Compounding Unit Planetary Roller Extruder

Planetary roller extruders (PREs) are currently being employed first and foremost to feed calender/lamination units, for pelleting, for compounding powdered paint and for the reuse of recyclate. In these disciplines it is the most successful multi‐screw extruder. The range of materials that are compounded extends from classical plasticised poly(vinyl chloride) (PVC), via poly(propylene) (PP) and acrylonitrile‐butadiene‐styrene (ABS), through to powdered rubber. The planetary roller extruders convince in comparison with other compounding machines through the thermally carefully compounding, the balanced ratio of shear and heat transfer and the narrow residence time distribution. Experimental investigations to analyze the process behavior of PREs were carried out for the first time.

Homogenization and dispersion at a material‐bank in the planetary roller extrusion test stand.     

Tensile Properties of Extruded Zein Sheets and Extrusion Blown Films

Zein‐based plastic sheets and films were formed by extrusion through a slit‐die or blowing head. Zein was plasticized with oleic acid and formed into a wet moldable mass (resin) to feed the extruders. Both single‐ and twin‐screw extruded sheets showed higher elongation at break, lower tensile strength, and lower Young's Modulus than non‐extruded samples. Stress‐strain plots for extruded samples showed evidence of plastic behavior. Observed necking of samples under tensile stress was also taken as evidence of plastic behavior. Small differences in tensile strength and elongation at break between single‐ and twin‐screw extruded samples were attributed to the effect of small voids observed by SEM in single‐screw extruded samples. Blown film extrusion was affected by feed moisture content and barrel temperatures. Optimal moisture content was determined at 14–15% while temperature at the three extruder zones was maintained at 20–25, 20–25, and 35 °C, respectively. Temperature at the blowing head was 45 °C. Film samples blown after either single‐ or twin‐screw extrusion showed similar tensile properties to those of slit die extruded samples.

Blown extrusion of zein film with single‐screw extruder.     

Study of Polyurethane Formulations Containing Diols Obtained via Glycolysis of Poly(ethylene terephthalate) (PET) by Oligoesters Diols through a Reactive Extrusion Process

Summary: The glycolysis of PET by oligoester diols in the presence of zinc acetate was carried out in two successive twin‐screw extruders with total residence times of 4 min and without solvent. These new glycolysates were analyzed and used in polyurethane formulation with a commercial polyol. The reactivity of these formulations was studied. The mechanical properties, thermal and swelling behavior of these polyurethanes were investigated. Mechanical properties are improved with the addition of glycolysate. The thermal behavior is not modified with the addition of glycolysate. The swelling behavior of the material depends on the solvent nature. The addition of glycolysate allows a decrease in material swelling in chloroform but increases this swelling in acetone.

     

Global Concept for Describing and Investigation of Wall Slip Effects in the Extrusion Process

When it comes to the design of extrusion line components such as single‐screw extruders or extrusion dies, no one has yet succeeded in developing a well‐functioning concept for wall‐slipping materials. This article examines the fundamental influences of the wall slippage effect on flow behavior in the extrusion die and plastification unit. New and extended methods of calculation for describing this flow phenomenon are presented for both these extrusion line components, and the general possibilities for linking the two approaches are discussed.

Diagram of the flow curve (τ = shear stress, = shear rate) of wall‐slipping plastics for constant pressure.     

Optimization of Extrusion Parameters for Preparing PCL‐Layered Silicate Nanocomposites Supported by Modeling of Twin‐Screw Extrusion

PCL‐based nanoclay (layered silicate) nanocomposites are prepared using a small scale intermeshing co‐rotating twin‐screw extruder. Improving the level of nanoclay dispersion in PCL nanocomposites is obtained by changing the extrusion parameters. Increasing the screw speed and decreasing the throughput leads to an improved dispersion quality, as observed from the improved mechanical properties of the nanocomposites as well as from their clearly affected rheological and crystallization behavior. Furthermore, a commercially available software that simulates the twin‐screw extrusion process (LUDOVIC) is used to asses the processing parameters applied for making the nanocomposites.

