Polymer Melts Research Articles

Molecular Insights into the Wall Slip Behavior of Pseudoplastic Polymer Melt in Nanochannels during Micro Injection Molding

Wall slip directly affects the molding quality of plastic parts by influencing the stability of the filling flow field during micro injection molding. The accurate modeling of wall slip in nanochannels has been a great challenge for pseudoplastic polymer melts. Here, an effective modeling method for polymer melt flow in nanochannels based on united-atom molecular dynamics simulations is presented. The effects of driving forces and wall–fluid interactions on the behavior of polyethylene melt under Poiseuille flow conditions were investigated by characterizing the slip velocity, dynamics information of the flow process, and spatial configuration parameters of molecular chains. The results indicated that the united-atom molecular dynamics model could better describe the pseudoplastic behavior in nanochannels than the commonly used finitely extensible nonlinear elastic (FENE) model. It was found that the slip velocity could be increased with increasing driving force and show completely opposite variation trends under different orders of magnitude of the wall–fluid interactions. The influence mechanism was interpreted by the density distribution and molecular chain structure parameters, including disentanglement and orientation, which also coincides with the change in the radius of gyration.

Effects of gas-assisted technology on polymer micro coextrusion

Abstract In this paper, a three-dimensional viscoelastic flow model of double-layer micro coextrusion with circular cross-section was established. The simulations were carried out by the finite element method and the influence of wall slip coefficient on micro coextrusion was studied. The results show that gas-assisted technology is suitable for polymer micro coextrusion forming. The differences between the gas-assisted and conventional micro coextrusion process were compared by analyzing the distribution of melts velocity, pressure, shear rate and first normal stress difference. The research results show that in the conventional micro coextrusion process there are pressure drop, shear rate, first normal stress difference and secondary flow. And there is a gradient distribution of melts velocity. The die swell and deformation vary with the forming process parameters, and it is difficult to control the product quality. But in the gas-assisted micro coextrusion process, there is no pressure drop, shear rate, first normal stress difference and secondary flow. The velocity of polymer melts is evenly distributed and the melts are extruded in a plunger shape. The melts do not swell and deform and it is independent of forming process parameters. It is easy to ensure the products quality and the inherent problems of polymer conventional micro coextrusion are well solved.

Understanding the role of cross-link density in the segmental dynamics and elastic properties of cross-linked thermosets.

Cross-linking is known to play a pivotal role in the relaxation dynamics and mechanical properties of thermoset polymers, which are commonly used in structural applications because of their light weight and inherently strong nature. Here, we employ a coarse-grained (CG) polymer model to systematically explore the effect of cross-link density on basic thermodynamic properties as well as corresponding changes in the segmental dynamics and elastic properties of these network materials upon approaching their glass transition temperatures (Tg). Increasing the cross-link density unsurprisingly leads to a significant slowing down of the segmental dynamics, and the fragility K of glass formation shifts in lockstep with Tg, as often found in linear polymer melts when the polymer mass is varied. As a consequence, the segmental relaxation time τα becomes almost a universal function of reduced temperature, (T - Tg)/Tg, a phenomenon that underlies the applicability of the "universal" Williams-Landel-Ferry (WLF) relation to many polymer materials. We also test a mathematical model of the temperature dependence of the linear elastic moduli based on a simple rigidity percolation theory and quantify the fluctuations in the local stiffness of the network material. The moduli and distribution of the local stiffness likewise exhibit a universal scaling behavior for materials having different cross-link densities but fixed (T - Tg)/Tg. Evidently, Tg dominates both τα and the mechanical properties of our model cross-linked polymer materials. Our work provides physical insights into how the cross-link density affects glass formation, aiding in the design of cross-linked thermosets and other structurally complex glass-forming materials.

Effects of Melt Temperature and Non-Isothermal Flow in Design of Coat Hanger Dies Based on Flow Network of Non-Newtonian Fluids.

