Residence time and conversion in the extrusion of chemically reactive materials

Twin‐screw extruders offer improved control of the residence time distribution (RTD) and mixing in materials such as plastics, rubber and food. Based on the flow and the heat transfer characteristics obtained for a self‐wiping, co‐rotating twinscrew extruder, the residence time and chemical reaction are studied by tracking the particles. For normally starve‐fed twin‐screw extruders, the length of the completely filled section is calculated as function of the process variables using the coupling of the flow with the die. With a model of the solid conveying section, the RTD for the whole extruder is calculated for corn meal at different screw speeds and flow rates. The calculated variation of RTD with the screw speed and the flow rate yields good agreement with observations from many experiments. The variation of the fully filled section length, chemical conversion and mixing effectiveness are also obtained under different operation conditions. Most of the results are in qualitative agreement with experimental results and may be used as guidelines for extruder design and determination of optimal operating conditions.     

Maleic anhydride modification of polyolefin in an internal mixer and a twin‐screw extruder: Experiment and kinetic model

There has been little effort. to quantitatively understand graft copolymerization in batch and continuous mixers. Little information exists on the evolution of grafting reactions with respect to residence time in an internal mixer or along the screw axis in a twin‐screw extruder. In this study, maleic anhydride was grafted onto polypropylene in both an internal mixer and a twin screw extruder. The influence of residence time on degree of grafting in an internal mixer and a twin screw extruder was studied through measuring reaction yields with respect to reaction time in the internal mixer as well as along the screw axis in the extruder. The dependence of the degree of grafting with monomer and peroxide concentration was determined. A free radical kinetic model of the process was developed and compared to experiment. Kinetic parameters were determined.     

半连续化直接缩聚法制备聚对苯二甲酰对苯二胺浆粕

采用啮合同向旋转的双螺杆挤出机作为主反应器,半连续化直接缩聚法制备了聚对苯二甲酰对苯二胺（PPTA）浆粕.结果发现,较低的预缩聚反应温度有利于得到高相对分子质量的PPTA浆粕;而在双螺杆挤出机中主反应温度则应控制在70℃左右为宜;物料在双螺杆中的停留时间超过3 min,才满足制备PPTA浆粕的工艺要求.螺杆的转速对PPTA 浆粕的相对分子质量的提高不显著,若转速太快,使物料在双螺杆中的停留时间缩短,反而不利于得到性能较好的PPTA浆粕.本研究为直接缩聚法制备PPTA浆粕的进一步放大打下了基础.     

Non-Newtonian and isothermal analysis of flow of poly(methyl methacrylate) in a model twin screw extruder. Part I

The flow analysis network (FAN) method was modified to analyze the flow of poly(methyl methacrylate) (PMMA) in a model counter-rotating nonintermeshing screw extruder. The numerical prediction of the pressure profiles was compared with the experimental results. Flow patterns in the screw elements of the model counter-rotating nonintermeshing twin screw extruder were also predicted. A new flow path method was developed to calculate the residence time distribution. This result will be applied to analyze the flow during the reaction in the model twin screw extruder.     

Styrene grafting onto a polyolefin in an internal mixer and a twin‐screw extruder: Experiment and kinetic model

There has been relatively little effort to quantitatively understand graft copolymerizaution in either batch mixers or twin‐screw extruders. Most efforts have concentrated on grafting maleic anhydride, which does not homopolymerize. In this paper we consider grafting with styrene, which may homopolymerize as well as graft. The influence of residence time on degree of grafting in an internal mixer and a twin‐screw extruder were studied by measuring reaction yields with respect to reaction time in a mixer and along the screw axis in a twin‐screw extruder. The degree of grafting increased with initial monomer and peroxide concentration. Grafting reactions with three different peroxides were also investigated. The degree of styrene grafting in an internal mixer is slightly higher than that in a twin‐screw extruder. The rate of reaction along the screw axis in terms of residence time seems higher than for the batch mixer. The melt viscosity dropped dramatically with addition of peroxide. A kinetic scheme is proposed and the experimental results are critically compared with it.     

Residence time distribution in non-intermeshing counter-rotating twin-screw extruders

This paper deals with the residence time distribution (RTD) in a non-intermeshing counter rotating twin screw extruder. The RTDs were measured in three vent zones of the extruder sparately, and in the adjacent zones combined, using a soluble dye as the tracer. Assuming that the RTDs in the adjacent zones are independent of each other, the overall RTD was also calculated using a previously developed statistical theory. The theory has also confirmed the consistency of the present measurements. A predictive RTD model for the non-intermeshing twin screw extruder, based on the flow analysis of the individual screw zones and their statistical superposition, was also developed. The predictions are in good agreement with experiment.     

