Processing-Structure-Property Relationships in Solid-State Shear Pulverization: Parametric Study of specific energy

Solid-state shear pulverization (SSSP) is a unique processing technique for mechanochemical modification of polymers, compatibilization of polymer blends, and exfoliation and dispersion of fillers in polymer nanocomposites. A systematic parametric study of the SSSP technique is conducted to elucidate the detailed mechanism of the process and establish the basis for a range of current and future operation scenarios. Using neat, single component polypropylene (PP) as the model material, we varied machine type, screw design, and feed rate to achieve a range of shear and compression applied to the material, which can be quantified through specific energy input (Ep). As a universal processing variable, Ep reflects the level of chain scission occurring in the material, which correlates well to the extent of the physical property changes of the processed PP. Additionally, we compared the operating cost estimates of SSSP and conventional twin screw extrusion to determine the practical viability of SSSP.

Morphology and properties of thermoplastic polyurethane nancomposites incorporating hydrophilic layered silicates

Hydrophilic layered silicate/polyurethane nanocomposites were prepared via twin screw extrusion and solvent casting. Good dispersion and delamination was achieved-regardless of processing route, illustrating that the need for optimised processing conditions diminishes when there is a strong driving for de for intercalation between the polymer and organosilicate. Evidence for altered polyurethane microphase morphology in the nanocomposites was provided by DMTA and DSC. WAXD results suggested that the appearance of an additional high temperature melting endotherm in some melt-compounded nanocomposites was not due to the formation of a second crystal polymorph, but rather due to more well-ordered hard microdomains. Solvent casting was found to be the preferred processing route due to the avoidance of polyurethane and surfactant degradation associated with melt processing. While tensile strength and elongation were not improved on organosilicate addition, large increases in stiffness were observed. At a 7 wt% organosilicate loading, a 3.2-fold increase in Young's modulus was achieved by solvent casting. The nanocomposites also displayed higher hysteresis and permanent set. (C) 2004 Elsevier Ltd. All rights reserved.

Développement et caractérisation de nouveaux nanocomposites polymères électriquement conductueurs pour plaques bipolaires de piles à combustible à membrane échangeuse de protons, PEMFC

Face à la diminution des ressources énergétiques et à l’augmentation de la pollution des énergies fossiles, de très nombreuses recherches sont actuellement menées pour produire de l’énergie propre et durable et pour réduire l’utilisation des sources d’énergies fossiles caractérisées par leur production intrinsèque des gaz à effet de serre. La pile à combustible à membrane échangeuse de protons (PEMFC) est une technologie qui prend de plus en plus d’ampleur pour produire l’énergie qui s’inscrit dans un contexte de développement durable. La PEMFC est un dispositif électrochimique qui fonctionne selon le principe inverse de l’électrolyse de l’eau. Elle convertit l’énergie de la réaction chimique entre l’hydrogène et l’oxygène (ou l’air) en puissance électrique, chaleur et eau; son seul rejet dans l’atmosphère est de la vapeur d’eau. Une pile de type PEMFC est constituée d’un empilement Électrode-Membrane-Électrode (EME) où la membrane consiste en un électrolyte polymère solide séparant les deux électrodes (l’anode et la cathode). Cet ensemble est intégré entre deux plaques bipolaires (BP) qui permettent de collecter le courant électrique et de distribuer les gaz grâce à des chemins de circulation gravés sur chacune de ses deux faces. La plupart des recherches focalisent sur la PEMFC afin d’améliorer ses performances électriques et sa durabilité et aussi de réduire son coût de production. Ces recherches portent sur le développement et la caractérisation des divers éléments de ce type de pile; y compris les éléments les plus coûteux et les plus massifs, tels que les plaques bipolaires. La conception de ces plaques doit tenir compte de plusieurs paramètres : elles doivent posséder une bonne perméabilité aux gaz et doivent combiner les propriétés de résistance mécanique, de stabilité chimique et thermique ainsi qu’une conductivité électrique élevée. Elles doivent aussi permettre d’évacuer adéquatement la chaleur générée dans le cœur de la cellule. Les plaques bipolaires métalliques sont pénalisées par leur faible résistance à la corrosion et celles en graphite sont fragiles et leur coût de fabrication est élevé (dû aux phases d’usinage des canaux de cheminement des gaz). C’est pourquoi de nombreuses recherches sont orientées vers le développement d’un nouveau concept de plaques bipolaires. La voie la plus prometteuse est de remplacer les matériaux métalliques et le graphite par des composites à matrice polymère. Les plaques bipolaires composites apparaissent attrayantes en raison de leur facilité de mise en œuvre et leur faible coût de production mais nécessitent une amélioration de leurs propriétés électriques et mécaniques, d’où l’objectif principal de cette thèse dans laquelle on propose: i) un matériau nanocomposite développé par extrusion bi-vis qui est à base de polymères chargés d’additifs solides conducteurs, incluant des nanotubes de carbone. ii) fabriquer un prototype de plaque bipolaire à partir de ces matériaux en utilisant le procédé de compression à chaud avec un refroidissement contrôlé. Dans ce projet, deux polymères thermoplastiques ont été utilisés, le polyfluorure de vinylidène (PVDF) et le polyéthylène téréphtalate (PET). Les charges électriquement conductrices sélectionnées sont: le noir de carbone, le graphite et les nanotubes de carbones. La combinaison de ces charges conductrices a été aussi étudiée visant à obtenir des formulations optimisées. La conductivité électrique à travers l’épaisseur des échantillons développés ainsi que leurs propriétés mécaniques ont été soigneusement caractérisées. Les résultats ont montré que non seulement la combinaison entre les charges conductrices influence les propriétés électriques et mécaniques des prototypes développés, mais aussi la distribution de ces charges (qui de son côté dépend de leur nature, leur taille et leurs propriétés de surface), avait aidé à améliorer les propriétés visées. Il a été observé que le traitement de surface des nanotubes de carbone avait aidé à l’amélioration de la conductivité électrique et la résistance mécanique des prototypes. Le taux de cristallinité généré durant le procédé de moulage par compression des prototypes de plaques bipolaires ainsi que la cinétique de cristallisation jouent un rôle important pour l’optimisation des propriétés électriques et mécaniques visées.

