. Consistently, DPC0.5, DPC1 and DPC1.5 gels had almost equivalent dissipated energies of 147.63, 188.43 and 188.62 kJ m−3, respectively, which was much higher than that of 43.10 kJ m−3 for HA gel. One could conclude that energy was dissipated much more efficiently by DPC gels than HA gel during the stretching and reverting, thus resulting in higher mechanical strength and toughness.
In order to enhance the stability of the pre-polymerization suspension and increase the mechanical properties of conventional single cross-linked HA gels, a reinforcing agent compatible with the polymer in water was required. LAPONITE® was applicable not only for the stabilization of the pre-polymerization suspension but also for the enhancement to the hydrogels, which played the role of cross-linking agent. Fig. 2B illustrates the angular frequency ω dependence of the storage modulus G′ and loss modulus G′′ for HA and DPC gels with different LAPONITE® content. It is obvious that G′ is always much higher than G′′ and appeared as a plateau over the observed frequency range for HA and all DPC gels, which indicates that cross-linked networks have been formed in these gels. It is noted that addition of only 0.5 wt% of LAPONITE® leads to an evident increase in G′ compared to HA gels. Moreover, higher LAPONITE® concentration gives rise to higher G′, which is consistent with the previous tensile tests of the hydrogels. At the frequency of 1 rad s−1, the G′ of DPC0.5 is 1872 Pa, higher than the 1143 Pa of HA, when the amount of LAPONITE® increased to 1.5 wt%, the G′ reached 3726 Pa, which is 226% higher than that of HA gel. These results suggest the excellent physically cross-linking effect provided by LAPONITE® appears in DPC hydrogels.
Ge = NRT | (2) |
For comparison, the network chain density was also estimated by using the elongation date following the method reported in the literature.43,44 For elongation, the effective network chain density N* is evaluated from the tensile stress τ and elongation ratio γ on the assumption of affine deformation and incompressible volume.
τ = N*RT[γ − (1/γ)2] | (3) |
Fig. 3 The effective network chain density of DPC gels (HA gel was expressed as DPC0) with varying LAPONITE® content. |
Fig. 4 SEM micrographs of (a1) HA gel, (a2) a local partial enlarged image of (a1), (b1) DPC1.5 gel, (b2) a local partial enlarged image of (b1). |
Self-healing ability of DPC gels was inherited from HA and NC gels. The self-healing process of DPC0.5 gel was shown in Fig. 5a. The hydrogel specimen was cut into two separate parts (Fig. 5a1), then the two pieces were connected immediately after a small amount of water was sprayed on the cut surfaces (Fig. 5a2). The self-healed DPC0.5 gel without any sign of a knife-cut was obtained by preserving the cut pieces at room temperature in wet-keeping cabinet for 3 days (Fig. 5a3). We further evaluated the self-healing efficiency of DPC0.5 gel by tensile measurements, which of HA gel was also investigated as a comparison. As depicted in Fig. 5b, both of the self-healed HA gel and DPC0.5 gel still possessed high extensibility and could be stretched to a large deformation without breaking. Interestingly, it was noted that the tensile modulus, strength of the self-healed DPC0.5 gel exceeded the original specimen (Fig. 5b1) in contrast with the sharp decrease in those of HA gel after self-healing (Fig. 5b2), suggesting the self-healing efficiency of DPC0.5 was superior to that of HA gel apparently and self-reinforcement of DPC gels could be attained by means of self-healing.
