Modification of commercial poly-lactide for extrusion coated food packaging applications

Poly-L-lactide (PLLA) is a widely used sustainable and biodegradable alternative to replace synthetic non-degradable plastic materials in the packaging industry. Conversely, its processing properties are not always optimal, e.g. insufficient melt strength at higher temperatures (necessary in extrusion coating processes). This thesis reports on research to improve properties of commercial PLLA grade (3051D from NatureWorks), to satisfy and extend end-use applications, such as food packaging by blending with modified PLLA. Adjustment of the processability by chain branching of commercial poly-L-lactide initiated by peroxide was evaluated. Several well-defined branched structures with four arms (sPLLA) were synthesized using pentaerythritol as a tetra-functional initiator. Finally, several block copolymers consisting of polyethylene glycol and PLLA (i.e. PEGLA) were produced to obtain a well extruded material with improved heat sealing properties. Reactive extrusion of poly-L-lactide was carried out in the presence of 0.1, 0.3 and 0.5 wt% of various peroxides [tert-butyl-peroxybenzoate (TBPB), 2,5-dimethyl-2,5-(tert-butylperoxy)-hexane (Lupersol 101; LOL1) and benzoyl peroxide (BPO)] at 190C. The peroxide-treated PLLAs showed increased complex viscosity and storage modulus at lower frequencies, indicating the formation of branched/cross linked architectures. The material property changes were dependent on the peroxide, and the used peroxide concentration. Gel fraction analysis showed that the peroxides, afforded different gel contents, and especially 0.5 wt% peroxide, produced both an extremely high molar mass, and a cross linked structure, not perhaps well suited for e.g. further use in a blending step. The thermal behavior was somewhat unexpected as the materials prepared with 0.5 wt% peroxide showed the highest ability for crystallization and cold crystallization, despite substantial cross linking. The peroxide-modified PLLA, i.e. PLLA melt extruded with 0.3 wt% of TBPB and LOL1 and 0.5 wt% BPO was added to linear PLLA in ratios of 5, 15 and 30 wt%. All blends showed increased zero shear viscosity, elastic nature (storage modulus) and shear sensitivity. All blends remained amorphous, though the ability of annealing was improved slightly. Extrusion coating on paperboard was conducted with PLLA, and peroxide-modified PLLA blends (90:10). All blends were processable, but only PLLA with 0.3 wt% of LOL1 afforded a smooth high quality surface with improved line speed. Adhesion levels between fiber and plastic, as well as heat seal performance were marginally reduced compared with pure 3051D. The water vapor transmission measurements (WVTR) of the blends containing LOL1 showed acceptable levels, only slightly lower than for comparable PLLA 3051D. A series of four-arm star-shaped poly-L-lactide (sPLLA) with different branch length was synthesized by ring opening polymerization (ROP) of L-lactide using pentaerythritol as initiator and stannous octoate as catalyst. The star-shaped polymers were further blended with its linear resin and studied for their melt flow and thermal properties. Blends containing 30 wt% of sPLLA with low molecular weight (30 wt%; Mwtotal: 2500 g mol-1 and 15000 g mol-1) showed lower zero shear viscosity and significantly increased shear thinning, while at the same time slightly increased crystallization of the blend. However, the amount of crystallization increased significantly with the higher molecular weight sPLLA, therefore the star-shaped structure may play a role as nucleating agent. PLLA-polyethylene glycol–PLLA triblock copolymers (PEGLA) with different PLLA block length were synthesized and their applicability as blends with linear PLLA (3051D NatureWorks) was investigated with the intention of improving heat-seal and adhesion properties of extrusion-coated paperboard. PLLA-PEG-PLLA was obtained by ring opening polymerization (ROP) of L-lactide using PEG (molecular weight 6000 g mol-1) as an initiator, and stannous octoate as catalyst. The structures of the PEGLAs were characterized by proton nuclear magnetic resonance spectroscopy (1H-NMR). The melt flow and thermal properties of all PEGLAs and their blends were evaluated using dynamic rheology, and differential scanning calorimeter (DSC). All blends containing 30 wt% of PEGLAs showed slightly higher zero shear viscosity, higher shear thinning and increased melt elasticity (based on tan delta). Nevertheless, no significant changes in thermal properties were distinguished. High molecular weight PEGLAs were used in extrusion coating line with 3051D without problems.