Analysis and experimental evaluation of twin screw extruders

Twin screw extruders can he classified according to their geometrical configuration. The main distinction is made between intermeshing and nonintermeshing extruders. Another distinguishing characteristic is the sense of rotation. The most important characteristics of the various twin screw extruders are examined, with particular emphasis on the effect of screw geometry on the conveying characteristics. A brief review is given of the state of the art in theoretical analysis of twin screw extruders. Experiments with two lab scale, intermeshing twin screw extruders are described, one co- and one counterrotating. Results are presented on power consumption, residence time distribution, and mixing characteristics of the two extruders. The counterrotating extruder exhibits a narrower residence time distribution and better dispersive mixing capability. The corotating extruder showed a better distributive mixing capability. These results can be explained in terms of the conveying and mixing mechanisms in both extruders. The overall extruder performance seems to be dominated by the effect of the intenneshing region. Any realistic, theoretical analysis of twin screw extruders should be centered around the flow behavior and mixing characteristics of the intermeshing region. The corotating extruder appears to be best suited for melt blending operations, while the counterrotating extruder seems to be preferred in operations where solid fillers have to be dispersed in a polymer matrix.     

The grafting of maleic anhydride on high density polyethylene in an extruder

The grafting of maleic anhydride (MAH) on high density polyethylene in a counter-rotating twin screw extruder has been studied. As the reaction kinetics appear to be affected by mass transfer, good micro mixing in the extruder is important. Due to the competing mechanisms of increasing mixing and decreasing residence times at increasing screw speed, and due to the complicated reaction scheme, various non-linearities exist that are prohibitive for simple optimization rules. The interaction diagram presented in this paper for a twin screw extruder as a MAH grafting reactor can be used for better understanding of the influence of the extruder parameters on the reaction process.     

Relationship between local residence time and distributive mixing in sections of a twin‐screw extruder

Local residence time and distributive mixing were measured in conveying sections and kneading blocks of a twin screw‐extruder. The residence time measurements were completed using carbon black as the tracer and an infrared temperature probe to detect the temperature decrease caused by the changing surface emissivity. The validity of this experimental technique was extensively evaluated. A mixing limited interfacial reaction between polymer tracers was used to directly measure the distributive mixing in the twin‐screw extruder. Possible relationships between mixing and residence time in the sections of the twin‐screw extruder were investigated by combining these two measurements. Distributive mixing in conveying sections was related to the local average residence time and the fill. In contrast, distributive mixing in kneading blocks was related to the local average number of screw revolutions experienced by the polymer. Forward stagger kneading discs achieved the greatest amount of distributive mixing, which was attributed to a combination of local stagnant flow regions and more frequent interfacial reorientation.     

Numerical nonisothermal flow analysis of non-Newtonian fluid in a nonintermeshing counter-rotating twin screw extruder

A simulation technique for nonisothermal flow analysis of non-Newtonian fluid in a nonintermeshing counter-rotating twin screw extruder was developed by modifying the flow analysis network (FAN) method. The local shear viscosity in the flow field was calculated by an iteration method combing the three types of mean shear rate functions. The modified Cross model and an Arrhenius-type function for temperature dependence were also introduced. Streamlines in the flow field are represented by computing the movements of fluid particles based on the flux fields. The computed residence time from the streamlines led us to solve the energy equation by replacing the coordinate system. The profiles of pressure, shear rate, shear viscosity, temperature, and residence time were simulated. The influence of operating and geometrical parameters on the screw characteristics are discussed. Further, residence time distribution (RTD), strain distribution function (SDF), and interfacial area growth are predicted from the computation of streamlines to analyze the mixing capabilities of the extruder.     

A study of residence time distribution in co‐rotating twin‐screw extruders. Part II: Experimental validation

In the first part of this paper, a new approach to model the residence time distribution (RTD) in a co‐rotating twin‐screw extruder was proposed. It consists of coupling a continuum mechanics approach with a chemical engineering one, yielding an RTD curve without any fitting parameter. However, the choice of ideal reactors that depict the behavior of each particular profile is not evident. In this second part, we present an experimental study based on two types of extruder (Leistritz 30–34 and Clextral BC45), different screw profiles and two measurement techniques (off‐line and in‐line). Global, partial and local RTD curves were obtained, both experimentally and by means of a deconvolution technique. This series of experiments permitted the definition of the best association between ideal reactors and screw elements. Using this association, a comparison has been made between experimental results and theoretical calculations. A good agreement was generally obtained in terms of the RTD shape, delay time, mean residence time and variance.     

Geometric mean vs. Arithmetic mean in extrusion residence time studies

Geometric mean residence time was compared with the arithmetic mean residence time for a residence time distribution study conducted on a twin‐screw extruder using a salt tracer and electrical conductivity measurements. Electrical conductivity of the cornmeal melt was measured at the die exit. All RTD curves obtained during the study were skewed to the right with very long tails that resulted in inflated arithmetic mean residence times. In order to alleviate the problem of long tails, different approaches were considered. Among these approaches, logarithmic transformation of the time scale to calculate the geometric mean residence time was shown to best represent the residence time distribution in terms of mean residence time and spread of the RTD. The log transformation of the time scale alleviates the problem of inappropriate shifting of the mean residence time due to long tails. The difference between the upper limits and lower limits for the log transformed data was found to be more appropriate to define the spreads of the distributions as the untransformed data resulted in quite variable spreads.     

