A novel fabrication method of temperature-responsive poly(acrylamide) composite hydrogel with high mechanical strength

High strength, stimuli-responsive poly(acrylamide) composite hydrogels (PAAm CH gels) were prepared by grafting polymerization of acrylamide (AAm) onto temperature-sensitive core–shell microgels. These microgels, composing of poly(N-isopropylacrylamide) as core and polyvinylamine (PVAm) as shell, were used as both initiator and crosslinker to form a robust three-dimensional network via bonding the poly(acrylamide) (PAAm) backbone. The CH gels exhibited a remarkably rapid shrinking rate and transmittance switch in response to the environmental temperature change, which the conventional chemically cross-linking PAAm hydrogels (PAAm OR) were short of. Even compared to the bulk PNIPAAm hydrogels (PNIPAAm OR) crosslinked with N,N′-methylenebisacrylamide (MBA), the CH gels were featured with faster responsive rate, which could be attributed to the formation of interconnected water transportation channels between the microspheres and PAAm gel matrix due to the fast shrinking of microgels. Moreover, the effects of microgel species and content on swelling and mechanical properties of CH gels were also systematically investigated. The results elaborated that the CH gels could be compressed almost 99% without breaking and completely recovered their original shape when the stress was removed. And the optimized compressive strength of CH gels could be up to 21.94 MPa. Based on the analysis of CH gel mechanical properties, the influence of microsphere content on effective network chains density of CH gels was discussed through rheology measurements. Finally, the essential reinforcement on mechanical properties was mainly contributed to the homogeneous microstructure of hydrogel network and the energy dissipation mechanism of microgels in gel matrix.     

Robust hydrogel of regenerated cellulose by chemical crosslinking coupled with polyacrylamide network

Regenerated cellulose/polyacrylamide (RC/PAAm) double network (DN) hydrogels are composed of cellulose crosslinked by epichlorohydrin (ECH) and chemical-crosslinked PAAm. The prepared RC/PAAm DN hydrogels present enhanced strength, good shape recovery property, excellent energy dissipation properties, decreased equilibrium water content, and low equilibrium swelling ratio (SR). The compressive strength and modulus of RC/PAAm hydrogel are about 4.3 and 11.5 times compared to that of RC hydrogel, respectively. Intriguingly, the chemical crosslinking between ECH and cellulose chains could increase the distance between cellulose chains. Consequently, the increasing molar ratio of ECH to glucose leads to larger SRs and decreased mechanical strength of the hydrogels. Additionally, higher PAAm contents lead to more densely crosslinked networks, and thus decreasing the SRs and improving the mechanical strength of the hydrogels. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47811.     

Enhancing mechanical strength of hydrogels via IPN structure

In this investigation, polyacrylamide (PAAm) as the flexible network is introduced to enhance the mechanical strength of hyaluronic acid–gelatin (HA–Gel) hydrogels by interpenetrating polymer network (IPN). The structure, mechanical property, and rheology property of the IPN hydrogels are investigated. It is found that the compressive strength of the HA–Gel/PAAm IPN hydrogels has increased five times higher than that of HA–Gel hydrogels. Rheological test demonstrates that elastic moduli (G′) and viscous moduli (G″) of HA–Gel/PAAm IPN hydrogels increase 100 times higher than those of HA–Gel hydrogels. Moreover, the HA–Gel hydrogels are fractured under the low compressive stress, whereas HA–Gel/PAAm IPN hydrogels are not broken under the high compressive stress. It is envisioned that the IPN hydrogels will be an effective approach to enhance the mechanical strength and broaden the range of hydrogels' applications. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44503.     