Desenvolvimento de bioblendas poliméricas a partir de gelatina bovina e de tilápia com amido de milho

The natural raw materials acquired special importance beside the mineral raw materials with the need for using alternative sources to oil, because they can be used to produce biopolymers. Gelatin, produced from the denaturation of collagen, and starch, an abundant polysaccharide in various plants, are examples of biopolymers which have several technological applications, especially in films. The objective of this work is to produce polymeric bioblends with gelatin and corn starch using two types of gelatin: commercial bovine gelatin and gelatin produced from mechanically separated flesh of tilapia (Oreochromis niloticus). For the extraction of tilapia gelatin 3 distinct pretreatments, followed by extraction in distilled water under heating were performed. The properties of gelatin extracted were similar to bovine gelatin, and the differences can be explained by the difference in extraction processes and sources. Blends of commercial gelatin and starch were produced in an internal mixer from a Haake torque rheometer, to study the behavior of the gelatin mixture with starch, thus, the same compositions were processed by twin screw extrusion, to define the mixing parameters. Subsequently, the extrusion of blends of tilapia gelatin and corn starch was carried out in the same twin screw extruder. The physico-chemical, rheological and morphological properties of the blends with thermoplastic starch and gelatin were studied. It was found that various properties vary linearly with increasing concentration of the components. The blends produced are immiscible, and among the two gelatins, tilapia gelatin showed a better interfacial adhesion with the corn starch. Regarding the morphology, gelatins formed the dispersed phase in all compositions studied, even in compositions rich in starch. Can be concluded that the procedure for tilapia gelatin extraction is feasible and advantageous, and the increasing in its scale to a reactor of 30 liters is possible, with a satisfactory yield. The bioblends of bovine gelatin/corn starch and tilapia gelatin/corn starch were successfully produced, and the processing conditions were appropriate

Pre-treatment of thermoduric spores in CO2 modified atmosphere and their survivability during food extrusion

