Chun-Rui Han

Studies on the properties and formation mechanism of flexible nanocomposite hydrogels from cellulose nanocrystals and poly(acrylic acid)

A novel series of nanocomposite hydrogels based on cellulose nanocrystals (CNCs) and poly(acrylic acid) (PAA) have been synthesized by in situ free radical polymerization within an aqueous medium. Rheological measurements were applied to monitor the gelation process and results indicated that the gelation took place as monomers (acrylic acid, AA) grafted from the CNC surface and PAA chains entangled to produce flexible CNC–PAA gels. By tailoring the concentration of CNC (CCNC) over a wide range of 0.02–1 wt%, two critical CCNC, C* and C**, were found which corresponded to polymer chains that occurred in overlapping entanglements and promoted conformational rearrangements on the basis of earlier gel precursors, respectively. The formation mechanism of CNC based nanocomposite hydrogels, in which the nanoparticles transformed from the isolated state below C* to the spatially continuous percolation structure above C**, was proposed. The CNC–PAA gels exhibited excellent, composition-dependent mechanical properties, such as a large elongation ratio (>1100%) and high tensile strength (>350 kPa). Transmission electron microscopy (TEM) revealed that the CNCs were surrounded by grafted chains and formed inter-connected network structures, where the CNCs acted as multifunctional cross-links with an average effective functionality of 75. The mechanical measurements indicated that the increase of CCNC led to an increase in the hydrogels viscous characteristics and contributed to the energy dissipating mechanism, which was responsible for CNC–PAA gels excellent flexibility. The swelling and partial dissolution behaviors of the hydrogels were examined, focusing on the effect of CCNC on the gels characteristic partial deswelling and gel-to-sol transition. Some new chain entanglements were formed under concentrated conditions after drying treatment above the glass transition temperature (Tg) which was verified by observation of the greater tensile strength and modulus. All the results corresponded to the self-consistent network structure model for CNC–PAA gels.

Synthesis and characterization of mechanically flexible and tough cellulose nanocrystals–polyacrylamide nanocomposite hydrogels

The unique combinations of hard and soft components with core/shell structures were proposed to synthesize high strength nanocomposite hydrogels. The elastomeric hydrogels containing rod-like cellulose nanocrystals (CNCs) core and polyacrylamide shell were made from aqueous solutions via free radical polymerization in the absence of chemical cross-links. The obtained hydrogels possessed greater tensile strength and elongation ratio when compared with chemically cross-linked counterparts. Oscillatory shear experiments indicated that CNCs interacted with polymer matrix via both chemical and physical interactions and contributed to the rubbery elasticity of the hydrogels. The nanocomposite hydrogels were more viscous than the chemical hydrogels, suggesting the addition of CNC led to the increase of energy dissipating and viscoelastic properties. The network structure model was proposed and it suggested that the high extensibilities and fracture stresses were related to the well-defined network structures with low cross-linking density and lack of noncovalent interactions among polymer chains, which may promote the rearrangements of network structure at high deformations.

Synthetic and viscoelastic behaviors of silica nanoparticle reinforced poly(acrylamide) core–shell nanocomposite hydrogels

The poor mechanical strength of traditional synthesized hydrogels remains the greatest challenge to their performance as tissue engineering materials. Unique combinations of hard and soft components were used to design and synthesize elastomeric nanocomposite hydrogels with a core–shell microstructure. The nanocomposite hydrogels consisting of multifunctional cross-links of silica nanoparticles (SNPs) as the nucleus and poly(acrylamide) (PAM) as the shell were prepared by mixing both components in solution, and photo-crosslinking by UV radiation. Transmission electron microscopy (TEM) observations confirmed the existence of a core–shell morphology, and dynamic light scatting (DLS) measurements were applied to monitor the particle conformation changes near the critical gelation condition. The results indicated that the concentration of the core significantly affected the mechanical properties of the hydrogel and the unique three-stage arrangement process exhibited an average effective functionality around 28. The molecular weight of grafted polymer chains was monitored and it was found that the grafted PAM chain had a high value of 2.46 × 105 g mol−1, and it remained almost constant when the SNP concentration (CSNP) exceeded the critical value. The mechanical behavior of the nanocomposite hydrogels was studied with elongation under large strains and it was found that the hydrogels exhibited excellent tensile properties, including a modulus 9–38 kPa, a fracture strain 700–1000%, and a fracture stress 80–250 kPa, depending on the SNP concentrations. Stress relaxation experiments indicated that the nanocomposite hydrogels were more viscous than comparable chemical gels and were more efficient at the energy dissipation process, which is related to the orientation of SNPs and relaxation of the PAM chains. Further development of the synthetic platform would potentially lead to valuable knowledge for the design of high performance hydrogels in biomedical and pharmaceutical applications.

Tough nanocomposite hydrogels from cellulose nanocrystals/poly(acrylamide) clusters: influence of the charge density, aspect ratio and surface coating with PEG

Cellulose-derived materials are usually characterized by sophisticated structures, leading to unique and multiple functions, which have been a source of inspiration for the fabrication of a wide variety of nanocomposites. Cellulose nanocrystals/poly(acrylamide) (CNCs/PAM) nanocomposite hydrogels were synthesized via in situ polymerization in the CNC suspension. The cellulose from pulp fiber under different sulfuric acid hydrolysis conditions, examined by conductometric titration and transmission electron microscopy, was applied to study how the effects of the surface charge and aspect ratio affect CNCs’ mechanical reinforcement in nanocomposites. The results indicated that the higher surface charge concentration resulted in better dispersibility in aqueous suspension, leading to a more efficient energy dissipation process. The CNC reinforcement behavior followed the percolation model where the greater aspect ratio of CNC contributed to higher mechanical properties. The preferential adsorption of poly(ethylene glycol) (PEG) on the CNC surface was characterized by zeta potential measurements where the fracture strength and fracture elongation of nanocomposites decreased with increasing PEG concentration. The adsorption of PEG on the CNC surface occupied the active sites for polymer chain propagation, which hindered the PAM cross-linking effect on the CNC surface and decreased the cross-linking density of the network.

Metal Ion Mediated Cellulose Nanofibrils Transient Network in Covalently Cross-linked Hydrogels: Mechanistic Insight into Morphology and Dynamics

Utilization of reversible interactions as sacrificial bonds in biopolymers is critical for the integral synthesis of mechanically superior biological materials. In this work, cellulose nanofibrils (CNFs) reinforced covalent polyacrylamide (PAAm) composite hydrogels are immersed into multivalent cation (Ca2+, Zn2+, Al3+, and Ce3+) aqueous solution to form ionic association among CNFs, leading to the ionic-covalent cross-linked hydrogels. The cations promote the formation of porous networks of nanofibrils by screening the repulsive negative charges on CNF surface and dominate the mechanical properties and self-recovery efficiency of the hydrogels, resulting in mechanically reinforced ionic hydrogels with stiff (Youngs modulus 257 kPa) and tough properties (fracture toughness 386 kJ/m3). The in situ Raman spectroscopy during stretching corroborates the stress transfer medium of CNF, and the microscopic morphologies of stable crack propagation validates that the multiple toughening mechanisms occur in a balanced energy dissipation manner, enabling synergistic combination of stiffness and toughness. Moreover, the depth-sensing instrumentation by indentation test also demonstrates that the CNF ionic coordination contributes simultaneous improvement in hardness and elasticity by as much as 600% compared to those pristine gels. This work demonstrates a facile way to transfer nanoscale building blocks to bulk elastomers with tunable dynamic properties and may provide a new prospect for the rational design of CNF reinforced hydrogels for applications where high-bearing capability is needed.