In‐line near‐infrared spectroscopy: A tool to monitor the preparation of polymer‐clay nanocomposites in extruders

In‐line diffuse reflectance and on‐line transmission near‐infrared spectroscopy (NIR) measurements are performed at the same location of the barrel of a twin screw extruder during the preparation of a polypropylene/clay nanocomposite. Their performance is evaluated by means of a 7‐parameter chemometric model using off‐line rheological and structural (FTIR) data obtained from samples prepared under different screw speed, compatibilizer content and clay loading, as well as a process‐related thermomechanical index. Despite the higher variability of the diffuse reflectance signal, the two models present analogous high quality indices. The aptness of the reflectance measurements is thus validated, which has direct practical advantages, as this probe can be fixed in any typical melt pressure transducer port. The probe is then used for the real‐time in‐line monitoring of the production of the same nanocomposite but now using different throughputs, and the chemometric‐based predictions are compared with experimental off‐line characterization data. The nonlinear effect of throughput is correctly anticipated. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Study of pseudo‐multilayer structures based on starch‐polycaprolactone extruded blends

This article is focused on the analysis of the structure‐process relationships of biodegradable materials. It is mainly focused on the analysis of phase separation phenomenon occurring during the extrusion of plasticized starch/polycaprolactone blends, in a slit die. Rheological characterizations are carried out, in‐line in an instrumented slit die at the exit of the extruder and, out‐line with different rheometers. In certain conditions, a pseudo‐multilayer structure can be generated with a polyester rich skin. Then, Electron Spectroscopy for Chemical Analysis (ESCA) and Fourier Transformed Infrared Attenuated Total Reflectance (FTIR‐ATR) analyses are conducted to evaluate semi‐quantitatively the polyester surface enrichment. In the range of available shear rates, the phase separation is mainly driven by the molecular weight of polycaprolactone, linked to its molten state viscosity. Three zones of surface enrichment, dependent on the molecular weights, are identified. Above 60,000 g·mol^?1, no surface enrichment could be detected; below 37,000 g·mol^?1, the phase separation occurs with no dependence on the processing conditions; between these two limits, the phase separation depends on both, the formulation and the processing conditions. A correlation between the rheological measurements and the phase separation is given. A predictive criterion based on the viscous behavior of the blend is established. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

The application of an extrusion slit die in the rheological measurements of polyethylene composites with calcium carbonate using an in‐line rheometer

This article has reported the results of rheological testing of low‐density polyethylene (LDPE) and its calcium carbonate composites containing 7, 14, 21, and 28 wt% filler, respectively. The polymer composites were produced in a twin‐screw extrusion process. The assessment of the rheological properties of the polymeric materials was made under extrusion process conditions, using an in‐line rheometer with an extrusion slit die (W = 20, H = 2, L = 150 mm), at temperatures of 170°C, 180°C, and 190°C, respectively. The rheological parameters were determined based on the Ostwald‐de‐Waele power law model. The employed testing stand enabled the assessment of the effect of filler addition and slit die temperature on the variations in viscosity, power law index (n), consistency index (K), maximum flow velocity (V_max), and maximum flow profiles (V_z), under the conditions of technological processing (extrusion) of plastics. POLYM. ENG. SCI., 59:E16–E24, 2019. © 2018 Society of Plastics Engineers     

Die design for rigid PVC—the effect of die land length on extrudate swell

PVC profile extrusion compounds have a unique morphology. While other polymers gradually decrease in extrusion die swell with increasing length/thickness (L/D) ratio, PVC profile extrusion compounds have a low die swell, quite independent of the die's L/D ratio in the range of 5 to 20. The fact that the die land length can be changed without changing the extrudate swell is an important consideration, which makes die design and balancing dies simpler and easier for PVC profile extrusion compounds. While other polymers substantially increase extrudate swell with increased shear rate, the swell of the PVC profile compounds is not much affected by shear or extrusion rate. This unique behavior allows wider processing latitude in profile extrusion and faster extrusion rates than with other polymers. Another unique factor in the rheology of PVC profile extrusion compounds is that extrusion die swell increases with increasing melt temperature, while other polymers have decreasing die swell with increasing melt temperature. The unusual rheology of PVC profile extrusion compounds is attributed to its unique melt morphology, where the melt flow units are 1 um bundles and molecules that have low surface to surface interaction and entanglement at low processing temperatures but increased melting and increased entanglement at higher processing temperatures. Other polymers, unlike PVC, have melt flow at the molecular level.     