     

Oxygen Barrier Properties of Poly(ethylene terephthalate) Nanocomposite Films

Nanocomposites of poly(ethylene terephthalate) and two different montmorillonite‐based organoclays were prepared by a co‐rotating twin screw extruder. Dispersion of nanoclays in the polymer matrix was examined by TEM and XRD. Nanocomposites with lower content of organoclay showed exfoliated morphology while by increasing the amount of organoclay the intercalated morphology was more prevalent. Both organoclays had a good intercalation with PET and were uniformly dispersed within the polymer. Oxygen permeability of thin films of nanocomposites showed that the nanocomposites had better oxygen barrier properties than the neat PET. Tensile and impact properties of the nanocomposites also were measured.

     

Extraction of Contamination of Automotive Gas Tank Material by Extrusion with Supercritical Carbon Dioxide

During their working life, plastics can be exposed to contaminating media which limit their recyclability. A continuous extraction process with supercritical CO₂ has been developed. Contaminated material is extruded through two twin‐screw extruders in a cascade. The first extruder purifies with scCO₂ and the second extruder is for degassing and hot‐cut pelletisation. Post‐consumer automotive diesel fuel tank material has been processed. A direct flow and a counter‐flow process with different screw configurations have been developed. Characterisation has been performed by headspace gas chromatography. Results show that contaminants were extracted out of the plastic for both process variants. However, direct flow yielded better extraction efficiency.

     

Blends of a Main Chain Liquid‐Crystalline Polyester with a Diepoxide and with a Diepoxide/Amine Mixture Prepared in a Twin‐Screw Extruder

Summary: Blending of the commercial LC‐polyester Rodrun LC‐3000 with the bisphenol‐A‐diglycidyl ether based diepoxide DOW D.E.R.330 alone and with the mixture of the diamine (MCDEA) and D.E.R.330 by means of a twin‐screw extruder has been investigated. Conditions to suppress curing of epoxide and amine during blending have been established. Due to the very low solubility of Rodrun in the diepoxide only LCP‐rich blends with a minimum content of 60 wt.‐% Rodrun could be obtained. The blends were investigated by SEM and thermal analysis (DSC, DMTA). Binary blends are immiscible while ternary blends appear miscible from DMTA up to 30 wt.‐% of epoxy/amine.

SEM micrograph of Rodrun moulded at 230 °C.     

Effect of Sample Configuration on the Morphology of Foamed LDPE/PP Blends Injection Molded by a Gas Counterpressure Process

Blends of isotactic poly(propylene) and low‐density polyethylene with different composition ratios were prepared through direct melt compounding on a twin‐screw extruder. The specimens with various geometric configurations were injection‐molded using a gas counterpressure process, using blends to which 0.5 wt.‐% of a blowing agent was added. The influence of blend composition and specimen geometry on the structure and morphology of the samples was investigated by SEM and WAXS. The thermal behavior of the blends was analyzed by DSC. It was found that the morphology of each region depended on the composition ratio and specimen geometry.

     

Telomerization of Butyl Methacrylate and 1‐Octadecanethiol by Reactive Extrusion

Butyl methacrylate and 1‐octadecanethiol telomers were prepared by radical reactive extrusion. The main advantages of the use of this processing technique are that mass reactions can be conducted and continuous production is achieved within a reduced reaction time and a correct temperature control. Preliminary studies concerned the choice of the reactants for the telomerization reaction and the adaptation of the telomerization reaction to the reactive extrusion process. The transfer constant to C₁₈H₃₇SH was measured, and then experimental studies were conducted to verify that the hypothesis and approximations made for kinetic modeling are realistic. Particularly, it was shown that the use of relatively high chain‐transfer agent to monomer concentration ratio had no perceptible effect on the monomer conversion kinetic. These results allowed the choice of reactive extrusion conditions. Telomers were prepared using a laboratory co‐rotating twin‐screw extruder. The effect of reaction conditions (temperature, 1‐octadecanethiol to monomer concentration ratio) and of processing conditions (throughput, screw rotation speed) on the residence time distributions, molar mass and monomer conversions were examined. This study allowed the continuous synthesis of butyl methacrylate telomers having variable controlled molar masses and complete monomer conversion.

Screw profile used in reactive extrusion telomerization.     

