Simulation of disk extruder operation

Mathematical simulation of thermoplastic polymer processing by a disk extruder was considered. The results were compared with experimental data obtained in an extruder of a 200 mm diameter. The developed technique of calculation allows selection of design parameters of operational parts and disk speed for preset output of the disk extruder as well as energy-power parameters of extrusion.     

Time-resolved detection of x-ray scattering for studies of relaxation phenomena

An instrument for time-resolved detection of small-angle and wide-angle x-ray scattering is described. The apparatus consists of a 12-kW rotating-anode x-ray generator, a linear position-sensitive detector, a two-parameter multichannel analyzer to record the time-dependence of x-ray scattering patterns, a servo-controlled hydraulic sample deformation device, a temperature-controlled environmental chamber, a programmable function generator, a programmable timer and a microcomputer. The programmable function generator is used to control the mechanical or thermal stimulus on the sample under variable conditions and to synchronize the x-ray data acquisition with the stimulus. The environmental chamber allows temperature control of the sample between ?100 and 300°C. Two experimental methods, involving transient and oscillatory experiments, for time-resolved studies with this apparatus are discussed. Experimental studies on kinetics of oriented crystallization of cross-linked polybutadiene and on lamellar deformation of tubular-extruded poly(1-butene) films are presented as typical applications of time-resolved x-ray scattering technique.     

Characteristics of solid-state extruded polyethylene

This paper describes the properties of solid-state extruded polyethylene as a function of two primary processing variables, extrusion temperature, and area reduction. The polymer was extruded in sheet form, giving a material having an orthotropic mode of orientation. Property data are presented for melting temperature and heat of fusion; sonic modulus, yield stress, and elongation at fracture; small-angle x-ray scattering; optical absorption coefficient; and morphology for material etched by ion bombardment at liquid nitrogen temperature. Combining the present results with data previously reported in the literature, it is found that over the temperature range of about 90–120°C, where polyethylene can be successfully extruded to large area reductions, many properties of the extrudates show a surprisingly small dependence on extrusion temperature. A notable exception to this behavior is the elastic modulus, which increases significantly with increasing extrusion temperatures. In contrast to extrusion temperature, area reduction is found to have a major effect on nearly all properties of solid-state extruded polyethylene. In most cases, the form of this dependence is such that the properties change rapidly at small area reductions and much more slowly at large reductions.     

Construction of a wheat-flour state diagram

We use pressure-variable differential scanning calorimetry to detect and characterize thermally induced transitions (glass, melting, gelatinization) in pre- and post-extruded wheat flour. The resulting data allow us to construct a two-dimensional state diagram which maps the physical states that pre- and post-extruded wheat flour can assume, at constant pressure, as a function of moisture content, temperature, and the specific mechanical energy, SME, generated in the extruder. We describe how this state diagram can be used to map the path of extrusion processing, to assess the impact of extrusion conditions, and, ultimately, to design formulations and processing conditions that result in desired end-product attributes. For the extrudates, we find that the extent of processing-induced fragmentation, as monitored by reductions in the extrudate glass transition temperature,T _g, increases with the SME generated in the extruder. We demonstrate that a wheat-flour state diagram, which includes the glass curve of the wheat-flour extrudates produced at various SME values, allows one to predict and control the impact of processing conditions on extrudate properties.     

Structure of amorphous poly-(ethylmethacrylate): a wide-angle x-ray scattering study

The local, temperature dependent structure of poly-(ethylmethacrylate) was studied with wide-angle x-ray scattering. The results were set into context to recent wide-angle neutron scattering results as well as to the results from a multitude of studies of the dynamics of this polymer. The temperature dependence of the wide angle x-ray results point to the development of local order which is backed by the neutron scattering results and which is connected to characteristic temperatures of the relaxation dynamic T(g) and T(c). The poly-(ethylmethacrylate) was studied in its predominantly syndiotactic as well as predominantly isotactic state displaying vastly different local structures as manifested in the x-ray results.     

Influence of pineapple leaf fiber and it's surface treatment on molecular orientation in,and mechanical properties of,injection molded nylon composites

The objective of his work is to show that pineapple leaf fiber (PALF) can be used successfully to reinforce a high melting polymer such as nylon. One of the most important barriers to the utilization of lignocellulosic materials in polymer matrix composites is their limited temperature resistance. As a consequence, they are mostly used to reinforce low melting temperature polymers such as polyethylene and polypropylene as well as polystyrene. However, this work reveals that PALF can be used to reinforce nylon. This is because of its very low lignin content. Nylon 6/66 composites containing a fixed amount of 20 wt % PALF in the form of short and fine fibers were prepared with a laboratory twin screw extruder and then injection molded. The mechanical properties of three types of PALF, i.e. untreated, alkaline- and silane-treated, were studied. Significant improvements in modulus and heat distortion temperature were obtained. The crystalline structure and orientation in the injected composites were investigated with synchrotron wide angle x-ray scattering (WAXS). It was found that both PALF and nylon crystallites oriented well along the flow direction and this is the key factor for the improvements observed.     