Effect of spatial gel inhomogeneity on the elastic modulus of strong polyelectrolyte hydrogels

Summary The effect of spatial inhomogeneity on the elastic modulus of ionic poly(acrylamide) (PAAm) hydrogels has been investigated with the static light scattering measurements. The gels were prepared by free-radical crosslinking copolymerization of acrylamide and 2-acrylamido-2-methylpropane sulfonic acid sodium salt (AMPS) monomers and N,N’-methylenebis(acrylamide) crosslinker. The crosslinker concentration of the hydrogels was fixed in our experiments while the mole fraction of AMPS in the comonomer feed (x_i) was varied over a wide range. Elasticity measurements show that the modulus of elasticity of gels increases with increasing x_i from 0 to 0.2. The excess scattering of gels, that is, the degree of spatial gel inhomogeneity rapidly decreases with increasing x_i and approaches to zero at x_i=0.05. Debye-Bueche analysis of the light scattering data indicates frozen concentration fluctuations in gel; the size of the static structures increases while the extent of concentration fluctuations reduces with increasing x_i. It was shown that the macroscopic elastic properties of PAAm gels are mainly controlled by the microscopic gel structure determined by the scattering measurements.     

Effects of cyclization and pendant vinyl group reactivity on the swelling behavior of polyacrylamide gels

A series of polyacrylamide (PAAm) gels were prepared by free-radical crosslinking copolymerization of acrylamide and N,N′-methylenebis(acrylamide) (BAAm) in water at various crosslinker (BAAm) and chain transfer agent (isopropyl alcohol, IPA) concentrations. It was shown that only 5% of the crosslinker used in the feed forms effective crosslinks in the final hydrogels. At BAAm contents as high as 3 mole%, the equilibrium swelling ratio of the gels in water is independent of the crosslinker content in the feed. This is due to the prevailing multiple crosslinking reactions during the gel formation process. At a fixed crosslinker content, the onset of gelation is shifted towards higher conversions and reaction times as the amount of IPA increases. Addition of IPA in the monomer mixture also increases the equilibrium swelling ratio of PAAm gels. It was shown that the gel crosslinking density increases on rising IPA concentration in the feed due to the increasing rate of intermolecular crosslinking reactions. Received: 30 May 1997/Accepted: 26 June 1997     

Mechanical and tribological behaviors of PVA/PAAm double network hydrogels under varied strains as cartilage replacement

The strain change of double network (DN) hydrogels during compressive mechanical and frictional tests is crucial for their performances. The positive effect of the sacrificed network for prohibiting crack in DN hydrogel is likely to be initiated by large strain. In this study, the mechanical and tribological properties of polyvinyl alcohol/polyacrylamide (PVA/PAAm) DN hydrogels are investigated from the viewpoint of strain. The compressive tangent modulus of PVA/PAAm DN hydrogel with 15 wt% AAm shows a sudden increase in the strain of 60% due to the sacrificed PAAm network. The optimized friction behavior is obtained from PVA/PAAm hydrogel with 5 wt% of AAm content, which is not consistent with the optimal compressive modulus at 15 wt% of AAm content. The variation of frictional coefficient of PVA/PAAm DN hydrogels with load is quite different for migrating and stationary contact configurations. The biphasic lubrication mechanism transited to solid–solid contact dominant mechanism is also induced by the high strain at heavy load.     

Water-swellable,tough, and stretchable inorganic–organic sulfoaluminate cement/polyacrylamide double-network hydrogel composites

Effectively improving the mechanical properties of the hydrogel can greatly broaden its application range. The design concept of forming a double-network structure by organic–inorganic hybridization can greatly enhance the mechanical properties of traditional hydrogels. Here, a series of organic–inorganic double-network (OIDN) polyacrylamide/(sulfoaluminate cement) (PAM/SAC) composite gels by solution polymerization were synthesized at room temperature. The OIDN composite gels not only retain the characteristics of water swelling but also exhibit excellent tensile properties (stress and strain are 12 MPa and 2500%, respectively) and compressive strength (stress and strain are 65 MPa and 80%, respectively). In the preparation process, a brittle inorganic network of hydrated sulfoaluminate (hydra-SAC) and a ductile network of polyacrylamide (PAM) were formed by the manner of interpenetrating. The phase composition and thermal stability of the OIDN composite gels were characterized and determined by FTIR, XRD, SEM, and TGA, respectively. The effect of SAC on swelling and mechanical performance of the OIDN composite gels was also investigated. The results show that the use of SAC hybrid hydrogels can effectively improve the mechanical strength, and the OIDN composite gels are expected to be a potential grouting and plugging functional material. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47905.     

