Blown films of high molecular weight high density polyethylene (HMW-HDPE) were produced from two resins of differing molecular weight (MW) and molecular weight distribution (MWD) using a high stalk bubble configuration. The processing conditions were varied such that three film gauges, each fabricated at three frost line heights (FLH), were produced. Crystalline orientation and tear resistance properties of the films were measured. Under appropriate conditions, the formation of two populations of lamellar stacks with their surface normals orthogonal to one another were observed. Increasing the FLH increased the amount of transverse direction (TD) stacked lamellae. This finding was related to bubble shape and relaxation behavior. Balanced in plane crystalline orientation was noted to give the best dart impact performance. Interestingly, for the lower Mw resin in the study, this could be achieved by down gauging. In a second project, structure-property-processing relationships were investigated in a series of high density polyethylene (HDPE) blown films. The use of metallocene and chromium oxide based resins allowed the effects of MW and MWD on orientation behavior to be studied. All films possessed Keller-Machin low stress morphologies oriented along the film MD. Under identical processing conditions, the narrower MWD resins produced films with greater orientation than the broader MWD resins of equivalent weight average MW. Greater processing stresses and shorter quench times were noted to produce higher levels of orientation. Moisture vapor transmission rate (MVTR) performance of these films was also measured. Orientation effects were seen to influence MVTR as permeation behavior did not scale directly with the crystalline content in the films. Additional studies investigated the relationship between comonomer content and the thermal and structural properties of novel poly(acrylonitrile-co-methyl acrylate) materials. Five polymers were studied with methyl acrylate (MA) content varying between 0 and 15 mol%. The MA decreased both the glass transition and melting temperatures. Melting point depression was sufficient in the two highest MA content copolymers to allow for complete melting prior to the onset of thermal degradation using modest heating rates (20 ºC/min). Insight into the heterogeneous structure of poly(acrylonitrile) homopolymer was gained through both conventional and modulated differential scanning calorimetry. / Ph. D.

The mixing of additives into a plastic is an extremely important step in the plastics industry, necessary for the manufacture of almost every conceivable product. Therefore the costs in developing new products can prove very expensive as the testing is usually carried out using full scale machines, usually using twin screw extruders because they are able to provide good dispersive and distributive mixing. This is particularly important when compounding difficult to disperse additives and nano-additives. What is required is a machine that can replicate the mixing abilities of a twin-screw extruder but on a laboratory scale. There have been attempts by industry to develop smaller machines, such as the Thermo Scientific HAAKE Minilab II Micro Compounder which processes on the scale of 7 cm3 of material volume. This can be too small for some needs and therefore a machine is required to produce material on the 10g to 100g scale. To this end a laboratory mixer of novel design was devised and its mixing performance was assessed using conductive carbon black and compared against the Thermo Scientific HAAKE Minilab II Micro Compounder, a 19 mm co-rotating twin-screw extruder and a 40 mm co-rotating twin-screw extruder. Carbon black was used because mixing performance can be assessed by measuring the minimum carbon loading necessary to induce electrical conductivity. It was found that the minimixer was able to induce electrical conductivity at loading of 5.75% but the comparison with the other machines proved difficult as the achievement of the threshold at which semi-conductivity occurred appeared independent of shear rate and mixing duration.