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.

Optimization of extrusion process for production of nutritious pellets

A blend of 50% Potato Starch (PS), 35% Quality Protein Maize (QPM), and 15% Soybean Meal (SM) were used in the preparation of expanded pellets utilizing a laboratory extruder with a 1.5 × 20.0 × 100.0 mm die-nozzle. The independent variables analyzed were Barrel Temperature (BT) (75-140 °C) and Feed Moisture (FM) (16-30%). The effect of extrusion variables was investigated in terms of Expansion Index (EI), apparent density (ApD), Penetration Force (PF) and Specific Mechanical Energy (SME), viscosity profiles, DSC, crystallinity by X-ray diffraction, and Scanning Electronic Microscopy (SEM). The PF decreased from 30 to 4 kgf with the increase of both independent variables (BT and FM). SME was affected only by FM, and decreased with the increase in this variable. The optimal region showed that the maximum EI was found for BT in the range of 123-140 °C and 27-31% for FM, respectively. The extruded pellets obtained from the optimal processing region were probably not completely degraded, as shown in the structural characterization. Acceptable expanded pellets could be produced using a blend of PS, QPM, and SM by extrusion cooking.

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.

Optimization of extrusion variables for the production of snacks from by-products of rice and soybean

This study aimed to define the process conditions to obtain snacks from the by-products of rice and soybean with physical characteristics suitable for marketing. Therefore, the effects of moisture and extrusion temperature on the expansion and color of the products obtained experimentally obtained were evaluated, and the proximate composition of the by-products and that of the snack with greater desirability were determined. Response surface methodology and rotational central composite design were used, and desirability test based on the regression models adjusted was applied. The most desirable snack, with the highest expansion index (3.39), specific volume (13.5 mL.g-1), and the chromaticity coordinate a* (2.79), was obtained under 12 g.100 g-1 moisture and 85ºC of temperature in the third zone of the extruder. The snack produced under these conditions attained content of protein and lipid content 41 and 64% higher than that of the traditional corn snack. It can be concluded that producing extruded snack made form a mixture of broken grains, rice bran, and soybean okara (81:9:10) is technologically feasible, enabling the development of a new product with good nutritional value that can improve the diet of children, the main consumers of this type of food.

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.

Recycling of NR Based Cured Latex Material Reclaimed with 2,2'-Dibenzamidodiphenyldisulphide in a TruckTire Tread Compound

It is observed that reclamation of natural rubber latex based rubber using 2,2'-dibenzamidodiphenvldisulphide as reclaiming agent is an optional methodology for recycling of waste latex rubber (WLR). For progressive replacement of virgin natural rubber by the reclaim, two alternatives curing system were investigated: adjustment or reduction of the curing system with increasing reclaim content, to compensate for the extra amount of curatives brought along by the reclaim. For fixed curing system, as if the reclaim were equivalent to virgin NR. The cure behavior, final crosslink density and distribution, mechanical properties, and dynamic viscoelastic properties of the blends with reclaimed WLR are measured and compared with the virgin compound. The morphology of the blends, sulfur migration, and final distribution are analyzed.The mechanical and dynamic viscoelastic properties deteriorate for both curing systems, but to a lesser extent for fixed curing system compared to adjusted curing system. With the fixed cure system, many properties like tensile strength and compression set do still deteriorate, but tan 6 and Mrrr„/Murxr, representative for the rolling resistance of tires are improved. On the other hand, with the adjusted cure system both mechanical and dynamic properties still deteriorate.

