Effect of polymer and ion concentration on mechanical and drug release behavior of gellan hydrogels using factorial design

Developing optimized hydrogel products requires an in-depth understanding of the mechanisms that drive hydrogel tunability. Here, we performed a full 4 × 4 factorial design study investigating the impact of gellan, a naturally derived polysaccharide (1%, 2%, 3%, or 4% w/v) and CaCl₂ concentration (1, 3, 7, or 10 mM) on the viscoelastic, swelling, and drug release behavior of gellan hydrogels containing a model drug, vancomycin. These concentrations were chosen to specifically provide insight into gellan hydrogel behavior for formulations utilizing polymer and salt concentrations expanding beyond those commonly reported by previous studies exploring gellan. With increasing gellan and CaCl₂ concentration, the hydrogel storage moduli (0.1–100 kPa) followed a power-law relationship and on average these hydrogels had higher liquid absorption capability and greater total drug release over 6 days. We suggest that the effects of gellan and CaCl₂ concentration and their interactions on hydrogel properties can be explained by various phenomena that lead to increased swelling and increased resistance to network expansion.     

Time‐dependent finite element simulations of a shear‐thinning viscoelastic fluid with application to blood flow

A new finite element method is developed to simulate time‐dependent viscoelastic shear‐thinning flows characterized by the generalized Oldroyd‐B model. The focus of the algorithm is improved stability through a free‐energy dissipative scheme by using low‐order piecewise‐constant finite element approximations for stress. The algorithm is further modified by incorporating a pressure‐projection method, a DG‐upwinding scheme, a symmetric interior penalty DG method to solve the elliptic pressure‐update equation and a geometric multigrid preconditioner. The improved stability and cost to accuracy is compared when using higher order discontinuous bilinear approximation, where in addition, we consider the influence of a slope limiter for these elements. The algorithm is applied to the 2D start‐up‐driven cavity problem, and the stability of the free energy is illustrated and compared between element choices. An application of the model to modelling blood in small arterioles and channels is considered by simulating pulsatile blood flow through a stenotic arteriole. The individual influences of viscoelasticity and shear‐thinning within the generalized Oldroyd‐B model are investigated by comparing results to the Newtonian, generalized Newtonian and Oldroyd‐B models. Copyright © 2014 John Wiley & Sons, Ltd.     

Korn inequality for a thin rod with rounded ends

We consider an elastic rod with rounded ends and diameter proportional to a small parameter h > 0. The roundness of the ends is described by an exponent m ∈ (0,1). We derive for the rod an asymptotically sharp Korn inequality with a special weighted anisotropic norm. Weight factors with m‐dependent powers of h appear both in the anisotropic norm and the Korn inequality itself, and we discover three critical values m = 1 ∕ 4, m = 1 ∕ 2 and m = 3 ∕ 4 at which these exponents are crucially changed. Copyright © 2014 John Wiley & Sons, Ltd.     

Physical gelation and macromolecular mobility of sustainable polylactide during isothermal crystallization

The mobility of free macromolecular chains is of importance to the growth of crystallites in a crystallizing sustainable polylactide (PLA), which was scarcely explored by rheology. In this study, the time‐resolved rheological properties for PLA during isothermal crystallization were investigated first, showing that the storage and loss modulus experience 2–3 decades of increase. The Avrami analysis reveals that the crystallization kinetics in rheological measurement protocol follows the homogeneous nucleation and three‐dimensional growth mechanism. The linear viscoelastic properties in the vicinity of physical gelation point were then studied at the inverse quenching temperature of 165 °C. The results show that physical gelation occurs when the critical absolute crystallinity reaches 13% as determined by the rheological method. Relaxation time spectra reveal that the interfacial relaxation is greatly retarded but the presence of growing spherulites possesses little constraint on the mobility of free chains in matrix especially before physical gelation point. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1235–1244     

Successive stepwise evolution of host layer‐stacking framework upon the intercalation of mobile vapor guests within side‐chain layers