In the design of coat hanger extrusion dies, the main objective is to provide a uniform flow rate at the die exit. Previously, a multi-rheology isothermal method model for coat hanger extrusion dies was developed to reach this objective. Polymer melts in extrusion dies commonly experience high shear rates. Viscous dissipation rooted by high shear rate may lead to significant temperature differences across the die. Due to temperature-dependency of viscosity, temperature differences may lead to nonuniform flow rates, which may significantly affect the flow rate at the die exit. As a result, a new design method is proposed to take into account the effects of temperature and viscous dissipation in the design of coat hanger dies. Although more non-Newtonian fluid rheology models can be adapted in the proposed study, as demonstration, temperature-dependent power-law and Carreau–Yasuda models are adapted in this study. Performances are compared with our isothermal method published earlier. In addition, the novel nonisothermal method is comprehensively examined where the effect of viscous dissipation is studied through Brinkman number of extrusion die. It is demonstrated that, for a low Brinkman number, both isothermal and nonisothermal design give similar flow uniformity level. However, for higher Brinkman numbers, the proposed nonisothermal method produces a design with more desirable velocity uniformity level along with a maximum improvement of over the isothermal method. In addition, dependency of flow field on temperature, due to temperature-dependent viscosity, is studied, and it is demonstrated that fully-developed velocity profile changes as temperature increases along the flow channel. Moreover, the effect of the temperature sensitivity parameter in temperature-dependent non-Newtonian models is considered. It is demonstrated that the temperature boundary condition with the Biot number of 1.0 gives adequate results for lower values of the temperature sensitivity parameter.

Manufacturing of tetrahedral metal effect pigment particles and analysis of their orientation in polymer melts

In this study, novel micro particles in the shape of irregular tetrahedrons in a two to three-digit micrometer size range are presented. The particle manufacturing feasibility was investigated in three different ways: shaping, casting and rolling. Rolling showed the potential for mass production. The suitability of tetrahedral particles for the use as metal effect pigment was assessed by comparison with conventional platelet-shaped metal effect pigments. Optical inspection showed a strongly reduced luminance inhomogeneity in weld line regions in the case of the tetrahedral particles. It was found by synchrotron X-ray tomography examination of particles in solidified polymethylmethacrylate (PMMA) that particle depletion is not the main reason for visible flow lines. The orientation of platelet-shaped pigment particles was identified to cause such flow lines. PMMA filled with tetrahedral particles, in contrast, shows homogenous optical properties independent from the particle orientation. Thus, flow lines in weld line regions can be omitted. • Tetrahedral effect pigment particles were produced by shaping, casting and a commercially relevant novel roll-to-roll-process. • Tetrahedral particles do not show flow lines in weld line regions. • Light microscopy and 3D X-ray tomography revealed particle orientation, not depletion, as main cause of flow lines.

In-line measurement and modeling of temperature, pressure, and blowing agent dependent viscosity of polymer melts

Abstract During processing and bubble growth processes, the melt viscosity changes with temperature, pressure, and blowing agent concentration. Therefore, measurement and prediction methods for viscosity characterization in terms of temperature, pressure, and blowing agent dependency are needed. This study demonstrates the applicability of in-line viscosity measurements during the foam injection molding process and a model for viscosity superposition and prediction. In the present study, polystyrene and a modified polylactide for foaming applications with nitrogen as blowing agent are investigated. By changing the injection speed, temperature, and blowing agent concentration, the process conditions are varied, and thus the resulting pressure drops within the in-line measurement die. The calculated shear rates and viscosities are shifted to a master curve by the application of superposition principles. The viscosity dependency on temperature is described by the Arrhenius equation, the pressure by the Barus equation, and for the blowing agent concentration, a novel Barus-like equation was derived and applied. The prediction of the master curve viscosity function was achieved by the power-law model in combination with the superposition principles and showed good agreement with the shifted in-line data. Finally, the in-line measurements and viscosity predictions are validated by comparing them to rotational and capillary rheometer measurements.

Numerical simulations of interfacial and elastic instabilities

<h2>Abstract</h2> The interplay of elasticity and capillarity in free-surface flows of viscoelastic fluids gives rise to intriguing flow instabilities. We present novel numerical simulations and analyse the physics related to the appearance of surface distortions on polymer melt extrudates, often referred to as "sharkskin" instability, and the abrupt increase in the rise velocity of a bubble in a viscoelastic solution. Regarding the extrusion process, the transition from smooth to wavy extrudate with increasing flow rate is attributed to a Hopf bifurcation, followed by a sequence of period-doubling bifurcations, which eventually lead to elastic turbulence under creeping flow. We suggest that the inception of these waves is related with intense stretch of polymer chains and subsequent recoil at the region where the melt detaches from the solid wall of the die. The ‘velocity discontinuity' of the rising bubble is attributed to a hysteresis loop, triggered by the change of shape of the rear pole into a tip that favors the formation of intense stress gradients, which reduce the fluid viscosity and facilitate the bubble translation. Finally, we discuss the numerical methodology that has allowed us to obtain stable numerical solutions in highly deformed meshes and for high values of the Weissenberg number.

