Nanocomposite hydrogels: Fracture toughness and energy dissipation mechanisms

In this study, fracture toughness of nanocomposite hydrogels is quantified, and active mechanisms for dissipation of energy of nanocomposite hydrogels are ascertained. Poly(N,N‐dimethylacrylamide) nanocomposite hydrogels are prepared by in situ free radical polymerization with the incorporation of Laponite, a hectorite synthetic clay. Transmission electron microscopy proves exfoliation of clay platelets that serve as multifunctional crosslinkers in the created physical network. Extraordinary high fracture energies of up to 6800 J m^?2 are determined by the pure shear test approach, which shows that these soft and stretchable hydrogels are insensitive to notches. In contrast to single‐ and double‐network hydrogels, dynamic mechanic analysis and stress relaxation experiments clarify that significant viscoelastic dissipation occurs during deformation of nanocomposite hydrogels. Similar to double‐network hydrogels, crack tip blunting and plastic deformation also contribute to the observed massive fracture energies. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1763–1773     

Hydrogen bond-reinforced double-network hydrogels with ultrahigh elastic modulus and shape memory property

Development of tough hydrogels has greatly expanded their applications as load-bearing materials. However, the elastic modulus of tough hydrogels is usually lower than 1 MPa. It remains a challenge to design tough hydrogels with high modulus. We report here a series of tough double-network (DN) hydrogels with ultrahigh elastic modulus (up to 200 MPa) by forming robust hydrogen bonds between the first poly(acrylic acid) network and the second poly(N-isopropyl acrylamide) network. The dense cooperative hydrogen bonds greatly reduce the segmental mobility and thus improve the rigidity of gel matrix. Owing to the dynamic nature of hydrogen bonds, the modulus of hydrogels is strongly influenced by temperature and pH, affording the gels shape memory property. The strategy by forming robust noncovalent bonds between interpenetrating networks should be applicable to other systems for designing tough and versatile hydrogels with diverse promising applications. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 1281–1286     

New silicone hydrogels based on interpenetrating polymer networks comprising polysiloxane and poly(vinyl alcohol) networks

A method for the synthesis of a new silicone hydrogel as a biphase material for soft contact lenses is considered. The method is based on the synthesis of sequential interpenetrating polymer networks (IPN) and includes the following stages: (1) cross‐linked silicone synthesis by the reaction of vinyl‐ and hydride‐containing oligosiloxanes; (2) silicone network saturation with vinyl acetate and cross‐linking monomer followed by UV‐initiated polymerization to form an IPN comprising the silicone and cross‐linked poly(vinyl acetate) (PVAc) network; (3) PVAc network alcoholysis with methanol to obtain silicone hydrogels comprising the silicone and cross‐linked poly(vinyl alcohol) (PVAl). A study of hydrophilic, optical, mechanical, and structural features of the silicone hydrogels showed that optical transparency is achieved for materials with the highest density of silicone network cross‐linking where the size of IPN structural units does not exceed 100 nm. The water content in hydrophilic networks of silicone hydrogel is found to be below the values typical of cross‐linked PVAl, leading to non‐additivity of IPN mechanical properties. Indeed, the elasticity moduli (E) of the hydrophilic and silicone networks are 0.4–0.7 and 0.7–1.8 MPa, respectively, whereas for some IPN this value reaches 3.0 MPa. The optimal parameters of synthesis providing the reduction of E to 0.8–1.6 MPa without deterioration of the required performance characteristics (optical transparency 90–92%, water content 20–39 wt%) are determined. Copyright © 2009 John Wiley & Sons, Ltd.     

Biomimetic double network hydrogels: Combining dynamic and static crosslinks to enable biofabrication and control cell-matrix interactions