The aim of this experiment was to evaluate how susceptible spores become to mechanical damage during food extrusion after being submitted to CO2. B. stearothermophilus spores sowed to corn and soy mix were submitted to 99% CO2 for 10 days and extruded in a single-screw extruder. The treatments were: T1 - spore-containing samples, extruded at screw rotational speed of 65 rpm and barrel wall temperature of 80 °C; T2 - as T1, except for screw rotational speed of 150 rpm; and T3 - as T2, except that samples were submitted to the modified atmosphere. The results for cell viability, minimum and maximum residence times, and static pressure were T1 - 19.90 ± 3.24%, 123.3 ± 14.50 seconds; 203.3 ± 14.05 seconds; 2.217 ± 62 kPa; T2 - 21.42 ± 8.24%, 70.00 ± 5.77 seconds; 170.00 ± 4.67 seconds; 2.310 ± 107 kPa; and T3 - 11.06 ± 2.46%, 86.00 ± 7.23 seconds; 186.00 ± 7.50 seconds; 2.403 ± 93 kPa, respectively. It was concluded that the extrusion process did reduce the cell count. However, screw rotational speed variation or CO2 pre-treatment did not affect cell viability.

Technological properties of precooked flour containing coffee powder and rice by thermoplastic extrusion

Although Brazil is a country of tradition in both the production and consumption of coffee, the most of the coffee is consumed as a beverage, which reduces greatly the competitiveness on international market, for reducing the chances of supplying the product under other forms of consumption. Owing to that, the aim of this study was developing a precooked mixed flour containing coffee powder and rice for use in coffee flavored products. Mixtures of rice and coffee in the proportions of 900:100, 850:150 and 800:200 g, respectively, were processed in a single screw extruder (Brabender DS-20, Duisburg, German) and the effect of the extrusion process on the variables moisture content (16%, 18% and 20%) and temperature in the third extruding zone (140 °C, 160 °C and 180 °C) was studied. The results for expansion index ranged from 2.91 to 11.11 mm in diameter; the water absorption index from 4.59 to 6.33 g gel/g sample and the water solubility index varied from 4.05% to 8.57%. These results showed that, despite coffee powder influenced the variables studied, the expanded product after milling resulted in a extruded mixture with good absorption and water solubility indices, which favors the use of the precooked mixed flour for human consumption.

Extrusion of blends of cassava leaves and cassava flour: physical characteristics of extrudates

A cassava-based puffed snack was produced using a single screw extruder to determine the effect of the raw material composition (cassava leaf flour and moisture) and the process parameters (extrusion temperature and screw speed) on the physical characteristics of an extruded-expanded snack. A central composite rotational design, including four factors with 30 treatments, was used with the following as dependent variables: expansion index, specific volume, water solubility index, water absorption index, color (L*, a*, b*), and hardness. Under conditions of low moisture content (12 to 14%), low percentage of cassava leaf flour (2 to 4%), and intermediate conditions of extrusion temperature (100°C) and screw speed (230rpm), it was possible to obtain puffed snack products with desirable characteristics.

Effects of Extrusion on the Emulsifying Properties of Rumen and Soy Protein

Defatted rumen protein and soy protein concentrate were extruded in a 15.5:1 L/D single-screw extruder at the optimum conditions for their expansion (150A degrees C and 35% moisture, and 130A degrees C and 35% moisture, respectively). Emulsions were produced with these proteins and studied by rheology and time domain low-resolution (1)H nuclear magnetic resonance (TD-NMR). Extrusion increased storage modulus of rumen protein emulsions. The opposite was observed for soy protein. Mechanical relaxation showed the existence of three relaxing components in the emulsions whose relative contributions were changed by extrusion. Likewise, spin-spin relaxation time constants (T (2)) measured by TD-NMR also showed three major distinct populations of protons in respect to their mobility that were also altered by extrusion. Extrusion increased surface hydrophobicity of both rumen and soy protein. Solubility of rumen protein increased with extrusion whereas soy protein had its solubility decreased after processing. Extrusion promoted molecular reorganization of protein, increasing its superficial hydrophobicity, affecting its interfacial properties and improving its emulsifying behavior. The results show that extrusion can promote the use of rumen, a by-product waste from the meat industry, in human nutrition by replacing soy protein in food emulsions.

