Polymer Melts Research Articles

Simulation of Structural Transition in an Isotropic Melt of Nematic and Smectic Polymers

The isotropic phases of four fractions of a mesogenic comb-shaped polymer were studied using the electric birefringence method. The fractions have either nematic – isotropic melt, or smectic-A – isotropic melt phase transition, depending on the degree of polymerization. All samples showed a structural transition in isotropic phase. Mathematical modeling of the electro-optical properties was performed based on the modified Landau-De Gennes theory using three- order parameters. The reason for the transition in the isotropic phase is the mutual rearrangement of the polar side groups of the polymer as a result of dipole-dipole interaction.

Study of Foaming Morphology in Microcellular Injection Molded TPU/MWCNT Composites under Gas Counter Pressure

Due to the global environmental issues, microcellular injection molding (MuCell) process with the advantages of the energy saving, environmentally friendly and light weighting has become more and more popular in industry. In order to improve the common defects of uneven cell size and cell rupture in MuCell, this study aims to ameliorate the issues of excessively large open-cell structure and density reduction caused by cell rupture in MuCell with thermoplastic polyurethane (TPU). TPU 1185A supplied by BASF was selected as the material, to which multi-walled carbon nanotubes (MWCNT) were added and a gas counter pressure (GCP) control was applied, subsequently. The cell structure change was observed via scanning electron microscope (SEM). The results showed that adding nanotubes to TPU can increase the viscosity of the polymer melt and lower the average cell size, which will significantly reduce the number of cells with a diameter greater than 100 μm. With the GCP technique employed, the overall cell size was further reduced as well as the number of cells with a diameter greater than 100 μm, and the cell density was further increased.

Formation mechanism of plug-like flow in nanoconfined polymer melts: Molecular dynamics study

The formation mechanism of plug-like flow in polymer melts between smooth and rough silicon walls was investigated through molecular dynamics simulations. As the driving velocity increased, plug-like flow occurred between rough silicon walls, while smooth silicon walls exhibited Poiseuille flow. The formation process of plug-like flow involved sprouting, shaping, and forming stages. Initially, the rising driving velocity in the rough silicon channel gradually increased shear stress on confined melts above a critical value. This initiated the elongation of polymer molecules near the wall from a curled to a horizontally straightened state, reducing internal viscous resistance and creating a velocity gradient gap between the near-wall and center areas, marking the sprouting of plug-like flow. In the shaping stage, horizontally straightened polymer molecules expanded from the near-wall area to the transition area, further widening the velocity gradient gap. Finally, steady plug-like flow formed when the velocity gradient gap exceeded a critical value, namely when nearly all polymer molecules in both the near-wall and transition areas were horizontally straightened. Conversely, shear stress on melts confined between smooth walls did not reach the critical value required for plug-like flow initiation. Furthermore, simulation results showed that the elongation of polymer molecules played a more significant role than boundary slip in the formation of plug-like flow-for polymer melts.

Capillary filling of star polymer melts in nanopores

The topology of a polymer profoundly influences its behavior. However, its effect on imbibition dynamics remains poorly understood. In the present work, capillary filling (during imbibition and following full imbibition) of star polymer melts was investigated by molecular dynamics simulations with a coarse-grained model. The reversal of imbibition dynamics observed for linear-chain systems was also present for star polymers. Star polymers with short arms penetrate slower than the prediction of the Lucas–Washburn equation, while systems with long arms penetrate faster. The radius of gyration increases during confined flow, indicating the orientation and disentanglement of arms. In addition, the higher the functionality of the star polymer, the more entanglement points are retained. Besides, a stiff region near the core segments of the stars is observed, which increases in size with functionality. The proportion of different configurations of the arms (e.g., loops, trains, tails) changes dramatically with the arm length and degree of confinement but is only influenced by the functionality when the arms are short. Following full imbibition, the different decay rates of the self-correlation function of the core-to-end vector illustrate that arms take a longer time to reach the equilibrium state as the functionality, arm length, and degree of confinement increase, in agreement with recent experimental findings. Furthermore, the star topology induces a stronger effect of adsorption and friction, which becomes more pronounced with increasing functionality.

A Reactive Bead–Spring Model for Associative Polymer Melts In and Out of Equilibrium

A Reactive Bead–Spring Model for Associative Polymer Melts In and Out of Equilibrium

Expansion Injection Molding Process Using Clamping Force for Melt Compression.