Dual-crosslinked hydrogels with metal coordination from novel co-polyaspartamide containing 1,2-dihydroxy and imidazole pendant groups

Herein, a series of new polyaspartamide derivatives, PolyAspAm(API/APD)s, is prepared from polysuccinimide, which is the thermal polycondensation product of aspartic acid, via successive ring-opening using 1-(3-aminopropyl)imidazole (API) and 3-amino-1,2-propanediol (APD). Metal-coordinated hydrogels are generated by adding divalent metal ions (Cu²⁺, Zn²⁺) to the aqueous polymer solution. The resulting gels can adhere strongly to various substrates. Further, novel dual-crosslinked hydrogels are prepared, where the first network is generated via acetal formation between the massive 1,2-hydroxyl groups of the polymer and glutaldehyde as the crosslinker. Subsequent immersion of the product gel in various metal ion-containing solutions forms a second network via metal coordination, thereby affording mechanically robust hydrogels. Multiple metal-coordination interactions are expected to occur between the imidazole functional groups and metal cations. The mechanical properties of resulting gel vary depending on the metallic species. These novel kinds of hydrogels are expected to find biomedical applications as adhesives and antibacterial soft matter.     

Autonomic self-healing in covalently crosslinked hydrogels containing hydrophobic domains

Self-healing hydrogels suffer from low mechanical strength due to their reversible breakable bonds which may limit their use in any stress-bearing applications. This deficiency may be improved by creating a hybrid network composed of a combination of a physical network formed via reversible crosslinks and a covalent network. Here, we prepared a series of hybrid hydrogels by the micellar copolymerization of acrylamide with 2 mol % stearyl methacrylate (C18) as a physical crosslinker and various amounts of N,N′-methylenebis(acrylamide) (BAAm) as a chemical crosslinker. Rheological measurements show that the dynamic reversible crosslinks consisting of hydrophobic associations surrounded by surfactant micelles are also effective within the covalent network of the hybrid hydrogels. A significant enhancement in the compressive mechanical properties of the hybrid gels was observed with increasing BAAm content. The existence of an autonomous self-healing process was also demonstrated in hybrid gels formed at low chemical crosslinker ratios. The largest self-healing efficiency in hybrids was observed in terms of the recovered elastic modulus, which was about 80% of the original value.     

Effect of swelling on spatial inhomogeneity in poly(acrylamide) gels formed at various monomer concentrations

The effect of swelling on the spatial inhomogeneity in poly(acrylamide) (PAAm) gels has been investigated with the static light scattering measurements. Four sets of gels were prepared using N,N′-methylenebis(acrylamide) (BAAm) as a crosslinker at various initial monomer concentrations. The crosslinker ratio X (the mole ratio of BAAm to the monomer acrylamide) was fixed at 1/50, 1/61.5, 1/66, and 1/100 in each set of gels. The gels, both at the state of preparation and at the equilibrium swollen state in water, exhibit a maximum degree of spatial gel inhomogeneity at a critical monomer concentration (ν_2,cr⁰). ν_2,cr⁰ shifts toward smaller concentrations as X is decreased or, as the gel swells beyond its swelling degree after preparation. Swelling enhances the extent of spatial inhomogeneity in PAAm gels and, this enhancement mainly occurs at low crosslinker ratios. The theoretical prediction of the Panyukov-Rabin theory was found to be in qualitative agreement with the experimental findings. It was also shown that three different effects, namely crosslinker, concentration, and swelling effects determine the extent of inhomogeneities in gels formed at various monomer concentrations.     