It was reported that the conventional HA gels were endowed self-healing ability due to the reversible dissociation process of the physical cross-linking inside the hydrogel network.46,47 Unfortunately, the absence of long and flexible polymer chain entanglements after cut usually led to a significant decrease in mechanical strength even after the HA specimen was healed. Thus self-reinforcement was totally unrealizable for HA gels without the aid of cross-linking effect supplied by LAPONITE®. The unique polymer–clay dual cross-linked network structure formed in DPC gels by the introduction of LAPONITE® played an essential role in improving the strength of DPC gels after healed. Once the DPC gel was obtained after polymerization, numerous dangling polymer chains with only one end anchored to LAPONITE® nanosheets and hydrophobically associated domains appeared in the hydrogel network (redlines in Scheme 2a), which contributed nothing to the mechanical properties of DPC gels. But when the two cut pieces (Scheme 2b) were connected, the mobility of polymer chains at the fresh-cut surfaces was enhanced owning to the lubrication of water, thus most of these dangling chains could be adsorbed onto the adjacent LAPONITE® nanosheets through chain diffusion and hydrogen bonding,48,49 which strengthened the cross-linking effect at the joint section. Meanwhile, additional cross-linking effect supplied by hydrophobic association domains was created again due to the structural reorganization of hydrophobically modified PAM chains.50,51 As a consequence, intensive cross-linked network was formed at the self-healing interface by the synergistic effect of dual recross-linking actions (Scheme 2d), resulting in a mechanical enhancement of DPC gels. That is, more hydrogen interactions between polymer chains and LAPONITE® nanosheets would appear in DPC gels after healed, which would need more energy for the breaking of the hydrogels. Thereby the tensile toughness of DPC0.5 after healed was also increased in obviously contrast with HA since the tensile toughness was defined as the area underneath the tensile stress–strain curve (Fig. S1†).
In addition to self-healing ability, the structural reorganization of hydrophobically modified PAM chains also endowed DPC gels with remolding capacity as well as HA gels.39 As shown in Fig. 6a, the forepart of the original DPC1.5 (Fig. 6a1) entirely copied the shape of a syringe nozzle after being forced into the syringe with pressing the plunger for 3 h at 50 °C (Fig. 6a2). The remolded part could still be stretched to a large deformation before breaking (Fig. 6a3). Tensile measurements were conducted to evaluate the mechanical strength of DPC1.5 after remolding (Fig. 6b). It was remarkable that the self-reinforcement emerged in the remolded part by comparison of tensile toughness, which was consistent with the self-healing results (Fig. S2†).
We suspected that the dangling chains on LAPONITE® played a crucial part again in enhancing DPC gels after remolding. When DPC1.5 was compressed in syringe, the distance between neighboring LAPONITE® nanosheets was shortened (Scheme 2c). Moreover, the motility of polymer chains was enhanced thanks to the elevated temperature, offering more opportunities for dangling chains to adhere onto the surfaces of LAPONITE® nanosheets. The cross-linking density would inevitably increase as long as the remolding process period was long enough (Scheme 2d), resulting a reinforcement in mechanical strength of DPC gels. Both hydrophobically associated domains and LAPONITE® nanosheets performed its own cross-linking effect in remolding process. Reversible cross-linking action of hydrophobically associated domains allowed DPC gels to reform into other shapes, at the same time the adsorption of dangling chains onto LAPONITE® contributed to the increase in mechanical strength of DPC gels after remolding. Therefore, not only could DPC gels be shape-molded in polymerization process, but also would be remolded by reforming process as thermoplastic resins to obtain stronger mechanical properties, which was totally impossible for hybrid dual cross-linked hydrogels because of the irreversible covalent cross-linked bonds.52 It was worth nothing that the self-reinforcement process achieved by self-healing and remolding could not be repeated unlimitedly owning to the limited number of dangling chain, which would be discussed in our further work.
Intriguingly, by combining the self-healing and remolding abilities, DPC gels could be employed as a sort of self-healing protecting film materials. In this scenario, we were triggered to verify the protective action of DPC gels on easily scratched materials. DPC1.5 gel was demonstrated as an example (Fig. 7a). By forcibly compressing DPC1.5 for 3 h, it completely remolded to be a thin film (Fig. 7b). Then we coated a coverslip with DPC1.5 as a protecting film (Fig. 7c). To imitate the scratch on materials in practical application, a wound was created through knife-cutting (Fig. 7d), which, however, did not appear on the surface of coverslip thanks to the protection of DPC1.5 film. After closing the notch together and spraying trace amount of water on the cut, the hydrogel film self-healed at room temperature after 3 days, which is found to be inseparable even if the film was stretched (Fig. 7e). The self-healed gel could be utilized again as protecting film on the coverslip (Fig. 7f). The results obtained here were expected to help widen the practical application of DPC gels due to their fantastic properties by combination of HA and NC hydrogel systems.