Hydrogels are promising candidates for recapitulation of the native extracellular matrix (ECM), yet recreating molecular and spatiotemporal complexity within a single network remains a challenge. Double network (DN) hydrogels are a promising step towards recapitulating the multicomponent ECM and have enhanced mechanical properties. Here, we investigate DNs based on dynamic covalent and covalent bonds to mimic the dynamicity of the ECM and enable biofabrication. We also investigate the spatiotemporal molecular attachment of a bioactive adhesive peptide within the networks. Using oxidized alginate (dynamic network, Schiff base) and polyethylene glycol diacrylate (static network, acrylate polymerization) we find an optimized procedure, where the dynamic network is formed first, followed by the static network. This initial dynamically cross-linked hydrogel imparts self-healing, injectability, and 3D printability, while the subsequent DN hydrogel improves the stability of the 3D gels and imparts toughness. Rheology and compression testing show that the toughening is due to the combination of energy dissipation (dynamic network) and elasticity (static network). Furthermore, where we place adhesive sites in the network matters; we find distinct differences when an adhesive peptide, Arg-Gly-Asp (RGD), is attached to the different networks. This DN strategy bring us closer to understanding and recreating the complex multicomponent ECM—pushing us past a materials view of cell adhesion—while enabling injectabiltiy and printing of tough hydrogels.     

New hydrogels from interpenetrated physical gels of agarose and chemical gels of polyacrylamide: Effect of relative concentration and crosslinking degree on the viscoelastic and thermal properties

In this article, we report on the viscoelastic and thermal properties of agarose–polyacrylamide (PAAm) interpenetrating polymer hydrogels (IPHs) and semi‐IPHs as a function of agarose concentration and PAAm crosslinking degree. The results demonstrated that the agarose is able to gel in the presence of crosslinked and linear IPHs. In addition, the reticulation of PAAm in the presence of agarose is confirmed for the case of IPHs giving rise to systems with dimensional stability at high temperatures. The formation of a fully IPH was ascertained at low agarose concentrations. A study of the morphology and nanoscale elasticity of the different systems has been carried out with atomic force microscopy/ultrasonic force microscopy (UFM). UFM data provide further evidence of interpenetration, allowing us to visualize—if present—phase‐separated domains with nanoscale resolution for the various crosslinking degrees and PAAm and agarose concentrations used during the formation of the IPHs. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010     

Mechanically robust hydrophobized double network hydrogels and their fundamental salt transport properties

Water swollen polymer networks are attractive for applications ranging from tissue regeneration to water purification. For water purification, charged polymers provide excellent ion separation properties. However, many ion exchange membranes (IEMs) are brittle, necessitating the use of thick support materials that ultimately decrease throughput. To this end, novel double network hydrogels (DNHs) with variable water content are prepared and characterized in terms of mechanical and ion transport properties to evaluate their potential utility as tough membrane materials. The first network contains fixed anionic charges, while the other is comprised of a copolymer with varied ratios of hydrophobic ethyl acrylate (EA) and hydrophilic dimethyl acrylamide (DMA) repeat units. Characterization of freestanding DNH films reveals a reduction in water content from 88 to 53 wt% and a simultaneous increase in ultimate stress and strain by ~3.5× and ~4.5×, respectively, for 95%/5% EA/DMA, relative to 100% DMA. Fundamental salt transport properties relevant to water purification, including permeability, solubility, and diffusivity, are measured and systematically compared with conventional membrane materials to inform the development of DNHs for membrane applications. The ability to simultaneously reduce water content and increase mechanical integrity highlights the potential of DNHs as a synthetic platform for future membrane applications.     

Structural design of stimuli‐responsive bioconjugated hydrogels that respond to a target antigen

Stimuli‐responsive bioconjugated hydrogels that can respond to a target antigen (antigen‐responsive hydrogels) were prepared by introducing antigen‐antibody bindings as reversible crosslinks into the gel networks. The preparation conditions of the antigen‐responsive hydrogels and the mechanism of the antigen‐responsive behavior were investigated, focusing on bioconjugated hydrogel structures. This article also focuses on the effect of semi‐interpenetrating polymer network (semi‐IPN) structures on the antigen‐responsive swelling/shrinking behavior of bioconjugated hydrogels with antigen‐antibody bindings. The preparation conditions and the network structures of the bioconjugated hydrogels are discussed in relation to designing antigen‐responsive hydrogels. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 2144–2157, 2009     

Substrate effect on the formation of hydrogels with heterogeneous network structure

