In‐line optical detection in the transient state of extrusion polymer blending and reactive processing

Using an opticaldetector we followed the transient state of blends and composites, including a reactive blending during extrusion. The detection system is composed of a slit‐die with transparent windows fixed at the extruder exit, an optical arrangement with a W incandescent light microbulb with fixed luminescence, and a CdS photocell. As the tracer passes though the light path, it absorbs and backscatters part of the light, reducing the total transmitted light intensity. This is followed by changes in the voltage induced by the photocell to an electric circuit. We calibrated the response of the photocell at room temperature using a set of various films with a second phase dispersed, and obtained a logarithmic relationship. The tracers were particulate (phthalocyanine, TiO₂) and polymeric (PS, PA6) phases that absorb and scatter light, producing a residence time distribution (RTD) curvelike trace. Measurements were taken from a twin‐screw extruder Werner‐Pfleiderer ZSK 30 equipped with K‐Tron gravimetric feeders operating at various screw configurations and speeds, and feeding rates. The transient state of PP/PA6 blends can be easily detected optically and recorded using one of the components (either PP or PA6) added as a pulse in a steady‐state flow of the other component. With the simultaneous addition of a compatibilizer (polypropylene grafted with acrylic acid (PP‐g‐AA)) with the PA6, the intensity of the detector signal is substantially increased as a result of the PA6/PP‐g‐AA reaction. Quantitative off‐line infrared spectroscopy of the total amide group corroborated the in‐line measurements. These observations suggest that an in‐line optical detector may be a fast and simple way to study the flow behavior of blends and composites, including reactive processing. POLYM. ENG. SCI. 45:11–19, 2005. © 2004 Society of Plastics Engineers.     

A new approach to analyzing residence time and mixing in a co-rotating twin screw extruder

A series of experiments was conducted to determine what correlations exist between an experimental parameter, percent drag flow, and other parameters such as head, tail and mean residence time. Experimentation was carried out on two polymer systems, a model system of near-Newtonian fluid and a viscoelastic system of polyisoprene with several additives. To aid in the residence time analysis, data from three literature sources were cited and replotted. A family of residence time curves for a partially filled system can be combined into one curve by plotting the number of screw revolutions carrying the tracer to the extruder exit versus the percent drag flow. This method of plotting the data for each screw configuration estimates the mean residence time for any throughput and screw speed once a few data points are taken. In all four sets of experiments, the number of screw revolutions carrying the tracer to the exit decreases with increasing percent drag flow. The filled volume of the extruder was calculated from residence time data to show that percent drag flow is linearly related to extruder filled volume. When percent drag flow increased in the viscoelastic system the following results were recorded: fraction of polymer residence time spent in conveying elements increased, fraction of residence time spent in mixing elements decreased, polymer Mooney viscosity increased, number and weight average molecular weights increased and polydispersivity increased.     

The Mixing Efficiency of an Eccentric‐Disc Kneading Zone in Intermeshing Co‐ and Counter‐Rotating Twin‐Screw Extruders

The distributive mixing efficiency of a twin‐screw extruder kneading zone consisting of eccentric disc elements was measured using an online video technique. Both co‐ and counter‐rotation were examined. Viscous Newtonian silicone oil was used as model liquid and black iron oxide pigment served as tracer substance. Under isoviscous, creeping flow and non‐diffusive conditions and for a fixed flow rate ratio of the colored and uncolored feed streams, the intensity of segregation S is only a function of the kinematic parameter Λ (the ratio of the imposed extruder throughput and the throughput at zero axial pressure gradient). The measured dependency of S on Λ is in qualitative agreement with the results of Pawlowski for a single screw extruder. The data was also plotted against the dimensionless speed of rotation, i.e. the product of the screw speed and the average residence time within the mixing section. This brings the abscissa ranges for mixers with different conveying capacity closer together, and differences in mixing efficiency between the tested configurations can be better interpreted. The energetic efficiency of the mixers investigated is compared by applying the concept of specific action. This helps to decide which mixer geometry and operating conditions produce a given homogeneity with the lowest amount of work done by viscous forces.     

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.     

Graft copolymerisation of N‐vinyl pyrrolidone onto polypropylene copolymer in melt: Effect of grafting on thermomechanical properties and paint adhesion