Stress softening was discovered in HA gels,39 namely, tensile force of HA gels tended to decrease for consecutive tests since some hydrophobic association micelles was broken in tensile process. However, polymer–LAPONITE® NC gels usually showed an enhanced mechanical behavior after stretching to a large deformation due to the orientation of LAPONITE® nanosheets in the NC gel during the elongation.15,48,53 The contradictory repeat tensile property between HA gels and NC gels naturally arouses our interest to investigate the repeat tensile property of DPC gels, whose system was a combination of HA and NC gels. Fig. 8 showed the stress–strain curves of DPC gels during the continuous elongations at a fixed strain of 1200% for five times. The stress increased with strain obviously during subsequent tensile after the first stretching. And no fracture appeared during the elongation, suggesting the outstanding tensibility and self-reinforcement property of DPC gels. Thus it could be concluded that the orientation of LAPONITE® nanosheets contributed a lot to enhance the mechanical strength and neutralize the reduction caused by the damage of hydrophobically associated micelles.
Fig. 8 Stress–strain curves for DPC0.5 (a), DPC1 (b) and DPC1.5 (c) gel under repeated stretching to a fixed strain at 1200% for five times. |
To sum up of this section, self-reinforcement of DPC gels can be realized by three methods: self-healing, remolding and repeated stretching to a constant strain, which may widen the application of hydrogels in the field of materials requiring recycling use.
A series of water soluble cationic dyes (MG, MB, MO, BF and CV) were used for studying the dye adsorption capacity of DPC gels (DPC1.5 was shown as an example in Fig. 9), the dye adsorption performance of DPC gels can be clearly observed by the change in depth of the dye colors. After immersing in each dye solution (10 mg L−1) (Fig. 9a) for 6 h at room temperature, DPC1.5 turned its color into the same color of the dye while the dye solution faded obviously (Fig. 9b). Then we took all the samples out and immersed them in excess deionized water for 6 h, no leakage was observed and the water always kept clear, indicating a perdurable dye adsorption capacity of DPC gels.
Fig. 9 Photographs of dye solutions (a) before and (b) after adsorption, (c) DPC gels after adsorption of dyes, and (d) DPC gels after immersed in excess deionized water for 3 h. |
To provide further insight and quantificational evidence for the improved dye adsorption capacity of DPC gels, equilibrium dye adsorption capacities of HA and DPC gels were investigated. The results are listed in Table 3. It can be seen from that HA gels have certain abilities to adsorb cationic dyes because of their high swelling ratio, whereas DPC gels possess preferable adsorption capacities compared with HA gels. To compare the dye adsorption capacity more quantificationally, time-dependent adsorption of CV on DPC1.5 and HA was conducted as an example (Fig. S3a†). Apparently, the adsorption rate of CV on DPC1.5 was much higher than that on HA, which was reflected by the higher initial slope of the adsorption kinetic curve. Impressively, the equilibrium adsorption amount of CV on DPC1.5 outperformed that on HA with an increase of about 740%, indicating that strong driving force for the adsorption of dyes was generated by the introduction of LAPONITE®. As for the pseudo-second-order equation, the correlation coefficients of CV on DPC1.5 and HA were 0.997 and 0.981, respectively (Fig. S3b†), suggesting that the adsorption kinetics was well in line with the pseudo-second-order model, which was usually used to forecast the amount of dye adsorbed on hydrogel at a certain time. Since there are a lot of negative charges existed on the surfaces of LAPONITE® nanosheets, which are able to interact with cationic dye molecules. Therefore, although the network of DPC gels is more compact, they tend to adsorb more cationic dye molecules instead of water molecules during the swelling process. By this way, DPC gels are endowed superior capacity to adsorb high amount of cationic dye molecules. Thus, with the introduction of LAPONITE®, the mechanical tough DPC gels can be widely used in the treatment of dye pollution.
Samples | Qe (mg g−1)/MG | Qe (mg g−1)/MB | Qe (mg g−1)/MO | Qe (mg g−1)/BF | Qe (mg g−1)/CV |
---|---|---|---|---|---|
HA | 19.912 | 17.398 | 14.265 | 36.868 | 11.737 |
DPC0.5 | 37.681 | 45.482 | 39.362 | 41.824 | 31.219 |
DPC1 | 61.273 | 49.420 | 42.529 | 44.221 | 57.851 |
DPC1.5 | 68.158 | 53.368 | 49.875 | 66.053 | 95.736 |
Footnote |
† Electronic supplementary information (ESI) available. See DOI: 10.1039/c5ra06361b |
This journal is © The Royal Society of Chemistry 2015 |