Starved Extrusion for the Improvement of Mechanical Properties of Rubber Vulcanizates

Filled compounds of natural rubber, isobutylene-isoprene rubber and styrene-butadiene rubber compounds were extruded through a laboratory extruder by varying the feeding rate at different temperatures and revolutions per minute. The extruded compounds were vulcanized up to their optimum cure times and the mechanical properties of the vulcanizates were determined. The properties suggest that there is a particular feeding rate in the starved fed region which results in maximum mechanical properties. The study shows that running the extruder at a slightly starved condition is an attractive means of improving the physical properties.

Significance of Feeding Rate in the Extrusion of Filled and Gum 11R Vulcanizates

Filled and gum compounds of Isobutylene-Isoprene rubber were extruded through a laboratory extruder at various feeding rates, different temperatures and revolutions per minute. The extruded compounds were vulcanized up to their optimum cure times and the mechanical properties of the vulcanizates were determined. The properties suggest that there is a particular feeding rate in the starved fed region, which results in maximum mechanical properties. The study shows that running the extruder at a slightly starved condition is an attractive means of improving the physical properties.

Modification of Polyethylenes by Reactive Extrusion

The main aim of the study was to optimise the reactive extrusion conditions in the conventional modification processes of polyethylenes in a single screw extruder.The optimum conditions for peroxide crosslinking of low density polyethylene (LDPE), linear low density polyethylene (LLDPE) and their blend were determined in a torque rheometer. The actual reactive extrusion was performed in a laboratory single screw extruder using the optimum parameters. The influence of the coagent, triaUyl cyanurate (TAC), on the cross linking of low density polyethylene in the presence of peroxide was also investigated. The peroxide crosslinking was found to improve the mechanical properties and the thermal stability of the polyethylenes. The efficiency of crosslinking was found to be improved by the addition of coagent such as TAC.The optimum conditions for silane grafting viz temperature, shear rate, silane and DCP concentrations were determined on a torque rheometer in the case of LDPE, LLDPE and their blend. Silane grafting of LDPE in the presence of peroxide was performed with and without addition of water. Compounding of such mixtures in the melt at high temperatures caused decomposition of the peroxide and grafting of alkoxy silyl groups to the polyethylene chains.The optimum parameters for maleic anhydride modification of LDPE, LLDPE and their blend were determined. The grafting reaction was confinned by FTIR spectroscopy. Modification of polyethylenes with maleic anhydride in the presence of dicumyl peroxide was found to be useful in improving mechanical properties. The improvement was found to be mainly due to the grafting of carboxyl group and formation of crosslinks between the chains. The cross linking initiated improvements indicate extended property profiles and new application fields for polyethylenes.On the whole the study shows that the optimum conditions for modifying polyethylenes can be determined on a torque rheometer and actual modification can be performed in a single screw extruder by employing the optimum parameters for improved mechanical! thermal behaviour without seriously affecting their processing behaviour.

Effect of Feeding Rate in Polymer Extrusion ”

Starve feeding of single screw extruder was described as an important means of improving the performance characteristics of the extruder. In addition to such improvement with versatility, the starve feeding technique also may affect the mechanical properties of the extrudate since the heat transfer an(l mixing characteristics in the starve fed and Hood fed extruders are not the same. Since the material is more loosely packed in the channels of the starve fed extruder, there may be greater bed mobility and uniformity. Further, the. thermal an(l shear induced degradation are also less since possibilities of developing local high temperatures are less compared to a densely compacted extruder bed. This study has been undertaken mainly to explore the effect of feeding rate on the mechanical properties of rubber and plastic extrudates since the effect of feeding rate has not been analysed from this angle so far.

Growth of the lava dome and extrusion rates at Soufrière Hills Volcano, Montserrat, West Indies: 2005–2008