For the ordered phases of hairy‐rod semiconductive poly(2,5‐bis(3‐tetradecylthiophene‐2‐yl)thieno[3,2‐b]thiophene) (PBTTT) sandwiched in between crystalline platelets of hexamethylbenzene, the successive stepwise evolution of layer‐stacking framework upon guest intercalation has been studied in this research. The direct consequence of the guest intercalation into side‐chain layers is evaluated to cause the lateral shift of thiophene backbones along π–π stacking, resulting in stepwise shift of ultraviolet absorption wavelength. The thermal motions of vapor guests within disordering side‐chain layers subsequently cause progressive expansion of host stacking framework. With the increase in side‐chain length, thicker layers of disordering side chains in liquid crystals (LCs) accommodate additional vapor guests and larger amplitudes of thermal motions of guests, hence promoting the level of reversible d‐spacing change. The mixing between mobile vapor guests and aliphatic side chains is clarified as the mechanism of guest intercalation, which rationalizes successive guest intercalation during heating and the contribution of disordering side‐chain layers. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1448–1456     

Recovery performance and characteristics in shape memory effects of aliphatic polyether urethane

The analysis on the recovery performance and characteristics in shape memory effects is helpful for the optimal design and engineering applications of shape memory polymers and their composites. To investigate the relationships among recovery performance, material parameters, and loading conditions, by taking aliphatic polyether urethane as an example, the researchers simulate the shape memory behaviors numerically using a three‐dimensional viscoelastic model. The material parameters for this model are taken from stress relaxation tests, rather than dynamic mechanical analysis tests. Both the unconstrained and the constrained recovery behaviors during strain‐controlled shape memory processes are analyzed. The results reveal that the unconstrained recovery occurs at the same temperature regardless of the applied strain values. Another interesting result is that the shape recovery temperature in unconstrained recovery situations increases and the maximum recovery stress under constrained recovery conditions decreases with the increase of heating rates. Copyright © 2013 John Wiley & Sons, Ltd.     

A critical analysis of the effect of crosslinking on the linear viscoelastic behavior of styrene–butadiene rubber and other elastomers

The linear viscoelastic behavior in dynamic shear and tensile creep at temperatures from −30 to 70 °C is measured for an styrene–butadiene rubber (SBR) elastomer cured with dicumyl peroxide to crosslinking densities between 0 and 23.5 × 10⁻⁵ mol/cm³. The G′, G″, and tan δ isotherms are analyzed by time–temperature superposition (TTS), where the tan δ master curves are consistent with those of Mancke and Ferry. However, to achieve the TTS in the lightly crosslinked SBR systems, an anomalous vertical shift is required in the narrow temperature region from 10 to 30 °C. The vertical shift factor in this temperature region is not the standard from rubber elasticity. No anomalous behavior is detected in the equilibrium modulus, which is a linear function of temperature in accordance with the classical theory of rubber elasticity. In contrast to SBR, standard vertical shifts are required to effect TTS for uncrosslinked polybutadiene and an ethylene propylene diene monomer elastomer. © 2013 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013     

The initial value problem for creeping flow of the upper convected Maxwell fluid at high Weissenberg number

We consider the equations for time dependent creeping flow of an upper convected Maxwell fluid. For finite Weissenberg number, these equations can be reformulated as a coupled system of a hyperbolic equation for the stresses and an elliptic equation for the velocity. In the high Weissenberg number limit, however, the elliptic equation becomes degenerate. As a consequence, the initial value problem is no longer uniquely solvable if we just naively let the Weissenberg number go to infinity in the equations. In this paper, we make an a priori assumption on the stresses, which is motivated by the behavior in shear flow. We formulate a systematic perturbation procedure to solve the resulting initial value problem. Copyright © 2014 JohnWiley & Sons, Ltd.     

Long‐time behavior of a nonlinear viscoelastic beam equation with past history

This paper is concerned with the existence of a global attractor for the nonlinear viscoelastic beam equation with past history memory where g(u_t) is a damping like | u_t | ^ru_t and f(u) is a source term like | u | ^αu ? | u | ^βu, by considering 0 ≤ β < α and r > 0. Copyright © 2014 John Wiley & Sons, Ltd.