Abstract This thesis correlates rheological data into a non-linear blown film model that describes the stress and cooling-induced morphological transformations in the axial and flow profiles of the blown films. This will help to improve the physical and mechanical properties of the films in a cost effective way, which will in turn be of great benefit to the food and packaging industries. In this research, experimental and numerical studies of a blown film extrusion were carried out using two different low-density polyethylenes (LDPEs). In the experiment, the key parameters measured and analysed were molecular, rheological and crystalline properties of the LDPEs. In the numerical study, blown film simulation was carried out to determine the bubble characteristics and freeze line height (FLH). A new rheological constitutive equation was developed by combining the Hookean model with the well known Phan-Thien and Tanner (PTT) model to permit a more accurate viscoelastic behaviour of the material. For experimental verification of the simulation results, resins were processed in a blown film extrusion pilot plant using identical die temperatures and cooling rates as used in the simulation study. Molecular characteristics of both LDPEs were compared in terms of their processing benefit in the film blowing process. Based on the experimental investigation, it was found that molecular weight and its distribution, degree of long chain branching and cooling rate play an important role on melt rheology, molecular orientation, blown film processability, film crystallinity and film properties. Effect of short chain branching was found insignificant for both LDPEs. Statistical analysis was carried out using MINITAB-14 software with a confidence level of 95% to determine the effect of process variables (such as die temperature and cooling rate) on the film properties. Film properties of the LDPEs were found to vary with their molecular properties and the process variables used. Blown film model performance based on the newly established PTT-Hookean model was compared with that based on the Kelvin model. Justification of the use of PTT-Hookean model is also reported here using two different material properties. From the simulation study, it has been found that predictions of the blown film characteristics conformed very well to the experimental data of this research and previous studies using different materials and different die geometries. Long chain branching has been found as the most prominent molecular parameter for both LDPEs affecting melt rheology and hence the processability. Die temperature and cooling rate have been observed to provide similar effect on the tear strength and shrinkage properties of blown film for both LDPEs. In comparison to the Kelvin model, the PTT-Hookean model is better suited for the modelling of the film blowing process. It has also been demonstrated in this study that the PTT-Hookean model conformed well to the experimental data near the freeze line height and is suitable for materials of lower melt elasticity and relaxation time.

The mixing of additives into a plastic is an extremely important step in the plastics industry, necessary for the manufacture of almost every conceivable product. Therefore the costs in developing new products can prove very expensive as the testing is usually carried out using full scale machines, usually using twin screw extruders because they are able to provide good dispersive and distributive mixing. This is particularly important when compounding difficult to disperse additives and nano-additives. What is required is a machine that can replicate the mixing abilities of a twin-screw extruder but on a laboratory scale. There have been attempts by industry to develop smaller machines, such as the Thermo Scientific HAAKE Minilab II Micro Compounder which processes on the scale of 7 cm3 of material volume. This can be too small for some needs and therefore a machine is required to produce material on the 10g to 100g scale. To this end a laboratory mixer of novel design was devised and its mixing performance was assessed using conductive carbon black and compared against the Thermo Scientific HAAKE Minilab II Micro Compounder, a 19 mm co-rotating twin-screw extruder and a 40 mm co-rotating twin-screw extruder. Carbon black was used because mixing performance can be assessed by measuring the minimum carbon loading necessary to induce electrical conductivity. It was found that the minimixer was able to induce electrical conductivity at loading of 5.75% but the comparison with the other machines proved difficult as the achievement of the threshold at which semi-conductivity occurred appeared independent of shear rate and mixing duration. / EPSRC / The following files are not available online: Americhem raw data; Carbon Black raw data; Videos.

La biomasse représente l’une des principales alternatives à l’utilisation du pétrole dans la plasturgie. Grâce à leurs propriétés fonctionnelles, les caséinates sont une matière première prometteuse pour la fabrication de films plastiques pour des applications dans l’emballage biodégradable et hydrosoluble. La transformation du caséinate de sodium par les techniques habituellement utilisées dans la plasturgie a été démontrée. Des extrudats de caséinate plastifié au glycérol ont été obtenus au moyen d’une extrudeuse bi-vis corotative. La caractérisation physico-chimique du matériau obtenu a confirmé la thermostabilité de cette protéine et a montré la dépendance du comportement du matériau vis-à-vis de l’humidité ambiante. Pour une variation du taux d’Humidité Relative, de 40 à 90% et une augmentation de la concentration du glycérol, plastifiant hygroscopique, le matériau passe d’un état vitreux (rigide) à un état caoutchouteux (mou). Des films fins ont été ensuite réalisés, à partir des extrudats thermoplastiques, par extrusion gonflage. La perméabilité à la vapeur d’eau des films de caséinate de sodium a été étudiée et a montré que ces matériaux sont de mauvaises barrières à l’humidité. La deuxième partie a été consacré à l’étude de mélanges caséinate de sodium/caséinate de calcium d’un côté et caséinate de sodium/PBAT de l’autre. Le mélange des deux caséinates a permis d’augmenter la tenue mécanique du mélange, à partir de 50% de caséinate de calcium, et de retarder le transfert hydrique à travers le film. Dans le même sens, l’ajout du PBAT, a augmenté jusqu’à deux fois plus, le module d’Young des mélanges mais a baissé la résistance au transfert d’humidité du film à cause de l’incompatibilité des deux polymères / Biomass is one of the main alternatives to the use of oil in plastics field. Due to their various functional properties, caseinates are considered as an interesting raw material for making biodegradable and water-soluble packaging. The transformation of sodium caseinate by the processes used for synthetic plastics industry has been demonstrated. A corotating twin-screw extruder was used to get glycerol plasticized caseinate pellets. The physicochemical properties of the obtained material have confirmed the thermal stability of this protein and demonstrated the influence of surrounding moisture on material behavior. With the Relative Humidity varying from 40 to 90% and increasing the glycerol content, an hydrous plasticizer, the mechanical properties of sodium caseinate based materials changed from those of glassy (rigid) to rubbery (soft) plastics. The pellets were then taken over to make film using a blown-film extruder. The water vapour permeability of blown film was studied and showed that sodium caseinate based films are a poor moisture barrier. The second part dealt with the sodium caseinate blend. Sodium caseinate/calcium caseinate and sodium caseinate/PBAT blends was performed. Adding calcium caseinate, started from 50%, improved the mechanical properties and delayed hydrous transfer through the film. Concerning the sodium caseinate/PBAT blends, adding PBAT increased until twice more the material’s Young modulus but decreased the moisture transfer resistance because of the incompatibility between the two polymers