Poly(hydroxamic acid) hydrogels from poly(acrylamide): preparation and characterization

Summary Poly(hydroxamic acid) (PHA) hydrogels from crosslinked poly(acrylamide) (PAAm) hydrogels containing different type crosslinkers such as such as N, N'-methylene bisacrylamide (N) and ethyleneglycol dimethacrylate (E). The effect of crosslinkers on some physical properties was investigated. The structure of hydrogels was characterized spectroscopically and thermally. The swelling parameters of PHA in distilled water, such as percent equilibrium swelling (S_eq%), initial swelling rate (r_o), maximum equilibrium swelling (S_max), diffusional exponent (n), network parameter (k) and diffusion coefficient (D) were calculated. It has been found that the ionogenity of PHA and the structure of the used crosslinkers during the synthesis have been effective on the swelling behaviour of the hydrogels. Received: 12 February 2001 / Revised version: 30 June 2001 / Accepted: 11 July 2001     

Sorption of Methylene Blue onto Ionic Composite Hydrogels Based on Polyacrylamide and Dextran Sulfate: Kinetics,Isotherms, and Thermodynamics

Ionic composite hydrogels based on polyacrylamide (PAAm) and dextran sulfate (DxS) have been prepared by radical polymerization at two temperatures: +20°C and ?18°C, using DxS as physical entrapped polymer, acrylamide (AAm) monomer, N,N^’-methylenebis(acrylamide) (BAAm) as cross-linking agent, ammonium persulfate as radical initiator, and N,N,N’,N’-tetramethylethylenediamine as accelerator of free-radical polymerization. The PAAm/DxS composite hydrogels were tested as sorbents for Methylene Blue (MB) from aqueous solution by the batch procedure. The effect of contact time, initial dye concentration, and temperature on the dye sorption onto composite hydrogels has been investigated. The modeling of the experimental data by applying different kinetic and isotherm models was also performed.     

Suppression of inhomogeneities in hydrogels formed by free-radical crosslinking copolymerization

Network microstructures of poly(acrylamide) (PAAm) and poly(N,N-dimethylacrylamide) (PDMA) hydrogels were compared by static light scattering and elasticity measurements. The hydrogels were prepared by free-radical crosslinking copolymerization of the monomers acrylamide (AAm) or N,N-dimethylacrylamide (DMA) with N,N′-methylenebis(acrylamide) as a crosslinker. During the formation of PAAm gels, the reaction time dependence of the scattered light intensity exhibits a maximum at a critical reaction time, while in case of PDMA gels, both a maximum and a minimum were observed, corresponding to the chain overlap threshold and the gel point, respectively. This difference in the time-course between the two gelling systems is due to the late onset of gelation in the DMA system with respect to the critical overlap concentration. Compared to the AAm system, no significant scattered light intensity rise was observed during the crosslinking polymerization of DMA. It was shown that, regardless of the crosslinker ratio and of the initial monomer concentration, PDMA gel is much more homogeneous than the corresponding PAAm gel due to the shift of the gelation threshold to the semidilute regime of the reaction system. The results suggest that the spatial gel inhomogeneity can be controlled by varying the gel point with respect to the critical overlap concentration during the preparation of gels by free-radical mechanism.     

Swelling behavior of semi‐interpenetrating polymer network hydrogels composed of poly(vinyl alcohol) and poly(acrylamide‐co‐sodium methacrylate)