It was found that when an aqueous solution of vinyl monomers is polymerized on a hydrophobic substrate, obvious heterogeneity occurs in the region of the interface. This substrate effect was observed on polytetrafluroethylene (Teflon), polypropylene (PP), polyethylene (PE), polystyrene (PS), and polyvinylchloride (PVC), but not on hydrophilic substrates. Compared with synthesis on hydrophilic surfaces, the surfaces of hydrogels synthesized on a hydrophobic substrate exhibit a larger degree of swelling, a lower surface coefficient of friction and elastic modulus, weaker interfacial adhesion, and reduced interaction with biological cells. This substrate effect has been observed for many types of aqueous monomer solutions. It was found that the above properties are related to the loosely cross-linked architecture, containing some graft-like polymer chains, that is formed on the gel surface when the gel is prepared on a hydrophobic substrate. To understand the mechanism of the substrate effect, two novel optical methods, electric speckle pattern interferometry (ESPI) and real-time laser sheet refraction (RT-LSR), were developed. It was found that oxygen trapped in the composite interface between the monomer solution and rough hydrophobic substrates played an important role in the substrate effect.     

Effect of polymer entanglement on the toughening of double network hydrogels

The mechanical strength of double network (DN) gels consisting of highly cross-linked poly(2-acrylamido-2-methylpropanesulfonic acid) (PAMPS) as the first component and linear polyacrylamide (PAAm) as the second component has been investigated by varying the molecular weight of the second polymer PAAm, M(w). The experimental results reveal that, for toughening of the DN gels, (1) M(w) is one of the dominant parameters; (2) there is a critical value of M(w) = 10(6) for a remarkable enhancement; (3) the fracture energy of DN gels with a M(w) larger than 10(6) reaches a value as high as 10(3) J/m(2). By plotting the strength of DN gels (fracture stress sigma and fracture energy G) against a characteristic parameter of c[eta], where c is the average concentration of PAAm in the DN gels and [eta] is the intrinsic viscosity of PAAm, it is found that the dramatic increase in the mechanical strength of the DN gels occurs above the region where linear PAAm chains are entangled with each other. Thus, we conclude that the entanglement between the second component PAAm plays an important role of the toughening mechanism of DN gels. This result supports the heterogeneous model, which predicts the presence of "voids" of the first network PAMPS with a size much larger than the radius of the second polymer PAAm.     

Hydrophilic silicone hydrogels with interpenetrating network structure for extended delivery of ophthalmic drugs

In the current work, hydrophilic silicone hydrogels were prepared for extended drug delivery applications. The preparation method was based on sequential interpenetrating network synthesis. A hydrophilic network was prepared by radical copolymerization of hydrophilic monomers 2‐hydroxyethyl methacrylate and poly(ethylene glycol) diacrylate. A hydrophobic silicone network was obtained by crosslinking polymerization of bifunctional methacrylated polydimethylsiloxanes macromonomer. The morphology of the silicone hydrogels was characterized by transmission electron microscopy. The result showed that the silicone hydrogels exhibited heterogeneous morphology. The properties of the silicone hydrogels such as equilibrium swelling ratio (ESR), mechanical property, oxygen permeability, contact angle, and protein repelling ability were investigated. Finally, the silicone hydrogels were loaded with timolol by pre‐soaking in drug solution to evaluate drug‐loading capacity and in vitro release behavior. The results showed that mechanical strength and oxygen permeability increased, and the ESR decreased with the increase of silicone component in the silicone hydrogels. The result of the contact angle measurement indicated that the silicone hydrogels possessed hydrophilic surfaces. The drug loading and in vitro releases were dependent on the composition of hydrophilic/hydrophobic phase of silicone hydrogels. Copyright © 2011 John Wiley & Sons, Ltd.     

Morphology,toughness mechanism,and thermal properties of hyperbranched epoxy modified diglycidyl ether of bisphenol A (DGEBA) interpenetrating polymer networks

New hyperbranched poly(trimellitic anhydride‐triethylene glycol) ester epoxy (HTTE) is synthesized and used to toughen diglycidyl ether of bisphenol A (DGEBA) 4,4′‐diaminodiphenylmethane (DDM) resin system. The effects of content and generation number of HTTE on the performance of the cured systems are studied in detail. The impact strength is improved 2–7 times for HTTE/DGEBA blends compared with that of the unmodified system. Scanning electron microscopy (SEM) of fracture surface shows cavitations at center and fibrous yielding phenomenon at edge which indicated that the particle cavitations, shear yield deformation, and in situ toughness mechanism are the main toughening mechanisms. The dynamic mechanical thermal analyzer (DMA) analyses suggest that phase separation occurred as interpenetrating polymer networks (IPNs) for the HTTE/DGEBA amine systems. The IPN maintains transparency and shows higher modulus than the neat epoxy. The glass transition temperature (T_g) decreases to some extent compared with the neat epoxy. The T_g increases with increase in the generation number from first to third of HTTE and the concentrations of hard segment. The HTTE leads to a small decrease in thermal stability with the increasing content from TGA analysis. The thermal stability increases with increase in the generation number from first to third. Moreover, HTTE promotes char formation in the HTTE/DGEBA blends. The increase in thermal properties from first to third generation number is attributed to the increase in the molar mass and intramolecular hydrogen bridges, the increasing interaction of the HTTE/DGEBA IPNs, and the increasing crosslinking density due to the availability of a greater number of end hydroxyl and end epoxide functions. Copyright © 2008 John Wiley & Sons, Ltd.     