Three dimensional finite element computation of the non-isothermal polymer filling process by the phase field model

In this paper, we numerically study the three dimensional non-isothermal non-Newtonian filling process using the phase field method. The Cahn-Hilliard equation is firstly attempted to capture the moving melt front between the Newtonian and non-Newtonian fluid. The governing equations of the flow field are able to be written in a unified form on the basis of phase field parameter. The unified Navier-Stokes equations are decoupled via the splitting scheme and then the traditional FEM and SUPG method are employed to solve the suitable equations. The Cross-WLF model is utilized to describe the variation of the viscosity of the polymer melt in the non-isothermal condition. We take the thin wall rectangular cavity as example and compare with the experimental data to illustrate the convergence, robustness and accuracy of numerical algorithm. In addition, we consider the thin wall cavity with a cylindrical obstacle and analyze the influences of the inlet velocity and the size of the injection gate on the filling process. The numerical results agree well with the experimental data and also exhibit good mass conservation property.

Analysis of Melt Front Behavior of a Light Guiding Plate during the Filling Phase of Micro-Injection Molding

When the size of a liquid crystal display (LCD) increases, the light guiding plate (LGP) as the main part of the LCD must adopt a wedge-shaped plate to reduce its weight (the thickness of the LGP decreases because of this) and guide the light to the LCD screen. Micro-injection molding (MIM) is commonly used to manufacture LGPs. During the filling phase of MIM, the entire entering polymer melt front of the LGP should reach the end of the mold cavity at the same time. In this way, there will be no shrinkage or warpage of the LGP in its subsequent application, but it is difficult for the wedge-shaped LGP to meet these requirements. Therefore, the authors hoped to investigate MIM process parameters to change this situation. Otherwise, the LGP is easily deformed during the manufacturing process. Flow characteristics of LGPs were investigated during the filling phase of MIM in this study. Experimental and 3D numerical simulations were used to analyze the hysteresis, i.e., the advance of the polymer melt front of the LGP in MIM. Study results showed that a low injection speed caused a hysteresis effect of the plastic melt front, the solution was to increase the injection speed to improve the situation and an injection speed of 10 cm/s could achieve uniformity of the melt front in MIM. The research results showed that the filling situation of the LGP of MIM in the experiment was very close to that of the 3D numerical simulation.

Rheological characterization of complex fluids through a table-top 3D printer

3D printing is changing the way we conceive, design, and build 3D objects in mechanical, biomedical, aerospace, construction, automotive and maritime industries. In the current work, the nonlinear rheological behaviour of polymer melts is measured through a table-top 3D printer (3D RheoPrinter) that, smartly modified, allows inline investigation of viscosity, extrudate swell and melt fracture. By using a piezoresistive mini-transducer, the innovative system is designed to be applicable to all Fused Deposition Modelling (FDM) 3D printers by a simple and cost-effective modification of a state-of-art nozzle. The measurements of the nonlinear rheological behaviour are compared with traditional, rotational rheology. Two biodegradable polymers, i.e. polylactic acid and polycaprolactone, are investigated as model systems to test the 3D RheoPrinter. The results of the shear viscosity and the first normal stress difference coefficient, as function of shear rate, show a good agreement between the 3D RheoPrinter and rotational rheometer with an error of about 6% for a confidence interval of 96%. Moreover, the 3D RheoPrinter can still be used as 3D printer. In the last part of this work, it is presented a printing test for building 3D structures in which the results show controllable resolution by means of the measured rheological information such as the extrudate swell. The vision of this work is that an inline rheological characterization, possible with the developed 3D RheoPrinter, can enable automatic process optimization and quality assurance to the 3D printing community. The social and scientific impacts of this work are maximized by the cost-efficiency and simplicity of the design that makes it within reach of the general public. The 3D RheoPrinter opens for a rheological experimentation to a broad audience and it offers important insights to bring FDM to the next level of resolution.

Probing the elongational rheological behaviour at interfaces of immiscible polymer melts using dilational tensiometry: effect of viscosity and temperature on the interfacial properties

Probing the elongational rheological behaviour at interfaces of immiscible polymer melts using dilational tensiometry: effect of viscosity and temperature on the interfacial properties

Entanglement on Nucleation Barrier of Polymer Crystal

We propose a theoretical approach to quantitatively account for the role of entanglement in the nucleation of polymer melts, which is the unique feature of polymer differentiated from small molecules. By performing molecular dynamics simulations, we obtain the nucleation barriers of polymer systems with different entanglement densities, which exhibits an opposite trend compared to the prediction of the classic nucleation theory (CNT). To amend the deficiency of the CNT in polymer crystallization, we introduce the entanglement free energy to reflect the role of entanglement in polymer nucleation. Specifically, the polymer nucleation not only involves free energies of monomers inside and on the surface of a nucleus as considered in the CNT, but also affects the entanglement network around the nucleus. Our theoretical approach provides a reasonable interpretation for the unsolved nucleation phenomena of polymers in simulations and experiments.