Interpenetrating polymer network (IPN) hydrogels based on poly(vinyl alcohol) (PVA) and poly(acrylamide‐co‐sodium methacrylate) poly(AAm‐co‐SMA) were prepared by the semi IPN method. These IPN hydrogels were prepared by polymerizing aqueous solution of acrylamide and sodium methacrylate, using ammonium persulphate/N,N,N¹,N¹‐tetramethylethylenediamine (APS/TMEDA) initiating system and N,N¹‐methylene‐bisacrylamide (MBA) as a crosslinker in the presence of a host polymer, poly(vinyl alcohol). The influence of reaction conditions, such as the concentration of PVA, sodium methacrylate, crosslinker, initiator, and reaction temperature, on the swelling behavior of these IPNs was investigated in detail. The results showed that the IPN hydrogels exhibited different swelling behavior as the reaction conditions varied. To verify the structural difference in the IPN hydrogels, scanning electron microscopy (SEM) was used to identify the morphological changes in the IPN as the concentration of crosslinker varied. In addition to MBA, two other crosslinkers were also employed in the preparation of IPNs to illustrate the difference in their swelling phenomena. The swelling kinetics, equilibrium water content, and water transport mechanism of all the IPN hydrogels were investigated. IPN hydrogels being ionic in nature, the swelling behavior was significantly affected by environmental conditions, such as temperature, ionic strength, and pH of the swelling medium. Further, their swelling behavior was also examined in different physiological bio‐fluids. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 302–314, 2005     

Effect of poly(ethylene glycol)-derived crosslinkers on the properties of thermosensitive hydrogels

Three crosslinkers, poly(ethylene glycol) diacrylate (PEGDA), glycerol ethoxylate triacrylate (GETA) and citric acid-(PEG acrylate)₃ (CA-PEGTA) derived from poly(ethylene glycol) (PEG) were synthesized at first. The three series of poly (N-isopropylacrylamide) (PNIPAAm) hydrogels were prepared by photopolymerization with the crosslinkers and compared with a hydrogel based on commercial crosslinker, N,N′-methylene bis-acrylamide (NMBA). The influence of the crosslinker structures and contents on the swelling behaviour, mechanical properties, and drug release of the hydrogels was investigated. The results showed that the hydrogels based on PEGDA and NMBA exhibited the highest and the lowest swelling ratio, respectively. The content of crosslinker of all hydrogel series showed good thermosensitivity and thermo-reversibility. The critical gel transition temperature (CGTT) appeared at 32 °C for the hydrogel based on NMBA, but appeared at about 34 °C for other hydrogels due to higher hydrophilicity of the crosslinker. In the mechanical properties, three-arms crosslinker GETA and CA-PEGTA led to higher mechanical strength than a linear crosslinker PEGDA. A hydrogel based on GETA (NG6) showed the highest shear modulus of 656.9 kPa and Young’s modulus of 1655.0 kPa. The hydrogels containing higher content of crosslinker revealed lower swelling ratio and higher mechanical strength. In the drug release, the hydrogels with higher swelling ratios showed higher drug absorbed. The highest release percentage of caffeine and vitamin B12 for hydrogel based on PEGDA (NP6) could reach 68.3% and 75.4%, respectively. In addition, the bound water and toxicity of the hydrogels were also investigated.

     

A versatile approach to develop porous hydrogels with a regular pore distribution and investigation of their physicomechanical properties

Porous polyacrylamide (PAAm) hydrogels with enhanced mechanical properties and regular pore distribution have been synthesized by a unique and facile methodology, which involves formation of the hydrogel pores by leaching out chemically modified silica particles. To improve the pore distribution and mechanical properties of the hydrogel network, porogen particles have been modified with PAAm chains chemically attached to the silica surface. Grafting polymerization initiated by peroxide groups immobilized on the particle surface has been used for this modification. The grafted PAAm layer on the silica surface improves the dispersibility of the porogen material in the hydrogel composition, and simultaneously forms pore “walls” reinforcing the hydrogel network, after leaching out the silica particles. The proposed synthetic way for the development of porous hydrogels includes three steps: (i) tethering of PAAm chains to silica particles due to the grafting polymerization initiated by an adsorbed polyperoxide macroinitiator (PPM), (ii) simultaneous crosslinking of grafted PAAm chains and PAAm forming hydrogel network, and (iii) pore formation by leaching out silica particles in the presence of hydrofluoric acid. The PPM has been synthesized by a free radical copolymerization of the peroxide monomer (PM) N‐(tert‐butylperoxymethyl)acrylamide with acrylamide. Both PM and PPM have been developed in our lab, and applied for the synthesis of porous polymeric hydrogels. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Investigation of double network hydrogel with controllable swelling behavior by response surface methodology