Melt expansion followed by compression has been utilized for high-speed filling. In general, this technology was developed for a machine level. Recently, mold-level technology has been tried. In this study, an expansion injection molding process was examined, which included compressing a polymer melt through cylinder action facilitated by the movement of the platen, followed by the expansion of the polymer melt into a mold cavity. A mold system including temperature control and valve actions, similar to hot runner systems, was designed and built. The test results show good filling when the injection pressure was high. Simulations were also carried out, highlighting consistent pressure and filling trends, while revealing limitations tied to the characteristics of the state model. This research indicates promise for expansion injection molding through platen compression but emphasizes the need for the seamless integration of valve action with the injection molding machine for large-scale production.

Flow analysis of screw extrusion in three-dimensional concrete printing

Recent advances in three-dimensional concrete printing necessitated the detailed understanding of the operation and performance of screw extruders. This paper shows that the volumetric output rate can be approximated using the rotating barrel and stationary screw assumption (drag flow equation), which is used routinely in polymer melt extrusion calculations. Verification is provided by comparisons to experimental results available in the literature and to computer flow simulations for fluids with yield stress. Significant insight is obtained using fully three-dimensional simulations. This includes particle pathlines, which form “a helix within a helix,” axial pressure profiles, and the effect of yield stress, which is relatively small on the output rate but large on torque and power. The computer simulation also predicts unyielded flow zones in the extruder channel at low screw rotation speeds.

Confinement effect of inter-arm interactions on glass formation in star polymer melts.

We utilized molecular dynamic simulation to investigate the glass formation of star polymer melts in which the topological complexity is varied by altering the number of star arms (f). Emphasis was placed on how the "confinement effect" of repulsive inter-arm interactions within star polymers influences the thermodynamics and dynamics of star polymer melts. All the characteristic temperatures of glass formation were found to progressively increase with increasing f, but unexpectedly the fragility parameter KVFT was found to decrease with increasing f. As previously observed, stars having more than 5 or 6 arms adopt an average particle-like structure that is more contracted relative to the linear polymer size having the same mass and exhibit a strong tendency for intermolecular and intramolecular segregation. We systematically analyzed how varying f alters collective particle motion, dynamic heterogeneity, the decoupling exponent ζ phenomenologically linking the slow β- and α-relaxation times, and the thermodynamic scaling index γt. Consistent with our hypothesis that the segmental dynamics of many-arm star melts and thin supported polymer films should exhibit similar trends arising from the common feature of high local segmental confinement, we found that ζ increases considerably with increasing f, as found in supported polymer films with decreasing thickness. Furthermore, increasing f led to greatly enhanced elastic heterogeneity, and this phenomenon correlates strongly with changes in ζ and γt. Our observations should be helpful in building a more rational theoretical framework for understanding how molecular topology and geometrical confinement influence the dynamics of glass-forming materials more broadly.

A Novel In-Line Measurement and Analysis Method of Bubble Growth-Dependent Strain and Deformation Rates during Foaming.

Bubble growth processes are highly influenced by the elongational viscosity of the blowing agent-loaded polymer melt. Therefore, the elongational viscosity is an important parameter for the development of new polymers for foaming applications, as well as for the prediction of bubble growth processes. Thus, knowledge of the initial expansion and deformation behavior in dependency on the polymer, the blowing agent concentration, and the process conditions is necessary. This study presents a novel method for the in-line observation and analysis of the initial expansion and deformation behavior within the bead foam extrusion process. For this purpose, nitrogen as the blowing agent was injected into the polymer melt (PS and PLA) during the extrusion process. The in-line observation system consists of a borescope equipped with a camera, which was integrated into the water box of an underwater pelletizer. The camera is controlled by a developed trigger by means of angular step signal analysis of a rotary encoder on the cutter shaft of the underwater pelletizer. Thus, images can be taken at any time during the foaming process depending on the cutter position to the die outlet. It is shown that the developed method provides reliable results and that the differences of the initial expansion and deformation behavior during bubble growth can be analyzed in-line in dependency on real foaming process conditions and the type of polymer used.