Lightweight Polypropylene/Polylactic Acid Composite Foams with Controllable Hollow Radially Gradient Porous Structures for Oil/Water Separation

The structural characteristics of the polymer composite foams play an important role in their properties. Herein, the polypropylene/polylactic acid (PP/PLA) composite foams with the controllable hollow radially gradient porous structures are designed and prepared by the supercritical CO2-assisted foam extrusion coupled with postdrawing auxiliary technology. The above structures consist of the dense skin layer, hollow-core, closed-cell, and open-cell. Under the constant extrusion foaming temperature and pressure, the outer diameter of the as-prepared foams can be adjusted from about 9.8 mm to 5.7 mm, while the inner diameter changes from about 5.5 mm to 1.7 mm, by adding the PLA to regulate the viscoelasticity and thermodynamic differences of the polymeric melt. Besides, the formation mechanism of the hollow radially gradient porous structures is theoretically analyzed. The as-prepared PP/PLA composite foams exhibit outstanding oil/water separation performance, which show potential application in wastewater treatment.

Factors determining the flow erosion/part deformation of film insert molded thermoplastic products

Abstract Flow erosion and part deformation are unsolved molding problems that restrict the overall success of film insert molding. This work investigated, both experimentally and numerically, the factors that affect flow erosion and part deformation in film inset molded products. Three plate-with-thickness-variation geometries, namely flat, thin-to-thick, and thick-to thin, were molded for the products. Polystyrene films and polyethylene terephthalate (PET) resins were employed in the experiments. It was found that the thin-to-thick specimens exhibited the most severe flow erosion. Increasing the injection pressure or melt temperature worsened flow erosion. Meanwhile, for the processing parameters adopted in the experiments, part deformation generally increased with melt temperature and hold time, while it decreased with injection pressure and hold pressure. Additionally, a numerical software (Moldex® 3-D) was employed to simulate the temperature and shear stress distributions in molded products. The calculated results suggested that part deformation in insert molded products results mainly from the non-uniform temperature profile during the cooling stage, owing to the product configuration and the insert film, while flow erosion is induced by the high shear stress of the polymer melt in the filling stage.

Influence of Nature of Pigments and Dyes on Coloring Properties of Polymeric Superconcentrates

The article considers methods of manufacturing non-toxic films of a given color that meet technological requirements. The problem of reducing the shrinkage of the colored polymer in the casting mould during cooling and maintaining its technical characteristics is experimentally solved. To this end, the influence of the nature of pigments on the degree of polymer coloring is studied, and ways to improve the quality of color are investigated. The object of the study was selected pigment concentrate based on high pressure polyethylene brand 15803-003. The pigment has chosen technical carbon grades N220, P803. Surfactants were modifying additives. Tests of samples to determine the light fastness of dye, migration resistance, the number of agglomerates of pigments, toughness and strength, physical and mechanical properties showed that the most effective additive to improve the coloring properties of soot pigment brand N220 and improve the appearance of finished products introduced into the superconcentrate calcium stearate, which at the stage of mixing in the extruder acts as a surfactant and prevents the adhesion of the pigment and the formation of agglomerates in the polymer melt.

Deviatoric stress driven transient melting below the glass transition temperature in shocked polymers

The relaxation of polymers around and below their glass transition temperature is governed by a range of correlated unit processes with a wide range of timescales. The fast deformation rates of shock loading can suppress a significant fraction of these processes resulting in dynamical glass transition in rubbers. In this article, we report the inverse, a transient melting of a glassy polymer under shock loading. The large deviatoric stresses near the shock front induce fast transitions in backbone dihedral angles and a stress relaxation characteristic of polymer melts. This is followed by slower relaxation expected for glasses.