N‐vinyl pyrrolidone (NVP) was grafted onto a polypropylene copolymer (PP) in melt in a Brabender Plasticorder and single screw extruder. The effect of variation of dicumyl peroxide (DCP) and lupersol (LUP) concentrations alone and with 20 wt % NVP concentration in the Brabender Plasticorder on Melt Flow Index (MFI) and final torque values was studied. Variation of NVP concentration (1–10 wt %) at a fixed DCP concentration on percent grafting (G) and MFI was also studied in the single screw extruder. The graft copolymers (PP‐g‐NVP) obtained by reaction of PP with NVP were soxhlet extracted with isopropanol to remove homopolymer, dried, and finally characterized by Fourier transform infrared (FTIR), differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The PP‐g‐NVP (0–30 wt %) was used as an additive with PP, extruded in the single screw extruder, molded, and the mechanical properties and paint adhesion was measured. MFI values increased and torque values decreased with an increase in initiator concentration, indicating the dominance of the peroxide‐initiated scission reaction over grafting. DCP gave higher grafting compared to LUP. When NVP concentration was increased, MFI values increased initially due to more scission, and then decreased, indicating more graft copolymer formation. Mechanical properties increased by incorporation of PP‐g‐NVP as an additive than PP‐g‐NVP alone. Paint adhesion increased by the presence of PP‐g‐NVP as additive especially with polyurethane primer. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2173–2180, 2003     

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     

Measuring the residence time distribution in a twin screw extruder with the use of NIR‐spectroscopy

The mean residence time (MRT) and the residence time distribution (RTD) of polypropylene in a twin‐screw extruder was determined directly in‐line with the help of near infrared (NIR) spectroscopy and the use of an UV‐absorber as tracer. Different experiment alignments such as screw speed, mass throughput, back pressure as well as tracer content and their influence on MRT and RTD have been investigated. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 39919.     

利用往复扰动螺棱强化单螺杆挤出机内混合模拟表征

提出了采用副螺棱轴向往复运动提高单螺杆挤出机混合的结构并建立了相应的数学模型。对挤出机内牛顿流体三维周期性流动和混合过程进行了数值模拟。采用有限体积方法,变量分布采用交错网格,副螺棱的周期性运动边界通过叠加网格方式实现。采用4阶Runge-Kutta方法实现流体追踪计算,得到了示踪剂界面增长及累积停留时间分布。采用Poincaré 截面揭示混沌混合存在的区域,证实了副螺棱往复运动能够产生混沌混合效应提高螺槽内的混合效果,与其位置固定时相比,缩短了平均停留时间,停留时间分布变窄。作为对比,同时分析了常规的副螺棱位置固定的单螺杆挤出机内的相应混合行为。     

A laboratory spiral disk extruder for flow visualization

A laboratory spiral‐disk extruder for the study of gas entrainment phenomena is presented. The rotating plate is transparent, thus allowing for the direct observation of the steady liquid‐gas interface when operating under starve‐fed conditions. The extruder flow is modeled with the conventional single screw extruder approach. This leads to a simple working equation for the spiral screw, which is formally identical to the classical screw equation for standard extruders. The model is validated by comparing the predictions with experimental data taken in both closed and open die configurations.     

Continuous polymerization of ω‐lauryl lactam in an intermeshing corotating twin‐screw extruder

This article describes the synthesis of poly(ω‐lauryl lactam) by a reactive extrusion process. Anionic ring‐opening polymerization was performed in an intermeshing corotating twin‐screw extruder. We investigated the evolution of conversion of ω‐lauryl lactam as a function of reaction time, screw speeds, different feed rates, and different screw configurations along the screw axis in a twin‐screw extruder. For comparison with continuous polymerization in a twin‐screw extruder, we studied polymerization in an internal mixer, which was considered a batch reactor. We found the final conversion of ω‐lauryl lactam made in a twin‐screw extruder was higher than in an internal mixer. Higher molecular weights are found at lower screw speeds and feed rates. Melt viscosities and mechanical properties of the polymers were measured. Residence time, molecular weights, and shear mixing have the main effect on the mechanical properties of products. The twin‐screw extruder performance was interpreted in terms of commercial software. It was found that twin‐screw extruder reaction rate was higher than those in the batch reactor and increased locally with screw speed and feed rate. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1605–1620, 2005     

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.     

Tracer‐compatibilizer: Synthesis and applications in polymer blending processes

This article reports on a route to synthesizing fluorescent labeled graft copolymers, on the one hand; and on a concept of tracer‐compatibilizer for facile build‐up of emulsification curves of polymer blends, on the other hand. For these purposes, blends composed of polystyrene (PS) and polyamide 6 (PA6) are chosen. The synthesis of the corresponding tracer‐compatibilizer consists of three steps: (1) copolymerization of styrene with 3‐isopropenyl‐α,α'‐dimethybenzyl isocyanate (TMI); (2) conversion of a fraction of the isocyanate moieties of the resulting copolymer into anthracene ones upon reacting with 9‐(methylamino‐methyl)anthracene (MAMA); and (3) polymerization of ε‐caprolactam (CL) from the remaining isocyanate moieties. The resulting fluorescent labeled graft copolymer, denoted as PS‐g‐PA6‐Ant, is used to build up emulsification curves of PS/PA6 blends in a twin screw extruder (TSE), showing great usefulness of the concept of tracer‐compatibilizer. POLYM. ENG. SCI. 2012. © 2011 Society of Plastics Engineers     

同向双螺杆挤出机的停留时间分布及填充度

引 言 双螺杆挤出机在高分子材料加工中已被广泛地应用于聚合物共混改性、反应挤出及高分子可控降解等各个方面[1].但先前对挤出过程研究较少,一般仅停留在"黑箱"型经验操作的层面,主要以定性的机械设计为主.     