This study investigated the effect of chain extender epoxy based additive, Joncryl ADR 4368, on the rheological, thermal and mechanical properties of poly(lactic acid) with poly(butylene adipate-co-terephthalate) (PLA/PBAT) blends in the blown films form. Compositions with 40% and 60% by weight PLA were selected for production of such blown films. These dispersed phase content was chosen because the literature does not present mechanical behavior studies of tubular film blends with high concentration of the dispersed phase. Rheological analysis in dynamic oscillatory regime showed the reaction of epoxy group with end chain in both polymers, and a higher reactivity of the chain extender with PLA. The films produced exhibited different morphologies according to the blend composition and chain extender content. Films containing 40% PLA presented the dispersed phase morphology in a fibrillar form; however in the presence of chain extender, the dispersed phase is presented as ellipsoids. This change in morphology resulted in a reduction in the mechanical properties of these films in tensile tests. Films containing 60% PLA had a coarse morphology with dispersed phase in the ribbons-like form. The addition of extender yielded a refinement of the dispersed phase morphology from ribbon to elongated fibril form, which is responsible for the mechanical properties improvement of these films. Despite the low adhesion between matrix and dispersed phase, the proper setting of the morphology of the blends as a function of additive content, allowed to produce films with mechanical properties quite different from each other. / Neste trabalho foi estudado o efeito do aditivo extensor de cadeia à base de epóxi, Joncryl ADR 4368, nas propriedades reológicas, térmicas e mecânicas de filmes tubulares de blendas de poli(ácido láctico) com poli(butileno adipato-co-tereftalato) (PLA/PBAT). Composições com 40% e 60% em peso de PLA foram selecionadas para produção destes filmes tubulares. Estes teores de fase dispersa foram escolhidos pelo fato da literatura não apresentar estudos de comportamento mecânico de filmes tubulares de blendas com alta concentração da fase dispersa. Análises reológicas em regime dinâmico oscilatório evidenciaram a reação do grupo epóxi com finais de cadeia de ambos os polímeros, e evidenciaram uma maior reatividade do extensor com o PLA. Os filmes produzidos apresentaram diferentes morfologias de acordo com a composição da blenda e o teor de extensor de cadeia adicionado. Filmes contendo 40% de PLA apresentaram uma morfologia da fase dispersa na forma fibrilar; já na presença do extensor, a fase dispersa se apresentou na forma de elipsóides. Esta mudança na morfologia acarretou em uma redução nas propriedades mecânicas destes filmes em ensaios de tração. Filmes contendo 60% de PLA apresentaram uma morfologia grosseira com a fase dispersa na forma de fitas. A adição do extensor proporcionou um refinamento na morfologia da fase dispersa com formação de fibrilas alongadas, responsável pelo ganho nas propriedades mecânicas destes filmes. Apesar da baixa adesão entre matriz e fase dispersa, o ajuste apropriado da morfologia das blendas, em função do teor de aditivo, possibilitou produzir filmes com propriedades mecânicas bastante diferenciadas entre si.