Effect of acrylic processing aids on PVC die swell

The die swell behavior of PVC melts is a manifestation of melt elasticity and is of considerable commercial as well as fundamental importance. This behavior is a critical issue in extrusion blow molding application where die swell (i.e. parison thickness) needs to be controlled. Advantageously, the addition of high molecular weight acrylic processing aids to PVC provides better die swell control, thus, improving dramatically the processability of PVC. Hence, knowledge of molecular weight variables of such acrylic processing aids is important from both the commercial and rheological point of view. Various acrylic processing aids were prepared by polymerization designed to provide systematic variation of molecular parameters. Molecular weight distribution of the polymers was characterized by GPC, and their die swell behavior in a typical PVC blow molding formulation was determined at 200°C over various range of residence times using different L/D capillary dies. The results are presented showing effects of specific molecular variables.     

The effect of crystallites on the rheological properties of microphase‐separated PVC‐PBA‐PVC triblock copolymers obtained by single electron transfer‐degenerative chain transfer living radical polymerization

Linear and nonlinear rheological properties of poly(vinyl chloride) (PVC)‐poly(n‐butyl acrylate)‐PVC triblocks of different compositions, obtained by single electron transfer‐degenerative chain transfer living radical polymerization, are investigated, focusing on the effect of crystallites. Dynamic mechanical thermal analysis results show the existence of two glass transition temperatures, denoting microphase segregation. However, rather than phase separation, it is the presence of two types of crystals that melt at T_m1 = 127 ± 0.8°C and T_m2 = 185 ± 2°C, respectively, the factor that determines the rheological response of the copolymers. To the difference with PVC homopolymers, extrusion flow measurements at very low temperatures (T = 100°C) are possible with the copolymers. A change in the viscosity‐temperature dependence is observed below and above the lowest melting temperature. Notwithstanding the microphase separation and the presence of crystallites, experiments carried out in conditions similar to industrial processing reveal a remarkable viscosity reduction for our copolymers with respect to PVC obtained by single electron transfer‐degenerative chain transfer living radical polymerization, conventional PVC, and PVC/[diethyl‐(2‐ethylhexyl) phthalate] compounds. Extrudates free of surface instabilities are obtained at low extrusion temperatures, such as 90–100°C. J. VINYL ADDIT. TECHNOL., 21:24–32, 2015. © 2014 Society of Plastics Engineers     

In‐line Rheological Behaviors of Gun Propellant Substitute Assisted with Supercritical CO2 in Extrusion Processing

To improve the rheological behaviors of gun propellants, SC‐CO₂ was injected into the gun propellant substitute in extrusion processing. A slit die rheometer was used to investigate the in‐line rheological behaviors of CA solution. A Power model was applied to describe the rheological behaviors of CA/SC‐CO₂ mixtures. The viscosity and pressure of CA solution obviously decrease with the assistance of SC‐CO₂. The viscosity of CA solution reduces by 16.64 % at 55 °C and 10 s⁻¹ with the presence of SC‐CO₂. Increasing the processing temperature makes the viscosity of CA/SC‐CO₂ mixture decrease remarkably, but it weakens the plasticization of SC‐CO₂ to CA. Although the increasing solvent content improves the flow of the CA/SC‐CO₂ mixture, it lowers the strength of CA/SC‐CO₂ mixture, which is not in favor of the quality of product. The investigation of the in‐line rheological behaviors of CA/SC‐CO₂ mixture is fundamental and important for the safe extrusion of gun propellants assisted with SC‐CO₂.     

