Modeling flow induced crystallization in film casting of polypropylene

Data from iPP film casting experiments served as a basis to model the effect of flow on polymer crystallization kinetics. These data describe the temperature, width, velocity and crystallinity distributions along the drawing direction under conditions permitting crystallization along the draw length. In order to model the effect of flow on crystallization kinetics, a modification of a previously defined quiescent kinetic model was adopted. This modification consisted in using a higher melting temperature than in the original quiescent model. The reason for the modification was to account for an increase of crystallization temperature due to entropy decrease of the flowing melt. This entropy decrease was calculated from the molecular orientation on the basis of rubber elasticity theory applied to the entangled and elongated melt. The evolution of molecular orientation (elongation) during the film casting experiments was calculated using a non-linear dumbbell model which considers the relaxation time, obtained from normal stress difference and viscosity functions, to be a function of the deformation rate. The comparison between experimental distributions and model based crystallinity distributions was satisfactory

Physiologically Based Pharmacokinetics: A Simple, All Purpose Model

To predict the drug hemeatic levels after administration is a goal of great interest in the design of novel pharmaceutical systems and in therapies management. The most reliable approach in pharmacokinetic modeling consists in analyzing the physiology of the living beings and in describing tissues and organs as different biochemical reactors. These models have been identified as physiologically based pharmacokinetic models (PBPK). They can be very detailed in the description, but, in this case, they also claim for the knowledge of an high number of parameters which are difficult to be determined by experiments. In this work, a review of the most complete PBPK models proposed in literature was performed, and a novel PBPK model was developed and validated by comparison with in vivo data available in the literature. The appeals of the novel model are its simplicity and the limited number of parameters required. Last but not least, it was proved able to predict the hemeatic drug levels after different kinds of administrations (intravenous injection, oral assumption of delayed release tablets)

SHEAR-INDUCED NUCLEATION AND GROWTH IN ISOTACTIC POLYPROPYLENE

The possibility of controlling the final morphology, and thus the resulting mechanical and functional properties, of semicrystalline polymers based on the study of polymer crystallization stimulated by flow is highly intriguing. Recent advances in experimental techniques that allow in situ measurements of material morphology under deformation have escalated research in this subject area. However, despite of the huge efforts spent, the description of the evolution of morphology under shear conditions is still challenging and even the basic principles of the phenomenon are not well understood yet. In this work, experiments of nucleation density and growth rate of spherulites were carried out under continuous shear in a range of temperature (138-144 degrees C) and shear rate (0-0.30 s(-1)) which, although narrow in absolute, can be considered quite wide taking into account the experimental difficulties presented by this kind of tests. Collected data were analyzed with the aim of determining scaling rules which can describe the effect of flow on crystallization kinetics. It was found that a proportionality exists between nucleation rate and spherulitic growth rate under flow, suggesting that whatever the controlling mechanism for the enhancement of nucleation rate is, it has a similar effect also on growth rate. The effect of flow on nucleation and growth rates was attributed to the increase of the melting temperature due to flow. In turn, the melting temperature estimated for the tests conducted in the whole range of temperatures and shear rates was found to be dependent on the Weissenberg number

Modeling of morphology evolution in the injection molding process of thermoplastic polymers

A thorough analysis of the effect of operative conditions of injection molding process oil the morphology distribution inside the obtained moldings is performed, with particular reference to semi-crystal line polymers. The paper is divided into two parts: in the first part, the state of the art on the subject is outlined and discussed; in the second part, an example of the characterization required for a satisfactorily understanding and description of the phenomena is presented, starting from material characterization, passing through the monitoring of the process cycle and arriving to a deep analysis of morphology distribution inside the moldings. In particular, fully characterized injection molding tests are presented using an isotactic polypropylene, previously carefully characterized as far as most of properties of interest. The effects of both injection flow rate and mold temperature are analyzed. The resulting moldings morphology (in terms of distribution of crystallinity degree, molecular orientation and crystals structure and dimensions) are analyzed by adopting different experimental techniques (optical, electronic and atomic force microscopy, IR and WAXS analysis).Final morphological characteristics of the samples are compared with the predictions of a simulation code developed at University of Salerno for the simulation of the injection molding process