Surface defect passivation by ligand in polymeric melt encapsulated CsPbBr3 perovskite nanocrystals/PP composite with high X-ray imaging performance

In-situ growth method has been widely used in the preparation of metal halide perovskite nanocrystals/polymer composites. However, the ligand-free process tends to bring surface defects which always deteriorate the photoluminescence. The passivation effect of surface ligands on the defects of nanocrystals, which is of benefit to promote the photoluminescence performance of the composites, is often neglected in the preparation of perovskite nanocrystals/polymers. Here, we report a facile post-passivation treatment of CsPbBr3/polypropylene (PP) composite film with octylamine solution, and surface engineering of CsPbBr3 nanocrystals in PP molecular chain by swelling effect to passivate the surface defects of nanocrystals. The composite film achieves a significant photoluminescence enhancement by 27 times under UV light. In addition, when used as a scintillator material, the passivated CsPbBr3/PP composite film has a enhanced significant light response to X-ray, and the X-ray imaging ability of the metal spring in the capsule is preliminarily realized. Moreover, this post-treatment passivation strategy is easy to apply and expected to be applied to the performance improvement of other perovskite nanocrystals/polymer composites. Overall, this approach has the potential to design a new generation of perovskite nanocrystals/polymer-based scintillator materials.

An investigation into the mechanisms that influence laser sintered polyamide-12 top surfaces

Purpose The purpose of this paper is to elucidate the extent to which the mechanisms of polymer melt viscous flow and finish layer powder particle adhesion influence the top surface topographies of laser sintered polyamide (PA12) components. Design/methodology/approach Laser sintered specimens were manufactured at varying laser parameters in accordance with a full factorial design of experiments. Focus variation microscopy was used to ascertain insight into their top surface heights and peak/valley distributions. Subsequently, regression expressions were generated to model the former with respect to applied laser parameters. Auxiliary experimental analysis was also performed to validate the proposed mechanisms and statistical models. Findings Within the parameter range tested, this work found the root mean square (Sq) and skewness (Ssk) roughness responses of laser sintered PA12 top surfaces to be inversely related to one another, and both also principally influenced by beam spacing. Furthermore, it was demonstrated that using optimised laser parameters (to promote polymer melt dispersion) and building without finish layers (to avert subsequent powder particle adhesion) reduced the mean Sq roughness of resultant topographies by 30.8% and 47.9% relative to standard laser sintered PA12 top surfaces, respectively. Practical implications The scope to which laser sintered PA12 top surfaces can be modified was highlighted. Originality/value This research demonstrated the impact the mechanisms of polymer melt viscous flow and finish layer powder particle adhesion have on laser sintered PA12 top surfaces.

Numerical modelling of the viscoelastic polymer melt flow in material extrusion additive manufacturing

ABSTRACT In material extrusion (MEX), it is challenging to accurately predict the steady and transient feeding forces at various polymer extrusion rates when printing island and thin-walled structures involving rapid start/stop or acceleration/deceleration, especially for semi-crystalline polymers. This research presents a non-isothermal viscoelastic Computational Fluid Dynamics model to investigate the steady and transient feeding forces, as well as the phase transition process and viscoelastic behaviour of polylactic acid (PLA), a semi-crystalline polymer, during the extrusion process. The study establishes a relationship between polymer flow and viscoelastic stress, demonstrating that the elastic effect during extrusion is more significant than the viscous effect, particularly at higher feeding rates. Furthermore, the study uncovers critical aspects of PLA melt flow behaviour during the MEX process, laying the foundation for future research and optimisation of MEX printing processes.

Material-Sparing Feasibility Screening for Hot Melt Extrusion.

Hot melt extrusion (HME) offers a high-throughput process to manufacture amorphous solid dispersions. A variety of experimental and model-based approaches exist to predict API solubility in polymer melts, but these methods are typically aimed at determining the thermodynamic solubility and do not take into account kinetics of dissolution or the associated degradation of the API during thermal processing, both of which are critical considerations in generating a successful amorphous solid dispersion by HME. This work aims to develop a material-sparing approach for screening manufacturability of a given pharmaceutical API by HME using physically relevant time, temperature, and shear. Piroxicam, ritonavir, and phenytoin were used as model APIs with PVP VA64 as the dispersion polymer. We present a screening flowchart, aided by a simple custom device, that allows rapid formulation screening to predict both achievable API loadings and expected degradation from an HME process. This method has good correlation to processing with a micro compounder, a common HME screening industry standard, but only requires 200 mg of API or less.

