Properties of Mosquito Repellent-Plasticized Poly(lactic acid) Strands.

Poly(lactic acid) (PLA) is an attractive candidate for replacing petrochemical polymers because it is fully biodegradable. This study investigated the potential of PLA as a sustainable and environmentally friendly alternative material that can be developed into commercially viable wearable mosquito repellent devices with desirable characteristics. PLA strands containing DEET and IR3535 were prepared by twin screw extrusion compounding and simultaneously functioned as plasticizers for the polymer. The plasticizing effect was investigated by thermal and rheological studies. DSC studies showed that the addition of DEET and IR3535 into PLA strands reduced the glass transition temperature consistent with predictions of the Fox equation, thus proving their efficiency as plasticizers. The rheology of molten samples of neat PLA and PLA/repellents blends, evaluated at 200 °C, was consistent with shear-thinning pseudoplastic behaviour. Raman studies revealed a nonlinear concentration gradient for DEET in the PLA strand, indicating non-Fickian Type II transport controlling the desorption process. Release data obtained at 50 °C showed initial rapid release followed by a slower, near constant rate at longer times. The release rate data were fitted to a novel modification of the Peppas-Sahlin desorption model.

A Relatively Simple Look at the Rather Complex Crystallization Kinetics of PLLA.

This work demonstrates that, despite the existence of a significant number of works on PLA crystallization, there is still a relatively simple way, different from those already described, in which its complex kinetics can be observed. The X-ray diffraction (XRD) results presented here confirm that the PLLA under study crystallizes mostly in the α and α' forms. An interesting observation is that at any temperature in the studied range of the patterns, the X-ray reflections stabilize with a given shape and at a given angle, different for each temperature. That means that both α and α' forms coexist and are stable at the same temperatures so that the shape of each pattern results from both structures. However, the patterns obtained at each temperature are different because the predominance of one crystal form over the other depends on temperature. Thus, a two-component kinetic model is proposed to account for both crystal forms. The method involves the deconvolution of the exothermic DSC peaks using two logistic derivative functions. The existence of the rigid amorphous fraction (RAF) in addition to the two crystal forms increases the complexity of the whole crystallization process. However, the results presented here show that a two-component kinetic model can reproduce the overall crystallization process fairly well over a broad range of temperatures. The method used here for PLLA may be useful for describing the isothermal crystallization processes of other polymers.

Evaluation of the Curing of Adhesive Systems by Rheological and Thermal Testing.

The analysis of thermal processes associated to the curing of adhesives and the study of mechanical behavior once cured, provide key information to choose the best option for any specific application. The proposed methodology for the curing characterization, based on thermal analysis and rheology, is described through the comparison of three commercial adhesives. The experimental techniques used here are Thermogravimetric Analysis (TGA), Differential Scanning Calorimetry (DSC) and Rheology. TGA provides information about the thermal stability and filler content, DSC allows the evaluation of some thermal events associated to the cure reaction and to thermal changes of the cured material when subjected to temperature changes. Rheology complements the information of the thermal transformations from a mechanical point of view. Thus, the curing reaction can be tracked through the elastic modulus (mainly the storage modulus), the phase angle and the gap. In addition, it is also shown that although DSC is of no use to study the curing of moisture curable adhesives, it is a very convenient method to evaluate the low temperature glass transition of amorphous systems.

Dynamic rheological comparison of silicones for podiatry applications.

PURPOSE: This work shows an effective methodology to evaluate the dynamic viscoelastic behavior of silicones for application in podiatry. The aim is to characterize, compare their viscoelastic properties according to the dynamic stresses they can be presumably subjected when used in podiatry orthotic applications. These results provide a deeper insight which extends the previous creep-recovery results to the world of dynamic stresses developed in physical activity. In this context, it shoulod be taken into account that an orthoses can subjected to a set of static and dynamic shear and compressive forces. METHODS: Two different podiatric silicones, Blanda-blanda and Master, from Herbitas, are characterized by dynamic rheological methods. Three kinds of rheological tests are considered: shear stress sweep, compression frequency sweep and shear frequency sweep, all the three with simultaneous control of the static force at three different levels. The static force represents a static load like that produced by the weight of a human body on a shoe insole. In a practical sense, dynamic stresses are related to physical activity and are needed to evaluate the frequency effect on the viscoelastic behavior of the material. It is considered that the dynamic stresses can be applied in compression and shear since, in practice, the way the stresses are applied in real life depends on the orthoses geometry and its exact location with respect to the foot and shoe. The effects of static and dynamic loads are individualized and compared to each other through the relations between the elastic constants for isotropic materials. CONCLUSIONS: The overall proposed experimental methodology can provide very insightful information for better selection of materials in podiatry applications. This study focuses on the rheological characterization to choose the right silicone for each podiatric application, taking into account the dynamic viscoelastic requirements associated to the physical activity of user. Accordingly, one soft and one hard silicones of common use in podiatry were tested. Each of the two silicones exhibit not only different moduli values, but also, a different kind of dependence of the dynamic moduli with respect to the static load. In the case of the soft sample a linear trend is observed but in the case of of the hard one the dependence is of the power law type. Moreover, these samples exhibit very different Poisson's coefficient values for compression stresses lower than 20 kPa, and almost the same values for stresses above 40 kPa. That different dependence of the Poisson's ratio on the static load should also be taken into account for material selection in customized podiatry applications, where static and dynamic loads are strongly dependent on the individual weight and activity.