Rheological evaluation of metallocene polyethylenes with processing aids by multi‐wave oscillations

During the die flow of metallocene polyethylenes, flow instabilities may occur. Namely, wall slip, “sharkskin,” and stick‐slip (pressure oscillations) and gross fracture may be obtained depending on the volume flow rate and die geometry. It was reported that fluoroelastomers and boron nitride powders with hexagonal crystal structure can be used as suitable processing aids in melt extrusion processes. Fluoroelastomers at low concentrations act as die lubricants and may eliminate flow instabilities such as surface and stick‐slip melt fracture. On the other hand, specific boron nitride powders may not only eliminate surface and stick‐slip melt fracture, but also postpone gross melt fracture to higher volume flow rates. In this paper, a way for quantitative differentiation of the influence of polymer processing additives on rheological behavior is shown. Standard material functions show no clear‐cut differences. However, using multi‐wave oscillations with higher strain amplitudes make a quantitative assessment possible. Polym. Eng. Sci. 44:2047–2051, 2004. © 2004 Society of Plastics Engineers.     

Anomalous rheological behavior of polyethylene melts in the gross melt fracture regime in the capillary extrusion: Effect of long‐chain branching

During a capillary extrusion with several different polyethylenes, we observe an abnormal rheological behavior. The nominal viscosity of some polyethylene melt in the gross melt fracture regime does not change with the temperature. Several metallocene‐catalyzed linear low density polyethylene are investigated. Among them, polyethylenes, which have long‐chain branches in their main chain, show this abnormal rheological behavior. By capillary extrusion experiments with various dies of different L/D ratios, it is inferred that the abnormal rheological behavior is originated in the die land, not die entrance nor die exit. From various experiments, we notice that this abnormal phenomenon may be used to detect long‐chain branch of PE. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Rheological effects of the incorporation of chlorinated polyethylene compatibilizers in a HDPE/PVC blend

Small‐amplitude oscillatory measurements, creep and recoil experiments, capillary extrusion flow and shrinkage measurements have been performed to elucidate the effect of block and random chlorinated polyethylene (CPE) on the rheological properties of a ternary high density polyethylene (HDPE)/ poly(vinyl chloride) (PVC)/CPE system. It is observed that the storage modulus, the complex viscosity and the steady stale viscosity at low shear rates decrease when a small amount of CPE is incorporated to 50/50 (wt.) HDPE/PVC binary blend. However, at high shear rates, in experiments performed in extrusion flow, the trend is reversed, and the incorporation of CPE to the binary blend increases viscosity. The high melt elasticity of HOPE is severely reduced when this polymer is mixed with PVC, but when CPE is included as a third component, elastic recovery is considerably increased. All these rheological results, which are independent of type (block or random) of CPE used, are explained considering the morphological changes produced by CPE and during extrusion flow.     

Design and optimization of an extrusion die for the production of wood–plastic composite profiles

In this work, the optimization of an extrusion die designed for the production of a wood–plastic composite (WPC) decking profile is investigated. The optimization was performed with the help of numerical tools, more precisely, by solving the continuity and momentum conservation equations that govern such flow, and aiming to balance properly the flow distribution at the extrusion die flow channel outlet. To capture the rheological behavior of the material, we used a Bird‐Carreau model with parameters obtained from a fit to the (shear viscosity versus shear‐rate) experimental data, collected from rheological tests. To yield a balanced output flow, several numerical runs were performed by adjusting the flow restriction at different regions of the flow‐channel parallel zone cross‐section. The simulations were compared with the experimental results and an excellent qualitative agreement was obtained, allowing, in this way, to attain a good balancing of the output flow and emphasizing the advantages of using numerical tools to aid the design of profile extrusion dies. POLYM. ENG. SCI., 55:1849?1855, 2015. © 2014 Society of Plastics Engineers     

Adjustable Twin‐Slit Rheometer for Shear Viscosity Measurement of Extruded Complex Starchy Melts

An online rheometer with an innovative system of height‐adjustable and independently temperature‐controlled slits was designed to measure the shear viscosity of extruded wheat bran fiber‐containing starchy materials. The range of melt pressures and temperatures, obtained with a die, could be covered by the rheometer. A close ingredient thermomechanical history in the extruder was achieved both with the die and the rheometer, while covering an apparent shear rate from 5 to 30 s^–1. Although minor technical problems remained, first rheological data were obtained and showed a pseudoplastic flow behavior for all recipes. The flow curves were fitted by a power law model. Wheat bran fiber addition influenced both the K‐ and n‐values, leading to more shear‐thinning melt behavior and an increase in true shear viscosity. Only a limited effect on these values was found in these preliminary experiments when further increasing the fiber content.     