Peroxide‐controlled degradation of poly(propylene): rheological behaviour and process modelling

The control of the molecular weight distribution of poly(propylene) resins by peroxide degradation is widely used in polymer industry. It allows to adjust the viscosity of these resins to the level required for processing applications. The purpose of this work was to characterise the influence of peroxide degradation on the rheological behaviour of an homopolymer PP and a block copolymer PP/PE, and to use these results to obtain a predictive model of the degradation in a twin‐screw extruder. By coupling a thermomechanical model of the twin‐screw extrusion process, a kinetic model of the considered reactions and the rheological behaviour, it was possible to calculate the changes in molecular weight along the extruder, during the peroxide‐controlled degradation.     

同向啮合双螺杆挤出机挤出过程的计算机模拟

计算机模拟研究了聚苯乙烯在TSE-35A型同向啮合双螺杆挤出机的挤出过程.计算得到不同喂料速率与不同转速下的停留时间分布,并与在线荧光法测量值对比,二者基本相符.确定了停留时间与螺杆转速及喂料速率之间的函数关系式.模拟结果还预测了喂料速率、螺杆转速等工艺参数对双螺杆内流场变量,如温度、填充率、压力及粘度等的影响.模拟计算有助于了解双螺杆挤出机内部聚合物材料流动状态及停留时间长短,从而指导实际聚合物生产.     

Modelling non-homogeneous flow and residence time distribution in a single-screw extruder by means of Markov chains

Non-homogeneous velocity distribution of the flow in the channel of a single-screw extruder is taken into account by a new model developed on the basis of the Markov chains. This model allows calculating the Residence Time Distribution (RTD) as well as the influence of the operating conditions on the process at any velocity distribution in the channel. It has been used to represent experimental results on mass flow rate and RTD previously obtained by extrusion of an acrylic polymer, Eudragit E100, at different temperatures and screw rotation speeds. The diffusion coefficient is the only adjusting parameter of the model. It was shown that it does not depend on the screw rotation speed and a correlation between this diffusion coefficient and the barrel temperature was found. The model provides global understanding of the transport kinetics of the flowing material through the extruder according to its behaviour and better describes the progress of the polymer flow all along the barrel from the hopper to the die.     

Stress-induced crystallization of poly(ethylene terephthalate)

Quenched amorphous films of poly(ethylene terephthalate) (PET) are stretched at temperatures less than T_g; changes in density, wide-angle x-ray diffraction, and small-angle light scattering are observed. The density increase upon stretching is attributed to an increase in crystallinity accompanied by an increase in the intensity of somewhat diffuse wide-angle x-ray diffraction and of both V_V and H_V small-angle light scattering patterns. The formation of oriented rodlike superstructure may be discerned from small-angle light scattering. Annealing of these samples increases the crystallinity as measured from density and leads to an increase in the perfection of crystalline and supercrystalline structure as measured by wide-angle x-ray diffraction and small-angle light scattering. The rodlike morphology changes to form spherulitelike aggregates as observed by small-angle light scattering and light micrographs. A model is proposed to explain the observations. Studies are extended to stretching films of PET above their T_g and observing changes in birefringence, density, wide-angle x-ray diffraction and small-angle light scattering as a function of elongation and stretching temperature. The formation of defomed spherulitelike superstructure may be discèrned from light micrographs. Results are compared with those obtained upon stretching films below T_g.     

Vibrational spectroscopic studies of laboratory scale polymer melt processing: Application to a thermoplastic polyurethane nanocomposite

A laboratory scale twin screw extruder has been interfaced with a near infrared (NIR) spectrometer via a fibre optic link so that NIR spectra can be collected continuously during the small scale experimental melt state processing of polymeric materials. This system can be used to investigate melt state processes such as reactive extrusion, in real time, in order to explore the kinetics and mechanism of the reaction. A further advantage of the system is that it has the capability to measure apparent viscosity simultaneously which gives important additional information about molecular weight changes and polymer degradation during processing. The system was used to study the melt processing of a nanocomposite consisting of a thermoplastic polyurethane and an organically modified layered silicate.     