The third episode of lava dome growth at Soufrière Hills Volcano began 1 August 2005 and ended 20 April 2007. Volumes of the dome and talus produced were measured using a photo-based method with a calibrated camera for increased accuracy. The total dense rock equivalent (DRE) volume of extruded andesite magma (306 ± 51 Mm3) was similar within error to that produced in the earlier episodes but the average extrusion rate was 5.6 ± 0.9 m3s−1 (DRE), higher than the previous episodes. Extrusion rates varied in a pulsatory manner from <0.5 m3s−1 to ∼20 m3s−1. On 18 May 2006, the lava dome had reached a volume of 85 Mm3 DRE and it was removed in its entirety during a massive dome collapse on 20 May 2006. Extrusion began again almost immediately and built a dome of 170 Mm3 DRE with a summit height 1047 m above sea level by 4 April 2007. There were few moderate-sized dome collapses (1–10 Mm3) during this extrusive episode in contrast to the first episode of dome growth in 1995–8 when they were numerous. The first and third episodes of dome growth showed a similar pattern of low (<0.5 m3s−1) but increasing magma flux during the early stages, with steady high flux after extrusion of ∼25 Mm3

Sensory and instrumental analyses of volatiles generated during the extrusion cooking of oat flours

Three batches of oats were extruded under four combinations of process temperature (150 or 180 °C) and process moisture (14.5 and 18%). Two of the extrudates were evaluated by a sensory panel, and three were analyzed by GC-MS. Maillard reaction products, such as pyrazines, pyrroles, furans, and sulfur-containing compounds, were found in the most severely processed extrudates (high-temperature, low-moisture). These extrudates were also described by the assessors as having toasted cereal attributes. Lipid degradation products, such as alkanals, 2-alkenals, and 2,4-alkadienals, were found at much higher levels in the extrudates of the oat flour that had been debranned. It contained lower protein and fiber levels than the others and showed increased lipase activity. Extrudates from these samples also had significantly lower levels of Maillard reaction products that correlated, in the sensory analysis, with terms such as stale oil and oatmeal. Linoleic acid was added to a fourth oat flour to simulate the result of increased lipase activity, and GC-MS analysis showed both an increase in lipid degradation products and a decrease in Maillard reaction products.

Cyclic extrusion of a lava dome based on a stick-slip mechanism

Lava dome eruptions are sometimes characterised by large periodic fluctuations in extrusion rate over periods of hours that may be accompanied by Vulcanian explosions and pyroclastic flows. We consider a simple system of nonlinear equations describing a 1D flow of lava extrusion through a deep elastic dyke feeding a shallower cylindrical conduit in order to simulate this short-period cyclicity. Stick-slip conditions depending on a critical shear stress are assumed at the wall boundary of the cylindrical conduit. By analogy with the behaviour of industrial polymers in a plastic extruder, the elastic dyke acts like a barrel and the shallower cylindrical portion of the conduit as a die for the flow of magma acting as a polymer. When we applied the model to the Soufrière Hills Volcano, Montserrat, for which the key parameters have been evaluated from previous studies, cyclic extrusions with periods from 3 to 30 h were readily simulated, matching observations. The model also reproduces the reduced period of cycles observed when a major unloading event occurs due to lava dome collapse.

Measuring large topographic change with InSAR: lava thicknesses, extrusion rate and subsidence rate at Santiaguito volcano, Guatemala

Lava flows can produce changes in topography on the order of 10s-100s of metres. A knowledge of the resulting volume change provides evidence about the dynamics of an eruption. We present a method to measure topographic changes from the differential InSAR phase delays caused by the height differences between the current topography and a Digital Elevation Model (DEM). This does not require a pre-event SAR image, so it does not rely on interferometric phase remaining coherent during eruption and emplacement. Synthetic tests predicts that we can estimate lava thickness of as little as �9 m, given a minimum of 5 interferograms with suitably large orbital baseine separations. In the case of continuous motion, such as lava flow subsidence, we invert interferometric phase simultaneously for topographic change and displacement. We demonstrate the method using data from Santiaguito volcano, Guatemala, and measure increases in lava thickness of up to 140 m between 2000 and 2009, largely associated with activity between 2000 and 2005. We find a mean extrusion rate of 0.43 +/- 0.06 m3/s, which lies within the error bounds of the longer term extrusion rate between 1922-2000. The thickest and youngest parts of the flow deposit were shown to be subsiding at an average rate of �-6 cm/yr. This is the first time that flow thickness and subsidence have been measured simultaneously. We expect this method to be suitable for measurment of landslides and other mass flow deposits as well as lava flows.