Measurements of residence time distribution for the peroxide degradation of polypropylene in a single-screw plasticating extruder

Measurements of the residence time distribution (RTD) in a single-screw plasticating extruder were carried out during experimental studies of the peroxide-initiated controlled chemical degradation of polypropylene (PP). A radioactive tracer method was employed, and the effect of screw speed, temperature, and reaction on the RTD was examined. An increase of the peroxide concentration resulted in a broader distribution whereas an increase of the extrusion temperature was found to result in a narrower distribution. Use of low screw speeds simply increased the time delay through the extruder without affecting considerably the breadth of distribution. Results obtained from the present experiments were compared with several theoretical models.     

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.     

Assessing local residence time distributions in screw extruders through a new in‐line measurement instrument

This work aimed at developing a new instrument to measure in real time the residence time distribution (RTD) in screw extruders. The instrument followed the same principle as the one reported in the literature but possessed several important advantages. For example, the detection system had two probes that allowed to simultaneously measure RTDs at any two different locations of an extruder, thus providing the possibility of calculating the local RTD between them by a deconvolution method based on a statistical theory for the RTD. Its performance was evaluated on a corotating twin‐screw extruder using anthracene as tracer and polystyrene as flowing material. The effects of various process parameters such as feed rate and screw speed on the RTDs were investigated. The emphasis was placed, however, on the effect of the staggering angle of kneading discs on local RTDs both in the kneading zone itself and its neighboring upstream and downstream screw zones. This work is in support of an ongoing project on the simulation of flow in corotating twin‐screw extruders. POLYM. ENG. SCI., 46:510–519, 2006. © 2006 Society of Plastics Engineers.     

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。     

Modeling of a cokneader for the manufacturing of composite materials having absorbent properties at ultra‐high‐frequency waves. Part 1: Modeling of flow from residence time distribution investigations

The purpose of this study is to gain better understanding of flow patterns and mixing conditions in a particular single‐screw extruder: the Buss Cokneader. To this end, the residence time distribution (RTD) of the polymer was investigated experimentally for different combinations of the operating variables (i.e. feed rate, screw rotation speed). The measurement of RTD used a standard stimulus‐response technique. Two kinds of tracer were used: free anthracene and anthracene grafted on the polymer. It was shown that only the second could characterize the actual flow of the polymer in the extruder. It does not perturb the flow and has the same rheological behavior as the studied fluid. Thanks to the RTD data, a model of the extruder based on the combination of ideal reactors, such as continuous stirred tank reactors or plug flow reactors, was finally set up. The establishment of relationships between model parameters and extrusion conditions allowed the prediction of RTD with good agreement.     

Chaotic mixing in a single‐screw extruder with a moving internal baffle

A geometry in which the mixing of a single‐screw extruder was enhanced by a reciprocating baffle is proposed in this article. The effect of the baffle's amplitude on the mixing kinematics of the screw channel was investigated. A model with the baffle lower than the screw channel and the corresponding mathematical model were developed. The periodic flow and mixing performance of Newtonian fluid in such an extruder were numerically simulated. The finite volume method was used, and the flow domain was meshed by staggered grids with the periodic boundary conditions of the barrier motion being imposed by the mesh supposition technique. Fluid particle tracking was performed by a fourth‐order Runge–Kutta scheme. Distributive mixing was visualized by the evolution of passive tracers initially located at different positions. The growth of the interface stretch of tracers with time and the cumulative residence time distribution were also obtained. Poincaré sections were applied to reveal the geometrical scale of chaotic mixing patterns and the regions with embedded regular laminar flows. For comparison, the mixing performance in a conventional single extruder with fixed baffle was also investigated. POLYM. ENG. SCI., 54:198–207, 2014. © 2013 Society of Plastics Engineers     

Evolution of peroxide‐induced thermomechanical degradation of polypropylene along the extruder

An experimental study of the peroxide‐induced degradation of polypropylene in a corotating twin‐screw extruder, operating under various conditions, was reported. Runs were performed without and with peroxide in different concentrations. The evolution of the chemical reactions along the extruder was characterized by on‐line rheological measurements and by determination of the molecular weight of samples collected at the same locations. The results evidenced the relationships between peroxide concentration and processing conditions with rheological properties and molecular structure of the modified materials. The concept of chain‐scission distribution function elucidated the mechanisms involved in the thermomechanical degradation of PP, which is by chain scission and is dependent on the level of stress imposed by the screw elements, temperature, and concentration of hydrogen‐abstracting agents. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91:2711–2720, 2004