Effects of processing on the structure of zein/oleic Acid films investigated by x-ray diffraction

Zein films plasticized with oleic acid were formed by solution casting, by the stretching of moldable resins, and by blown film extrusion. The effects of the forming process on film structure were investigated by X-ray diffraction. Wide-angle X-ray scattering (WAXS) patterns showed d-spacings at 4.5 and 10 A, which were attributed to the zein alpha-helix backbone and inter-helix packing, respectively. The 4.5 A d-spacing remained stable under processing while the 10 A d-spacing varied with processing treatment. Small-angle X-ray scattering (SAXS) detected a long-range periodicity for the formed films but not for unprocessed zein, which suggests that the forming process-promoted film structure development is possibly aided by oleic acid. The SAXS d-spacing varied among the samples (130-238 A) according to zein origin and film-forming method. X-ray scattering data suggest that the zein molecular structure resists processing but the zein supramolecular arrangements in the formed films are dependent on processing methods. Structural model for a zein molecular aggregate (based on Matsushima et al.10). Rectangular prisms of individual zein molecules are hexagonally aligned parallel to each other.     

On-line small-angle and wide-angle x-ray scattering studies on melt-spinning poly(vinylidene fluoride) tape using synchrotron radiation

On-line small-angle and wide-angle x-ray scattering experiments were performed during the melt spinning of polyvinylidene fluoride using the DESY synchrotron light source. In these studies, the melt-spinning apparatus consisting of a screw extruder, a metering pump, and a take-up motor system were assembled on two separate stepper-motor-driven platforms. To investigate the structure development during crystallization, the tape location at the desired distance from the die could be positioned at the beam level with synchronous vertical movement of extruder and take-up platforms. Small-angle and wide-angle x-ray patterns were taken simultaneously with a two-dimensional wire detector and one-dimensional wire detector. In a separate study, two-dimensional WAXS data were also taken under identical processing conditions to observe the off-equator diffraction behavior during the crystallization. The data obtained for a variety of take-up speeds generally indicate that SAXS d-spacings first appear large in the early stages of crystallization and gradually decrease along the spin-line (as the crystallization progresses). As the take-up speed increases, the crystallization onset position moves away from the die and d-spacings observed at the onset increase. In addition, the shape of the discrete scattering pattern starts as a meridional streak and converts to a teardrop shape with the tip of the pattern pointing toward the beam stop at the early stages of crystallization for high take-up speeds. This does not occur at low take-up speeds and is attributed to the differences in crystallization behavior which is spherulitic or sheaflike to row nucleated crystallites. Our studies also showed that SAXS patterns appear earlier than the wide-angle crystalline diffraction peaks indicating the SAXS technique to be more sensitive to the structural changes at these stages. An idealized model is developed to explain the observed patterns at high take-up speeds. This consists of two regimes. In regime 1, the periodic fluctuations due to the alternating crystalline and amorphous regions form along the regions where eventually the “shish” structures develop. In the second stage, a volume filling crystallization takes place between the existing crystallites along the shish structure and simultaneously radial overgrowth of crystallites (i.e., the “kebabs”) takes place. This causes the observed reduction in the average d-spacing. © 1993 John Wiley & Sons, Inc.     

Optical studies of the crystallization of trans 1,4-polybutadiene in stretched networks

The stress-induced crystallization of trans 1,4-polybutadiene was studied by observing changes in birefringence, stress, x-ray diffraction, and low angle light scattering during the course of crystallization. From these data, the degree of crystallinity was determined as a function of time, temperature, and elongation. Data were fitted to the Avrami equation, leading to an exponent of the order of unity. Light-scattering patterns suggested the simultaneous existence of two stretched forms: a rod-like structure oriented preferentially parallel to the stretching direction and a deformed spherulitelike growth with its greatest extension perpendicular to the stretching direction.     

The Use of In-line Quantitative Analysis to Follow Polymer Processing

In this work it is presented three applications of real time analysis during extrusion process using an optical device developed by our research group, which applies the concepts of light extinction. Monitoring of polymer blends morphology takes place to infer data concerned to dispersed phase size and concentration. The detector also enables information about melting temperature of polymer during extrusion and the level of viscous heating, and the exfoliation step during processing of a polymer-clay nanocomposite.     