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.     

Rheological behavior and thermal properties of poly(butyl acrylate‐co‐2‐ethylhexyl acrylate)‐grafted vinyl chloride resin

The rheological behavior and thermal properties of a poly(butyl acrylate‐co‐2‐ethylhexyl acrylate) [P(BA‐EHA)]‐grafted vinyl chloride (VC) composite resin [P(BA‐EHA)/poly(vinyl chloride) (PVC)] and its materials were investigated. The rheological behavior, thermal stability, and Vicat softening temperature (VST) of P(BA‐EHA)/PVC were measured with capillary rheometry, thermal analysis, and VST testing, respectively. The effects of the P(BA‐EHA) content and the polymerization temperature of grafted VC on the rheological behavior of the composite resin were examined. The weight loss of the composite resin and its extracted remainder via heating were analyzed. The influence of the content and crosslinking degree of P(BA‐EHA) and the polymerization temperature of the grafted VC on VST of the materials was determined. The results indicated the pseudoplastic‐flow nature of the composite resin. The flow property of the modified PVC resin was improved because of the incorporation of the acrylate polymer. The molecular weight of PVC greatly influenced the flow behavior and VST of the composite resin and its materials. The flowability of the composite resin markedly increased, and the VST of its materials decreased as the polymerization temperature of the grafted VC increased. The initial degradation temperature of the composite resin increased as the P(BA‐EHA) content increased. The VST of the samples was enhanced a little as the content of the crosslinking agent increased in P(BA‐EHA). As expected, the composite resin, with good impact resistance, had better heating stability and flowability than pure PVC, whereas the VST of the material decreased little with increasing P(BA‐EHA) content. Therefore, P(BA‐EHA)/PVC resins prepared by seeded emulsion polymerization have excellent potential for widespread applications. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 419–426, 2005     

Investigation of combination of finite element formulation and element type on the accuracy of 3D modeling of polymeric fluid flow in an extrusion die

The aim of this work is to investigate the effect of finite element formulation and element type on the accuracy of 3D modeling of generalized Newtonian fluid flow in complex domains. Computer models based on three finite element solution schemes (mixed, continuous, and discrete penalty), and two element types (hexahedral and tetrahedral) in a 3D framework were developed. The well‐known Carreau model was used to reflect the rheological behavior of the fluid. To determine the validity of the developed computer simulations, the flow of two high‐density polyethylene (HDPE) melts with different viscosities through an extrusion die was simulated and compared with experimentally measured data. Comparison showed that the three methods produced nearly the same results with the hexahedral elements. However, continuous penalty method using tetrahedral elements demonstrated an extreme discrepancy from the experimental data. Discrete penalty method was unable to predict secondary variable (pressure) accurately using tetrahedral elements. The best results were obtained by the use of mixed method in conjunction with tetrahedral elements. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of dynamic cross‐linking on melt rheological properties of polypropylene/ethylene‐propylene‐diene rubber blends

Study of melts rheological properties of unvulcanized and dynamically vulcanized polypropylene (PP)/ethylene‐propylene‐diene rubber (EPDM) blends, at blending ratios 10–40 wt %, EPDM, are reported. Blends were prepared by melt mixing in an internal mixer at 190°C and rheological parameters have been evaluated at 220°C by single screw capillary rheometer. Vulcanization was performed with dimethylol phenolic resin. The effects of (i) blend composition; (ii) shear rate or shear stress on melt viscosity; (iii) shear sensitivity and flow characteristics at processing shear; (iv) melt elasticity of the extrudate; and (v) dynamic cross‐linking effect on the processing characteristics of the blends were studied. The melt viscosity increases with increasing EPDM concentration and decreased with increasing intensity of the shear mixing for all compositions. In comparison to the unvulcanized blends, dynamically vulcanized blends display highly pseudoplastic behavior provides unique processing characteristics that enable to perform well in both injection molding and extusion. The high viscosity at low shear rate provides the integrity of the extrudate during extrusion, and the low viscosity at high shear rate enables low injection pressure and less injection time. The low die‐swell characteristics of vulcanizate blends also give high precision for dimensional control during extrusion. The property differences for vulcanizate blends have also been explained in the light of differences in the morphology developed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1488–1505, 2000     