Strikingly improved toughness of nonpolar rubber by incorporating sacrificial network at small fraction

It poses a huge challenge to create nonpolar rubber with high fracture toughness. In the present letter, inspired by the concept of sacrificial bonding associated with many biological materials, we propose that a small fraction of additional sacrificial network can strikingly improve the fracture toughness of nonpolar rubbers. As a proof of concept, we created the additional “fragile” epoxidized natural rubber (ENR) network in commercially available SBR rubber in a facile process. With addition of only 10 phr ENR, the SBR/ENR double network (DN) exhibits a fracture energy nearly fourfold higher than that for the neat SBR. The formation of DN formation and the correlation between the high toughness and presence of the second brittle network have been fully discussed. This is the first time sacrificial networks are created in diene‐based rubber towards high toughness elastomers in a facile and efficient way. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 781–786     

Dual temperature‐ and pH‐sensitive hydrogels from interpenetrating networks and copolymerization of N‐isopropylacrylamide and sodium acrylate

Hydrogels responsive to both temperature and pH have been synthesized in the forms of sequential interpenetrating networks (IPNs) of N‐isopropylacrylamide (NIPAAm) and sodium acrylate (SA) and compared with the crosslinked random copolymers of N‐isopropylacrylamide and SA. Whereas the stimuli‐sensitive behaviors of copolymer hydrogels were strongly dependent on the ionic SA contents, the IPN hydrogels exhibited independent swelling and thermal behaviors of each network component. The sequences and media in the synthesis of IPNs influenced the swelling capacities of the IPNs, but not the temperature or pH ranges at which the swelling changes occurred. In IPNs, a more expanded primary gel network during the synthesis of the secondary network contributed to the better swelling of the final IPNs. Both the swelling and thermal behaviors of the IPNs suggest that poly(N‐isopropylacrylamide) and poly(sodium acrylate) are phase separated regardless of their synthesis conditions. The presence of the poly(sodium acrylate) network did not influence the temperature or the extent of phase transition of the poly(N‐isopropylacrylamide) network in the IPNs, but did improve the thermal stability of the IPNs. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3293–3301, 2004     

Electric field sensitivity of conducting hydrogels with interpenetrating polymer network structure

In this article, we reported the synthesis, structure and electric field sensitivity of polyacrylate/polyaniline (PAA/PANI) and poly(2-acrylamido-2-methyl propylsulfonic acid-acrylic acid)/polyaniline [P(AMPS-AA)/PANI] conducting hydrogels with an interpenetrating polymer network (IPN) structure. Scanning electron microscope showed that the conducting hydrogels presented porous structures consisting of PANI nanofibers. The results of Fourier-transform infrared and X-ray diffraction revealed that the PANI was in its conductive emeraldine state and partial crystallization. The unique morphology and molecular structure of the conducting hydrogels were expected to show unusual electric field responses. The conducting hydrogels were subjected to an electric field in NaCl solution for bending behaviors. It was demonstrated that the electric field response was improved by increasing aniline dosage, applied voltage and concentration of aqueous NaCl solution. The bending mechanism was attributed to polyelectrolyte hydrogel matrix and emeraldine PANI nanofibers.     

Correlation between the fractal dimension of fracture surfaces and fracture toughness for ductile polymer materials

A microcrack-shear band chain model for the fracture of ductile materials is proposed. The fractal dimension (D) of the fracture surfaces is derived and correlated with the fracture toughness (K_Ic) of ductile materials. The fractal dimension of the fracture surface is predicted to have an inverse trend with the fracture toughness. The theoretical results are consistent with the experimental results of some polymers and metals. © 1994 John Wiley & Sons, Inc.     