Processing window for extrusion foaming of hydroxypropyl methylcellulose

Foamed materials are gaining an increased interest due to their good mechanical properties in relation to their low densities and an increased industrial demand can be expected. A few less attractive issues can however be associated with commodity foamed products. For instance the raw-material often originates from non-renewable, fossil-based, sources. Furthermore, degradation in nature is slow, therefor the disposed product is burned or end up in landfills. One possibility to reduce the impact on nature could be to produce foams from natural polymers such as starch or cellulose. In this study the possibility to produce foams from hydroxypropyl methylcellulose (HPMC) with water as blowing agent, by continuous extrusion, was investigated. A pre-study using a capillary viscometer, batch-extruder, was conducted to evaluate the foamability of HPMC. Due to promising results further experiments were conducted with a single-screw extruder. The goal was to find an adequate processing window for foaming. It was concluded that HPMC could successfully be foamed by continuous extrusion, although a careful tailoring of the processing parameters was required. Crucial parameters were here the temperature, pressure and residence time distribution in the extruder. Regions of the extruded foams were examined using optical and scanning electron microscopy and HPMC foams with a density in the range of that of fossil-based polymeric foams could be produced.     

Ethylene-Acrylic Acid Copolymers via Thermal Cracking

It has been found that ethylene-acrylic acid copolymers can be prepared by extruder cracking of ethylene-isopropyl acrylate copolymers. The cracking of the ester to the acid goes very smoothly to give 90-100% conversion; however, the melt index behavior of the product is quite complex. The melt index of the starting ester copolymer was 2.0, but the melt index of the thermally cracked product immediately after extrusion was only 0.1. On standing, the melt index of the product slowly increased to 30.0. This complex melt index behavior is related to anhydride formation and chain scission reaction in the extruder. The anhydride linkages give a pseudocross-linked structure and lead to an initial low melt index value. On standing, the anhydride groups are hydrolyzed with water from the atmosphere to give an uncross-linked acid copolymer. After the acid is formed, the main chain polymer scissions that have occurred during extrusion become evident and the high melt index value is observed.     

Crystal and amorphous orientation behavior of poly(chlorotrifluoroethylene) films in relation to crystalline superstructure

The relationship between the crystalline superstructure of polymer films and molecular orientation was studied in cold-drawn poly(chlorotrifluoroethylene) films by wide-angle x-ray diffraction, birefringence, and depolarized light scattering. By changing crystallization conditions, specimens with almost identical crystallinity but different crystalline superstructures were obtained; i.e., (1) a structure having a random array of crystallites, (2) a superstructure having a rod-like orientation correlation of the chains (a prespherulitic and sheaf-like superstructure), and (3) spherulitic superstructure. Upon stretching of specimens, crystallites initially randomly arranged orient with their chain axes along the stretching direction in accord with simple affine deformation. The amorphous chains also orient along the stretching direction. The orientation behavior of the specimens having the rod-like superstructure is similar to that of the specimens with a random array of crystallites, indicating that the interaction between the crystallites in the superstructure is relatively weak. The molecular orientation behavior of the spherulitic specimens, however, strongly deviates from simple affine deformation owing to strong interaction of the crystallites in the spherulites. The deviation can be interpreted in terms of spherulite deformation and of internal reorientation of chains within deformed spherulites.     

反应性挤出加工制备无卤阻燃高分子材料

聚合物反应性加工集聚合物加工与化学反应为一体,以聚合物加工装置为反应器,通过聚合物加工过程中的化学反应形成新物质和新结构,实现高分子材料的高性能化和功能化,是高分子材料科学的研究前沿之一.本文简要介绍了我们研究小组近年来采用反应性挤出加工制备高性能无卤阻燃高分子材料方面的研究进展.利用反应性挤出加工剪切力强、温度可控以及易于传质传热的特点实现了常规方法难以合成的高黏阻燃剂三聚氰胺磷酸盐季戊四醇酯（MPP）和三聚氰胺氰尿酸（MCA）的高效合成,制备了综合性能优良的聚丙烯/MPP、尼龙6/MCA等无卤阻燃高分子材料.研究所涉及的化学和物理方法,为聚合物无卤阻燃提供了高效、经济、环保和易于工业化的新技术,并拓宽了聚合物反应性加工的应用领域.     

The crystal structure of chitin and chitosan

Roentgenographic studies are performed to investigate the structural changes in chitin under pressure and shear during its solid-state processing using a twin-screw extruder and Bridgman anvils. The structure of chitosan synthesized by the solid-phase method is studied. Deformation under the conditions of dry extrusion grinding at room temperature reduces the crystallinity of the original chitin. Addition of water restores the crystallinity of the material up to the value characteristic of the original chitin. Extrusion processing of chitin at room temperature with addition of water virtually preserves the crystallinity and degree of ordering of the chitin crystal lattice, the same as ordinary dry grinding at an elevated (180°C) temperature. The maximum degree of amorphization of chitin is attained by its processing on Bridgman anvils. Solid-state synthesis of chitosan from chitin leads to a product with a more amorphous structure in comparison with chitosan produced by the suspension method.