Manufacture of rigid PVC/wood‐flour composite foams using moisture contained in wood as foaming agent

Relatioships between the density of foamed rigid PVC/wood‐flour composites and the moisture content of the wood flour, the chemical foaming agent (CFA) content, the content of all‐acrylic foam modifier, and the extruder die temperature were determined by using a response surface model based on a four‐factor central composite design. The experimental results indicated that there is no synergistic effect between teh CFA content and the moisture content of the wood flour. Wood flour moisture could be used effectively as foaming agent in the production of rigid PVC/wood‐flour composite foams. Foam density as low as 0.4 g/cm³ was produced without the use of chemical foaming agents. However, successful foaming of rigid PVC/wood‐flour composite with moisture contained in wood flour strongly depends upon the presence of all‐acrylic foam modifier in the formulation and the extrusion die temperature. The lowest densities were achieved when the all‐acrylic foam modifier concentration was between 7 phr and 10 phr and extruder die temperature was as low as 170°C.     

Flow behavior of polypropylenes with different molecular structures in a coat‐hanger die

An experimental investigation of the flow behavior of three polypropylene melts with different molecular structures during extrusion through a coat‐hanger die is presented. Two linear and one long‐chain branched material, rheologically characterized in shear and elongation, were investigated. Using laser–Doppler velocimeter measurements of the velocity profiles across the gap height were performed at five various locations along the die. The uniformity of the velocity distribution along the die has been assessed using the maximum velocities v₀ of the corresponding velocity profiles across the gap. The velocity distribution along the die changes with throughput and temperature. Regarding the rheological properties, it was found that the power‐law index of the viscosity as a function of shear rate has a decisive influence on the uniformity of flow but that the pronounced strain hardening in elongation typical of the long‐chain branched polypropylene is not reflected by the velocity distribution along the die. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Rheological properties,flow visualization and extrudate swell of NR compound by rotating‐die rheometer

An experimental apparatus coupled with a rotating die system was especially designed and manufactured to study the rheological properties, flow patterns and swelling behavior of natural rubber (NR) compound for different shear rates and die rotating speeds at a test temperature of 110°C, the results being compared with those by the static capillary die. It was found that NR compound used exhibited psuedoplastic non‐Newtonian behavior. The rotation of the capillary die could reduce the extrusion load. The wall shear stress for any given shear rates increased with increasing die rotating speed. The fluctuation of the entrance pressure drop increased with increasing die rotating speed. The flow pattern development in the rotating‐die rheometer was different from that observed in the static die. The flow patterns in the rotating die were clearly unstable and contained two flow components which included axial flow along the barrel and circumferential flow at the die entrance. The size and shape of the axial and circumferential flows were more dependent on the piston displacement. It was found that the swelling ratio of the NR compound decreased with increasing die rotating speed. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers.     

Ultrasonic in‐line monitoring of polymer extrusion

In‐line ultrasonic monitoring of polymer co‐extrusion and twin‐screw extrusion are presented. Co‐extrusion of high density polyethylene (HDPE) and a thermoplastic elastomer based on polypropylene‐EPDM (ethylene‐propylene‐diene monomer) has been investigated by ultrasonic sensors consisting of piezoelectric transducers and clad buffer rods. One extremity of the rod (probing end) was installed flush with the die surface so as not to disturb the material flow. The other end was air cooled in order to protect the transducer from excessive heating. This approach has been demonstrated to be quite convenient for monitoring and controlling industrial material processes: first, it can work at temperatures up to 1000°C; second, the clad buffer rod probing end can be machined to the same shape as those of commercial temperature and pressure sensors commonly used in the extrusion process. Therefore, no modifications are required for the installation in the original equipment. The information obtained includes the position of the interface between polymers and the stability of the process. The same ultrasonic probe has also been installed on a barrel of a twin‐screw extruder. This study was performed using polyethylene and polystyrene. It has been verified that the ultrasonic sensor can be successfully operated along the extruder screw and that the ultrasound can give access to the material properties while the polymer is being processed. This means that the technique can be exploited to monitor and control in situ the characteristics of the polymer being transformed in operations typically performed on twinscrew extruders, such as compounding, visbreaking or reactive extrusion.