Amylase utilization for the extrusion of dog diets

Effects of amylase addition on extruder parameters, cost of extrusion, kibble quality and digestibility of dog food were measured in two separate experiments. In experiment 1, 120 kilo-novo-alpha-amilase-unit (KNU)/kg of heat stable alpha-amylase produced by Bacillus licheniformis was added in liquid form during a preconditioning period. In experiment 23684 KNU/kg of heat stable alpha-amylase produced by Aspergillus oryzae was mixed with the ingredients before extrusion. The diets were processed in a single screw extruder and submitted to digestibility and on experiment 1 also to palatability tests. Digestibility was tested using 12 dogs, six per diet. Data were submitted to analysis of variance followed by F-test. Amylase addition altered extrusion parameters in both experiments (P<0.05), with higher output (kg of dry matter [DM]/h: 28% and 43% higher in experiments 1 and 2) and less electric energy consumption (kW to produce 100 kg DM: 22% and 29% lower in experiments 1 and 2). Kibble appearance and quality [density (g/L), cutting force (g), and starch gelatinization degree (%)] did not change with enzyme treatment (P>0.05). Likewise, enzyme addition did not change nutrient digestibility, fecal dry matter or food palatability (P<0.05). Taken together our results suggest that amylase promoted the breakdown of amylose chains, thereby reducing the dough viscosity and resistance inside the extruder which allowed for higher product flow and less electricity energy consumption without altering food quality. (C) 2012 Elsevier B.V. All rights reserved.

Extrusion of flavored corn grits: Structural characteristics, volatile compounds retention and sensory acceptability

The effects of the moisture content of the raw material, extrusion temperature and screw speed on flavor retention, sensory acceptability and structure of corn grits extrudates flavored with isovaleraldehyde, ethyl butyrate and butyric acid were investigated. Higher temperature resulted in more expanded extrudates with lower density and cutting force, while higher moisture content increased ethyl butyrate retention. The most acceptable extrudates were those obtained with low moisture content, under conditions of high extrusion temperature and high screw speed, or low screw speed and low extrusion temperature, whereas the aroma intensity closest to the ideal was observed under conditions of low extrusion temperature and low moisture content of the raw material. © 2013 Elsevier Ltd.

Extrusion of blends of cassava leaves and cassava flour: physical characteristics of extrudates

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Automated optimization of polymer extrusion dies using finite element analysis

An extrusion die is used to continuously produce parts with a constant cross section; such as sheets, pipes, tire components and more complex shapes such as window seals. The die is fed by a screw extruder when polymers are used. The extruder melts, mixes and pressures the material by the rotation of either a single or double screw. The polymer can then be continuously forced through the die producing a long part in the shape of the die outlet. The extruded section is then cut to the desired length. Generally, the primary target of a well designed die is to produce a uniform outlet velocity without excessively raising the pressure required to extrude the polymer through the die. Other properties such as temperature uniformity and residence time are also important but are not directly considered in this work. Designing dies for optimal outlet velocity variation using simple analytical equations are feasible for basic die geometries or simple channels. Due to the complexity of die geometry and of polymer material properties design of complex dies by analytical methods is difficult. For complex dies iterative methods must be used to optimize dies. An automated iterative method is desired for die optimization. To automate the design and optimization of an extrusion die two issues must be dealt with. The first is how to generate a new mesh for each iteration. In this work, this is approached by modifying a Parasolid file that describes a CAD part. This file is then used in a commercial meshing software. Skewing the initial mesh to produce a new geometry was also employed as a second option. The second issue is an optimization problem with the presence of noise stemming from variations in the mesh and cumulative truncation errors. In this work a simplex method and a modified trust region method were employed for automated optimization of die geometries. For the trust region a discreet derivative and a BFGS Hessian approximation were used. To deal with the noise in the function the trust region method was modified to automatically adjust the discreet derivative step size and the trust region based on changes in noise and function contour. Generally uniformity of velocity at exit of the extrusion die can be improved by increasing resistance across the die but this is limited by the pressure capabilities of the extruder. In optimization, a penalty factor that increases exponentially from the pressure limit is applied. This penalty can be applied in two different ways; the first only to the designs which exceed the pressure limit, the second to both designs above and below the pressure limit. Both of these methods were tested and compared in this work.