In Situ Polymerisation of Polyamide‐6 Nanocompounds from Caprolactam and Layered Silicates

An in situ process for the production of polyamide‐6 nanocompounds is investigated as an alternative to melt compounding. During the in situ production, the layered silicates are dispersed in the monomer caprolactam before the polymerisation in a twin screw extruder, leading to an intercalation of the silicates. The production of a polyamide compound containing 0, 2 and 4 wt.‐% nanoscale silicates was successful. An improvement of the elastic modulus of approximately 30–60% was reached. The figure shows the TEM micrograph of a nanocompound containing 2 wt.‐% nanoclay at a magnification of 30 000×.

     

Preparation and Characterization of Organic/Inorganic Polymer Composites Based on Mg‐Silicates

Summary: An organic‐inorganic hybrid material consisting of a 3‐(methacryloxy)propyl functionalized SiO₂/MgO framework was synthesized. This hybrid was successfully reacted with styrene, butyl acrylate and butyl methacrylate via a free radical emulsion polymerization to form polymer composites. The polymer composites were investigated by means of FT‐IR spectroscopy, TGA, DSC and rheometry. It is shown that the polymer is linked covalently to the organic/inorganic hybrid. Although the polymer content is rather low, the composites exhibit a polymer‐like character and enhanced mechanical properties compared to the corresponding homopolymers.

     

Comparative Characterization of PP Nano‐ and Microcomposites by In‐Mold Shrinkage Measurements and Structural Characteristics

Poly(propylene)‐clay nanocomposites and poly(propylene) containing conventional inorganic fillers such as calcium carbonate (CaCO₃) and glass fiber were used in a comparative study focusing on dimensional stability, structure, mechanical and thermal properties. Micro‐ and nanocomposites were prepared by melt blending in a twin‐screw extruder. The relative influence of each filler was observed from dimensional stability measurements and structural analysis by WAXD, TEM, and thermal and mechanical properties. At equal filler loadings, PP/clay nanocomposites exhibit an improvement in dimensional stability and were the only composites capable of reduced shrinkage in both in‐flow and cross‐flow directions. The flexural modulus of PP increased nearly 20% by compounding with 4% organoclay, as compared to a similar performance obtained by compounding with 10 wt.‐% of CaCO₃ or approximately 6 wt.‐% of glass fiber. The HDT and thermal stability of PP were enhanced by using nanoclay as filler.

     

Influence of Screw Speed on Electrical and Rheological Percolation of Melt‐Mixed High‐Impact Polystyrene/MWCNT Nanocomposites

The influence of screw speed on the electrical and rheological percolation of HIPS/MWCNT composites prepared via melt mixing was investigated. Microscopic examination of these composites using POM, FESEM and HRTEM revealed optimum MWCNT dispersion was achieved at intermediate screw speeds. On addition of MWCNTs to HIPS, the electrical conductivity of HIPS increased by up to 12 orders of magnitude. At screw speeds up to 100 rpm an electrical percolation of 1–3 wt.‐% was achieved. This increased to 3–5 wt.‐% when the screw speed was increased to 150 rpm. The onset of a rheological percolation was detected for an MWCNT loading of 5 wt.‐%, irrespective of screw speed employed. An up‐shift in the Raman G‐band of 24 cm^?1 was observed, implying strong interfacial interaction between HIPS and MWCNTs.

     

Direct Melt Extrusion Processing of Nylon 6/Clay Nanocomposites Based on Pristine Montmorillonite

Summary: An original direct melt extrusion processing of nylon 6/clay nanocomposites was reported based on pristine (Na⁺‐based) montmorillonite as well as a simple approach using a typical two‐screw extruder. By the application of intercalation agents as the thermodynamic assistants, this method is as an appropriate procedure for industrialized manufacture together with much lowered production cost. Interestingly enough, the synergistic effects of montmorillonite with other inorganic particulates was observed for the first time here.

X‐ray diffraction patterns of pristine MMT and nylon 6/MMT composites with grouped intercalation agents.     