Film casting of polycarbonate/multi-walled carbon nanotubes composites using ultrasound-assisted twin-screw extruder: experiment and simulation

Abstract A one-step ultrasonic film casting process to manufacture nanocomposite films was developed, in which polycarbonate (PC) was mixed with multi-walled carbon nanotubes (CNT) and cast into films in one process. Numerical and experimental investigations of necking phenomenon were carried out for film casting of PC/CNT composites. Experimental results revealed that the necking along film line decreased with imposition of ultrasound and increasing CNT content, indicating that incorporation of CNT and imposition of ultrasound restrained the elongational flow behavior of melt, resulting in film of a larger width. Isothermal and nonisothermal numerical simulations of the process were performed. In isothermal simulations, the polymer melt was assumed to be maintained at the die temperature. In nonisothermal simulations, the temperature change along the film line was determined from heat transfer calculations with the WLF temperature-dependent viscosity. The simulated and experimental results on normalized film width, defined as a ratio of cast film width to die width, as a function of the distance from the die at various extension ratios were compared. The comparison indicated that changes in film width and thickness along the stretching direction in the nonisothermal process were in better agreement with experimental results than that in the isothermal process. Both experimental and simulated results showed a decrease of film width with take-up speed. Due to the presence of edge effect, the film width in experiment was lower than the simulated one. With incorporation of CNT, a better agreement between experimental and simulated results was obtained, due to a reduced edge effect in the film.

Geometric Predictors of Knotted and Linked Arcs.

Inspired by how certain proteins “sense” knots and entanglements in DNA molecules, here, we ask if local geometric features that may be used as a readout of the underlying topology of generic polymers exist. We perform molecular simulations of knotted and linked semiflexible polymers and study four geometric measures to predict topological entanglements: local curvature, local density, local 1D writhe, and nonlocal 3D writhe. We discover that local curvature is a poor predictor of entanglements. In contrast, segments with maximum local density or writhe correlate as much as 90% of the time with the shortest knotted and linked arcs. We find that this accuracy is preserved across different knot types and also under significant spherical confinement, which is known to delocalize essential crossings in knotted polymers. We further discover that nonlocal 3D writhe is the best geometric readout of the knot location. Finally, we discuss how these geometric features may be used to computationally analyze entanglements in generic polymer melts and gels.

AC electrospinning: impact of high voltage and solvent on the electrospinnability and productivity of polycaprolactone electrospun nanofibrous scaffolds

Electrospinning technology employs direct current high voltage to produce electrospun fibers from the polymeric liquid or melt. However, until now, the impact of alternating current (AC) high voltage on the spinnability of polymers remains inadequately explored. This work studies the effects of various less toxic solvents and AC high voltage (25 and 32 kVRMS) on the spinnability, morphology, and productivity of polycaprolactone (PCL) electrospun nanofibrous scaffolds (ENS). Besides this, cellular activity on various PCL ENS is also evaluated. Herein, formic acid (F), formic acid/acetic acid (FA), and formic acid/acetic acid/acetone (FAA) solvent systems are used to prepare various concentrations of PCL solutions. Preliminary polymer–solvent interaction studies confirm that FAA is the better solvent choice for PCL than FA and F. FAA-PCL exhibits higher viscosity than FA-PCL and F-PCL due to better polymer–solvent interactions and PCL stability. Consequently, FAA-PCL shows higher electrospun nanofiber productivity at 32 kVRMS (12.4 ± 0.3 g/h), followed by FA-PCL (6.9 ± 0.1 g/h) and F-PCL (2.2 ± 0.2 g/h). Finally, the cytotoxicity and in vitro experiments indicate that the fabricated ENS are noncytotoxic and biocompatible with 3T3-L1 mouse fibroblast cells. This study will inspire the academic and industrial communities to fabricate various polymeric nanofibers on a large scale using AC electrospinning technique.

Directional Migration and Distribution of Magnetic Microparticles in Polypropylene-Matrix Magnetic Composites Molded by an Injection Molding Assisted by External Magnetic Field.

Surface-functionalized polymer composites with spherical particles as fillers offer great qualities and have been widely employed in applications of sensors, pharmaceutical industries, anti-icing, and flexible electromagnetic interference shielding. The directional migration and dispersion theory of magnetic microparticles in polypropylene (PP)-matrix magnetic composites must be studied to better acquire the functional surface with remarkable features. In this work, a novel simulation model based on multi-physical field coupling was suggested to analyze the directed migration and distribution of magnetic ferroferric oxide (Fe3O4) particles in injection molding assisted by an external magnetic field using COMSOL Multiphysics® software. To accurately introduce rheological phenomena of polymer melt into the simulation model, the Carreau model was used. Particle size, magnetic field intensity, melt viscosity, and other parameters impacting particle directional motion were discussed in depth. The directional distribution of particles in the simulation model was properly assessed and confirmed by experiment results. This model provides theoretical support for the control, optimization, and investigation of the injection-molding process control of surface-functionalized polymer composites.