Coagent Modified Polypropylene Prepared by Reactive Extrusion: A New Look Into the Structure-Property Relations of Injection Molded Parts

Peroxide-mediated reactive extrusion of linear isotactic polypropylene (L-PP) was conducted in the presence of trimethylolpropane trimethacrylate (TMPTMA) and triallyl trimesate (TAM) coagents, using a twin screw extruder. The resulting coagent-modified polypropylenes (CM-PP) had higher viscosities and elasticities, as well as increased crystallization temperature compared to PP reacted only with peroxide (DCP-PP). Additionally, deviations from terminal flow, and strain hardening were observed in PP modified with TAM, signifying the presence of long chain branching (LCB). The CM-PP formulations retained the modulus and tensile strength of the parent L-PP, in spite of their lower molar mass and viscosities, whereas their elongation at break and the impact strength were better. This was attributed to the finer spherulitic structure of these materials, and to the disappearance of the skin-core layer in the injection molded specimens.

Effect of extrusion parameters on flavour retention, functional and physical properties of mixtures of starch and D-limonene encapsulated in milk protein

The purpose of this research was to investigate the retention of flavour volatiles encapsulated in water-insoluble systems during high temperature–short time extrusion process. A protein precipitation method was used to produce water-insoluble capsules encapsulating limonene, and the capsules were added to the extruder feed material (cornstarch). A twin-screw extruder was used to evaluate the effect of capsule level of addition (0–5%), barrel temperature (125–145 °C) and screw speed (145–175 r.p.m.) on extruder parameters (torque, die pressure, specific mechanical energy, residence time distribution) and extrudate properties [flavour retention, texture, colour, density, expansion, water absorption index, water solubility index (WSI)]. Capsule level had a significant effect on extrusion conditions, flavour retention and extrudate physical properties. Flavour retention increased with the increase in capsule level from 0% to 2.5%, reached a maximum value at capsule level of 2.5% and decreased when the capsule level increased from 2.5% to 5%. The die pressure, torque, expansion ratio, hardness and WSI exhibited the opposite effect with the presence of capsules.

Flow field analysis of some mixing and conveying screw element regions, within a closely intermeshing, co-rotating twin-screw extruder.

Grafting of antioxidants and other modifiers onto polymers by reactive extrusion, has been performed successfully by the Polymer Processing and Performance Group at Aston University. Traditionally the optimum conditions for the grafting process have been established within a Brabender internal mixer. Transfer of this batch process to a continuous processor, such as an extruder, has, typically, been empirical. To have more confidence in the success of direct transfer of the process requires knowledge of, and comparison between, residence times, mixing intensities, shear rates and flow regimes in the internal mixer and in the continuous processor.The continuous processor chosen for the current work in the closely intermeshing, co-rotating twin-screw extruder (CICo-TSE). CICo-TSEs contain screw elements that convey material with a self-wiping action and are widely used for polymer compounding and blending. Of the different mixing modules contained within the CICo-TSE, the trilobal elements, which impose intensive mixing, and the mixing discs, which impose extensive mixing, are of importance when establishing the intensity of mixing. In this thesis, the flow patterns within the various regions of the single-flighted conveying screw elements and within both the trilobal element and mixing disc zones of a Betol BTS40 CICo-TSE, have been modelled using the computational fluid dynamics package Polyflow. A major obstacle encountered when solving the flow problem within all of these sets of elements, arises from both the complex geometry and the time-dependent flow boundaries as the elements rotate about their fixed axes. Simulation of the time dependent boundaries was overcome by selecting a number of sequential 2D and 3D geometries, used to represent partial mixing cycles. The flow fields were simulated using the ideal rheological properties of polypropylene and characterised in terms of velocity vectors, shear stresses generated and a parameter known as the mixing efficiency. The majority of the large 3D simulations were performed on the Cray J90 supercomputer situated at the Rutherford-Appleton laboratories, with pre- and postprocessing operations achieved via a Silicon Graphics Indy workstation. A mechanical model was constructed consisting of various CICo-TSE elements rotating within a transparent outer barrel. A technique has been developed using coloured viscous clays whereby the flow patterns and mixing characteristics within the CICo-TSE may be visualised. In order to test and verify the simulated predictions, the patterns observed within the mechanical model were compared with the flow patterns predicted by the computational model. The flow patterns within the single-flighted conveying screw elements in particular, showed good agreement between the experimental and simulated results.