Scanning Nanocalorimetry at High Cooling Rate of Isotactic Polypropylene

A wide set of cooling scans and subsequent melting behavior of isotactic polypropylene (i-PP) were investigated using differential scanning calorimetry and nanocalorimetry at very high cooling rate. The latter technique offers, indeed, the distinctive possibility to perform heat capacity measurements at rates of more than 1000 K/s, both in cooling and in heating, to characterize the crystallization. When the i-PP sample was solidified with cooling rate larger than 160 K/s, a novel enthalpic process was observed that was related to the mesomorphic phase formation. Furthermore, at cooling rates higher than 1000 K/s, the i-PP sample did not crystallize neither in the α nor in the mesomorphic form. The subsequent heating scan starting from −15 °C showed an exothermic event, between 0 and 30 °C, ascribed to the mesophase cold crystallization

Analysis and modeling of swelling and erosion behavior for pure HPMC tablet

This work is focused on the transport phenomena which take place during immersion in water of pure hydroxypropylmethylcellulose tablets. The water uptake, the swelling and the erosion during immersion were investigated in drug-free systems, as a preliminary task before to undertake the study of drug-loaded ones. The tablets, obtained by powder compression, were confined between glass slabs to allow water uptake only by lateral surface and then immersed in distilled water at 37 °C, with simultaneous video-recording. By image analysis the normalized light intensity profiles were obtained and taken as a measure of the water mass fraction. The time evolutions of the total tablet mass, of the water mass and of the erosion radius were measured, too. Thus a novel method to measure polymer and water masses during hydration was pointed out. Then, a model consisting in the transient mass balance, accounting for water diffusion, diffusivity change due to hydration, swelling and erosion, was found able to reproduce all experimental data. Even if the model was already used in literature, the novelty of our approach is to compare model predictions with a complete set of experimental data, confirming that the main phenomena were correctly identified and described

Microencapsulation effectiveness of small active molecules in biopolymer by ultrasonic atomization technique

A method to produce biopolymeric (alginate) microparticles by ultrasonic assisted atomization, previously developed, has been applied to the production of microparticles loaded with a small active molecule (theophylline). Fine loaded alginate droplets have been cross-linked with divalent ions to produce microparticles. Once produced, the particles have been separated by centrifugation or filtration and then they have been dried. Drug release has been evaluated by dissolution tests, dissolving the dried particles in acidic solution at pH 1 for a given time and then at pH 7 to simulate the stomach and intestinal environment, respectively. The encapsulation efficiency and the drug loading have been investigated and the operating conditions have been changed to clarify the role of the transport phenomena on the overall process. To increase the drug loading, shorter separation time and better network’s structure were identified as the key operating parameters to allow the process to gain interest from a practical point of view

Intensification of biopolymeric microparticles production by ultrasonic assisted atomization

In this work ultrasonic atomization process is applied to produce biopolymer microparticles with potential applications in pharmaceutical and nutraceutical fields. Natural polymer (alginate)/water solution is atomized by ultrasonic assisted process and the droplets spray is reticulated using a solution of copper sulfate, where the Cu2+ ions cause the formation of a network structure (hard porous gel). Several operating parameters (solution concentration, flow rate, atomization power) are changed to study their effects on the produced microparticles. Literature correlations able to predict the features of the droplets as functions of process parameters are optimized using a statistical approach. Furthermore, the energy requirement for the drops production is compared with the energy required by traditional techniques to evaluate the intensification effect of the ultrasonic on the atomization process. doi:10.1016/j.cep.2009.08.00

An engineering approach to biomedical sciences: advanced testing methods and pharmacokinetic modeling

In this paper, the philosophy of a research in pharmacology field, driven by an engineering approach, was described along with some case histories and examples. The improvement in the testing methods for pharmaceutical systems (in-vitro techniques), as well as the proposal and the testing of mathematical models to describe the pharmacokinetics (in-silico techniques) are reported with the aim of pointing out methodologies and tools able to reduce the need of expensive and ethical problematic in-vivo measurements

Designing in-vitro systems to simulate the in-vivo permeability of drugs

In this work an engineering approach, consisting in an experimental procedure and a model to derive the data, was presented and applied to improve the testing methods of pharmaceuticals. The permeability of several active molecules have been evaluated across a synthetic membrane. The permeability of these drugs measured through the artificial membrane were successfully correlated to their in-vivo permeability. The relationship with in-vivo permeability was derived, and then a rule to design systems to simulate the intestinal absorption was proposed to reduce the need for expensive and ethical problematic in-vivo measurement