Poly(propylene)/Clay Nanocomposites Prepared by Reactive Compounding with an Epoxy Based Masterbatch

Summary: Poly(propylene) (PP)/clay nanocomposites have been prepared via a novel reactive compounding approach, in which an epoxy based masterbatch consisting of 20 wt.‐% clay was introduced to poly(propylene) with the aid of a maleic anhydride grafted PP (MAPP). The masterbatch was prepared using a recently developed “slurry compounding” technique. After melt compounding, most clay particles have been exfoliated and dispersed into small stacks with several clay layers. WAXD data shows that the dispersion of clay is better at low clay content or high MAPP content. Due to the novelty of the preparation process and complication of the system, the tensile properties of nanocomposites exhibit some unique tendencies with varying the content of MAPP or masterbatch. It is believed that the yield strength and Young's modulus can be dramatically improved after minimizing the excess of unreacted epoxy and optimizing the dispersion of clay.

TEM micrograph of PP/clay nanocomposites prepared with epoxy based masterbatch.     

Flexible Use of Single‐Screw Extruders through Multiple‐Process Optimization

Using general‐purpose screws to process different types of material offers considerable cost advantages over special‐purpose screws. Designing screws of this type is generally a difficult task, since modifications to different aspects of the geometry can run counter to each other in some cases. Optimization software is thus of particular benefit here. For this reason, a program was developed for the optimization of general‐purpose screws. A central feature of this program is an appraisal system for the computer‐aided evaluation of single‐screw simulations. The performance of the software was verified on the basis of actual extrusion experiments.

Temperature measuring cross for measuring thermal homogeneity.     

Investigation Into Poly(propylene)/Montmorillonite/Calcium Carbonate Nanocomposites

Summary: A novel method was used to prepare poly(propylene)/montmorillonite/calcium carbonate nanocomposites by melt‐mixing, using pristine montmorillonite (MMT), hexadecyltrimethylammonium bromide (C16), calcium carbonate (CaCO₃) and a matrix in a twin‐screw extruder. Two different sizes of calcium carbonate were used (nanosized CaCO₃ and micron‐sized CaCO₃, the average sizes being 60 nm and 12 μm respectively). The nanocomposite structure was evidenced using X‐ray diffraction (XRD), transmission electron microscopy (TEM) and high resolution electronic microscopy (HREM). Tensile tests and Izod notch impact tests suggested that the incorporation of nanosized CaCO₃ into PP/montmorillonite nanocomposites increased the mechanical properties of the composites, but the improvement in the micro‐sized CaCO₃‐filled PP/montmorillonite nanocomposites was found to be minimal. The thermal stability and flammability properties were characterized by thermogravimetric analysis (TGA) and a cone calorimeter respectively.

     

Extrusion Foaming of Poly(styrene‐co‐acrylonitrile)/Clay Nanocomposites Using Supercritical CO2

Supercritical CO₂ has been used as a blowing agent to foam poly(styrene‐co‐acrylonitrile)‐based materials in a single screw extruder specially adapted to allow fluid injection. The cellular morphology depends on foaming temperature, more regular cells being obtained with decreasing extrusion temperature. In a second step, a natural and an organomodified nanoclay have been added for the purpose of imparting some flame resistance to the foamed material. The filler efficiency in reducing sample combustion rate appeared to be dependent on its delamination level inside the matrix and better results were obtained when the organomodified clay was first delaminated in the polymer in an efficient twin screw extruder using water assistance, prior to foaming in the single screw extruder.

     

Coaxial Electrospinning with Triton X‐100 Solutions as Sheath Fluids for Preparing PAN Nanofibers

Coaxial electrospinning using surfactants as sheath fluid for preparing high‐quality polymer nanofibers is studied. PAN nanofibers are fabricated using this process with Triton X‐100 solutions in DMF. FESEM demonstrates that the Triton X‐100 solution has a significant influence on the quality of the nanofibers. The nanofiber diameters can be controlled by adjusting the concentration of Triton X‐100 in the sheath fluids with a scaling law D = 640 C^?0.32. The mechanism of the influence of Triton X‐100 solutions on the formation of PAN fibers is discussed and it is demonstrated that coaxial electrospinning with surfactant solution is a facile method for achieving high‐quality polymer nanofibers.