Hydrogel with high swelling ratio is extremely bad for its application in tissue engineering, which drastically degrades its mechanical properties and generates greater pressure on surrounding tissues. In this work, it is found that the swelling behavior of gelatin/acrylamide acrylate copolymer-Fe³⁺ hydrogels is highly depended on Fe³⁺ concentration and acrylic acid content. In order to know the swelling mechanism and optimize the nonswellable condition, a mathematical model is built based on response surface methodology. Herein, the computational data are in good correspondence to experimental results by combining the theoretical with experimental results. The hydrogels can endure a compressive stress up to 18 megapascals at 90% strain and maintain good shape recovery under multiple cycle compression. Our results demonstrate that swelling behavior of double network hydrogels can be controlled and the suppression of swelling is conducive to hydrogel with good mechanical strength under physiological conditions. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48805.     

Preparation and characterization of PAM/SA tough hydrogels reinforced by IPN technique based on covalent/ionic crosslinking

In order to fabricate tough hydrogels with superior formability, polyacrylamide/sodium alginate (PAM/SA) interpenetrating polymer network (IPN) hydrogels were produced with ionically crosslinked SA interpenetrated in covalently crosslinked PAM. TGA results show that the heat resistance of PAM/SA IPN hydrogel is improved as compared to that of the individual component. Swelling studies indicate that increasing either chemical crosslinker content or ionic crosslinking via adding more N,N′‐methylenebisacrylamide (MBA) or SA results in lower ESR. It is concluded by tensile test that loosely crosslinked PAM coupled with tightly crosslinked SA improve mechanical strength for hydrogels based on covalent/ionic crosslinking. PAM/SA hydrogels via “one‐pot” method can form different complex shapes with mechanical properties comparable to conventional double network (DN) gels. The fracture strength of PAM_0.05/SA₂₀ reaches level of MPa, approaching 2.0 MPa. The work strives to provide method to tune mechanical and physical properties for hydrogels, which is hopefully to guide the design of hydrogel material with desirable properties. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41342.     

Preparation and rheological investigation of tough PAAm hydrogel by adding branched polyethyleneimine

In this article, tough hydrogels are prepared by introducing the polyethyleneimine (PEI) with branched structure and a large number of  NH₂ and  NH groups into permanently crosslinked polyacrylamide (PAAm) hydrogels matrix. To investigate the effects of B-PEI and chemical crosslinking agent (Bis) on the strength and toughness of hydrogels, a series of B-PEI/PAAm hydrogels with different mass percentage of Bis and B-PEI were manufactured and the rheological and swelling properties were compared. For all hydrogels, the storage modulus (G′) was much higher than the loss modulus (G″) in the linear viscoelastic region through the whole frequency range. The solid-like behavior and elastic nature (G′ > G″) are attributed to the permanent covalence crosslinking. Therefore, G′ increased when more Bis was added. For the nonlinear oscillatory shear measurement, hydrogels with B-PEI broke at larger γ than the pure PAAm hydrogels, indicating that the toughness of B-PEI/PAAm hydrogels has been improved by introducing B-PEI. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48541.     

Inhomogeneities in poly(acrylamide) gels: position-dependent elastic modulus measurements

Summary The inhomogeneities in poly(acrylamide) (PAAm) gels and the formation mechanism of inhomogeneities were investigated using the results obtained by the mechanical measurements. The gels in the form of rods of 5.6 mm in diameter were prepared at various crosslinker (N,N'-methylene(bis)acrylamide) content. The initial monomer concentration was set to 5.1 w/v %. The results show that the elastic modulus of PAAm gels varies depending on the location, at which the mechanical measurements are carried out. The modulus increases with increasing distance from the bottom of the gel rod. The extent of modulus variation along the gel increases with increasing crosslinker content from 2.6 to 9 % BAAm. Received: 23 January 2001/Revised version: 17 May 2001/Accepted: 17 May 2001