Determination of twin‐screw extruder operational conditions for the preparation of thermoplastic vulcanizates on the basis of batch‐mixer results

In this study, we attempted to prepare a thermoplastic vulcanizate in a twin‐screw extruder by determining the screw configuration on the basis of batch‐mixer results. In this regard, two sets of information were used: (1) the time length, power consumption, and filling factor of different stages of the reactive blending process in the internal mixer and (2) the mean residence time and power consumption of the twin‐screw extruder. Morphological features of the samples taken from the melt‐mixing and dynamic vulcanization zones of the extruder with the selected screw configuration were found to be comparable with corresponding samples taken from an internal mixer reported in our previous study. The rheological and mechanical properties could provide valuable information to support the reliability of this study. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

啮合异向双螺杆挤出过程停留时间分布实验研究

通过对啮合异向双螺杆挤出过程常规螺纹元件螺杆组合及引入轴向循环段的螺杆组合停留时间的实验研究，分析了轴向循环段的引入对啮合异向双螺杆挤出过程停留时间及其分布的影响。     

Non-Newtonian and non-isothermal analysis of flow during polymerization of methyl methacrylate in a model twin screw extruder. Part II

The flow analysis network (FAN) method was modified to analyze the flow during polymerization of methyl methacrylate (MMA) in a model counter-rotating nonintermeshing screw extruder. The shear viscosity of the reactive mixture in the twin screw extruder was considered as a mixture of polymer and monomer. Thus, the reaction viscosity of the mixture of polymer and monomer was taken to be an explicit function dependent on the shear rate, temperature, conversion, and molecular weight. A new flow path method was developed to calculate the residence time distribution, which related to the degree of conversion. The numerical prediction of the velocity, temperature, viscosity, and pressure profiles during reaction in the model twin screw extruder is described.     

自洁型非对称同向双螺杆挤出机混合分析

设计了自洁型非对称同向双螺杆,并采用实验研究及数值模拟方法分析其混合特性。采用活性纳米CaCO3（nano CaCO3）填充线形低密度聚乙烯(PE LLD)的体系进行实验研究,在挤出量一定的前提下分别在自洁型非对称同向双螺杆挤出机以及普通同向双螺杆挤出机上造粒,通过扫描电子显微镜观察产品中nano CaCO3分布情况。结果表明,非对称双螺杆挤出PE LLD/nano CaCO3复合材料中nano CaCO3分布较为均匀,粒径尺寸更小,具有明显的增韧效果,这与数值模拟结果一致。     

The behaviour of an intermeshing twin screw extruder with catalyst immobilised screws as a three-phase reactor

The characteristics of an intermeshing co-rotating twin screw extruder were investigated as a three-phase reactor using a model reaction. The kinetics of the reaction and base line data were obtained using a high pressure stirred tank reactor. The feasibility of immobilisation of palladium on the surface of the screws as the catalyst was also studied. The behaviour of the extruder in batch and continuous mode and with slurry and non-slurry solutions was investigated. The results confirmed the superiority of the intermeshing co-rotating twin screw extruder as a novel three-phase reactor compared to the stirred tank reactor as a traditional three-phase reactor. The residence time distribution measurements indicated that the behaviour of the extruder approached perfect plug flow reactor with increasing viscosity of reaction solution.     

A study of residence time distribution in co‐rotating twin‐screw extruders. Part I: Theoretical modeling

A theoretical model to determine the residence time distribution (RTD) in a co‐rotating twin‐screw extruder is proposed. The method consists of coupling a continuum mechanics approach with a chemical engineering one and allows us to obtain the RTD without any adjustable parameter. The process parameters are obtained using Ludovic® twin‐screw modeling software, and ideal reactors are chosen to depict the screw profile. The influence of screw speed, feed rate and viscosity on RTD are described on a fictive screw profile. The predictions of the model are in qualitative agreement with literature data. The key point of this procedure is obviously the correct association between an ideal reactor and a screw element.     

Behavior of fully filled regions in a non‐intermeshing twin‐screw extruder

Twin‐screw extruders are operated with sequential filled and partially filled regions in order to perform the required unit processes. Channel fill length, defined as the length of fully filled regions in an extrusion screw, is gaining importance as a design parameter because of its implications on residence time distribution, distributive and dispersive mixing, and also process stability. A detailed study—experimental and theoretical—of the behavior of fill lengths in response to operating conditions (throughput, screw speed) and screw geometry is presented in this paper. Mean residence times were also measured for each geometry and operating condition. The apparatus consisted of a non‐intermeshing counter‐rotating twin‐screw extruder (NITSE) with a transparent (acrylic) barrel, fed with corn syrup (Newtonian at room temperature). Fill length exhibits a nonlinear relationship with specific throughput (Q/N), with the slope increasing monotonously as the throughput Q increases at a given screw speed N. The mean residence time exhibits a strong linear relationship with inverse specific throughput and inverse fill length. A theoretical model was developed to predict the filled length based on pressure‐throughput relationships taken from literature for this system, and the predictions were found to agree very well with experimental observations.