Effect of chemical structure on the properties of some hydrogels prepared by using gamma radiation polymerization

Several hydrogels were prepared using radiolytic polymerization of aqueous solutions of acrylamide or acrylamide containing appropriate comonomer such as acrylic acid, maleic acid, itaconic acid, and maleic anhydride. The hydrogels have been prepared at an irradiation dose of 30 kGy. The effects of the chemical structure of the monomer(s) and crosslinking agents on the yield of homopolymer(s) or copolymers have been studied. These crosslinking agents include N, N′‐methylene dimethacrylate (MDA) and N, N′‐methylene bisallyamide (MBA). The hydrogels obtained were characterized using swelling technique, thermal and spectroscopic analysis. The results obtained showed that the prepared samples are able to reject sodium ions and are not able to recover the Basic Blue Dye from their aqueous solution. © 2005 John Wiley & Sons, Ltd.     

Elucidation of the chemical and morphological structure of double-network (DN) hydrogels by high-resolution magic angle spinning (HRMAS) NMR spectroscopy

(1)H HRMAS NMR spectroscopy is applied to gain insight into the chemical and morphological structure of double-network (DN) hydrogels, prepared from poly(2-acrylamido-2-methyl-1-propanesulfonic acid) (PAMPS) and poly(acrylamide) (PAAm). The method enables one to obtain detailed information at the molecular level about the formation of covalent bonds between the two polymer networks through non-reacted double bonds of the cross-linker N,N'-methylene bis(acrylamide) (MBAA). Evidence to the existence of strong hydrogen-bond interactions based on the N-H group of the PAMPS as a hydrogen-bond donor and the C=O group of the PAAm as a hydrogen-bond acceptor is also provided. These findings clarify the origin of the toughening mechanism and the exceptionally strong mechanical properties of DN gels, further supported by microhardness data.     

Preparation and characterization of biodegradable gelatin-PAAm-based IPN hydrogels for controlled release of maleic acid to improve the solubility of phosphate fertilizers

In this study, interpenetrating polymer network (IPN) hydrogel systems including maleic acid (MA) were constituted to improve the solubility of phosphate fertilizers. A series of full and semi-IPN hydrogels were prepared from various gelatin/polyacrylamide mixtures by using two different cross-linkers. The effects of polymer composition on the morphological structures and swelling behaviors of the hydrogels were investigated. The swelling values of all hydrogels were found to be in between 435% and 830%. MA release from load0ed hydrogels was followed and it was determined that MA-loaded hydrogels efficiently decreased pH and improved the solubility of Ca₃(PO₄)₂ in releasing medium.     

Relationship between fracture toughness and domain size of liquid‐crystalline epoxy resins having polydomain structure

A liquid‐crystalline (LC) epoxy resin was cured at different temperatures and some types of curing systems having different phase structures (isotropic or polydomain, which have a microscopically ordered LC network structure) were obtained. The diameters of each domain in the polydomain system changed from the small to the larger size. The diameters of the LC domains were evaluated using a polarized optical microscope and the polarized microscopy FTIR mapping method. These systems were used to investigate the relationship between the network arrangement and mechanical properties. The fracture toughness of the cured systems was related to the enlargement of the ordered area in the network structures. With the toughness improvement, the meandering cracks were observed at the fracture surfaces. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 156–165, 2009     

Thermodynamics of water sorption in acrylic homonetworks and IPNs

The equilibrium thermodynamic properties of poly(hydroxyethyl acrylate) and poly(ethyl acrylate)-i-poly(hydroxyethyl acrylate) hydrogels are investigated starting from the water sorption isotherms of the systems. Partial enthalpy and entropy of the sorbed water in the gel differ markedly from the values of pure water at the lowest water contents, and tend to those of liquid water as saturation is approached. The residual mixing free energy is calculated, as a means of assessing the intensity of the water-polymer interaction. Its small positive magnitude shows that water-polymer hydrogen bonds are labile compared to water-water and polymer-polymer hydrogen bonds, and thus the stability of the gel state is still mainly due to the combinatorial entropic contribution to the mixing free energy. An equation correctly describing the sorption isotherms, when combined with the thermodynamic equations, can deliver the true water-polymer interaction parameter and its dependence on the polymer volume fraction in the gel.