Laun's rule for predicting the first normal stress coefficient in complex fluids: A comprehensive investigation using fractional calculus

Laun's rule [H. M. Laun, “Prediction of elastic strains of polymer melts in shear and elongation,” J. Rheol. 30, 459–501 (1986).] is commonly used for evaluating the rate-dependent first normal stress coefficient from the frequency dependence of the complex modulus. We investigate the mathematical conditions underlying the validity of Laun's relationship by employing the time-strain–separable Wagner constitutive formulation to develop an integral expression for the first normal stress coefficient of a complex fluid in steady shear flow. We utilize the fractional Maxwell liquid model to describe the linear relaxation dynamics compactly and accurately and incorporate material nonlinearities using a generalized damping function of Soskey–Winter form. We evaluate this integral representation of the first normal stress coefficient numerically and compare the predictions with Laun's empirical expression. For materials with a broad relaxation spectrum and sufficiently strong strain softening, Laun's relationship enables measurements of linear viscoelastic data to predict the general functional form of the first normal stress coefficient but often with a noticeable quantitative offset. Its predictive power can be enhanced by augmenting the original expression with an adjustable power-law index that is based on the linear viscoelastic characteristics of the specific material being considered. We develop an analytical expression enabling the calculation of the optimal power-law index from the frequency dependence of the viscoelastic spectrum and the strain-softening characteristics of the material. To illustrate this new framework, we analyze published data for an entangled polymer melt and for a semiflexible polymer solution; in both cases our new approach shows significantly improved prediction of the experimentally measured first normal stress coefficient.

The polymer melt swelling behavior in micro-extrusion process for preparation of continuous carbon fiber reinforced PP prepreg filament

The micro-extrusion process for polymer melt has been increasingly used for the production of high value-added prepreg filaments with applications in the fields of fused deposition modeling (FDM). In this study, the effect of characteristic scale, defined as the gap of die land in an annular micro-extrusion die, on the extrudate swelling behaviour of viscoelastic melt is analyzed through numerical simulations and micro-extrusion experiments. The results show that the swelling behaviour displays an obvious dependence on the characteristic scale. An increase in the characteristic scale reduces the swell ratio and retards the process to reach the equilibrium state. In contrast, a decrease in the characteristic scale results in a larger magnitude of change in velocity field and faster relaxation development of stress field. The location of the maximum velocity layer for the laminar flow gradually deviates from the geometric center of channel toward the wall of mandrel with the increase in the characteristic scale. It is imperative to consider the complicated swelling behavior and remarkable viscoelastic effect simultaneously in micro-extrusion process.

Two-relaxation-time lattice Boltzmann model of the velocity profiles and volumetric flow rate of generalized Newtonian fluids in a single-screw extruder

Single-screw extruders and injection molding machines are essential equipment in polymer processing. It is of great importance for the optimization of operating parameters and the design of extrusion screw to predict the throughput of an extruder and the metering time of an injection molding machine according to the geometric parameters of the screw, operating parameters, and the rheological behavior of materials. Most polymer melts exhibit non-Newtonian behavior. The lattice Boltzmann method has many advantages in simulating the flow of non-Newtonian fluids. Herein, the dimensionless velocity profiles and dimensionless volumetric flow rate of generalized Newtonian fluids in a screw channel have been studied using the two-relaxation-time lattice Boltzmann method (TRT–LBM). The numerical results of power-law fluids are in good agreement with the analytical solutions, which verifies the validity of TRT–LBM. Through research, the change rule of the dimensionless volumetric flow rate of Bingham fluids with dimensionless pressure gradient has been obtained. It was found that the rheological properties of polymer melts and the dimensionless pressure gradient significantly affect the dimensionless velocity profiles and dimensionless volumetric flow rate. The dimensionless volume flow rate has some unexpected changes with the increase of the dimensionless pressure gradient. This study can provide theoretical guidance for the optimization of operating parameters and the design of extrusion screws.

The influence of elongation-induced concentration fluctuations on segmental friction in polymer blends.

Recent experimental studies have revealed a lack of universality in the extensional behavior of linear polymers, which is not envisioned by classical molecular theories. These surprising findings, particularly the sharp contrast between polymer melts and solutions, have catalyzed the development of new theoretical ideas, including the concept of friction reduction in highly stretched polymer melts. By presenting evidence from rheology and small-angle neutron scattering, this work shows that deformation-induced demixing, which is due to the viscoelastic asymmetry in binary mixtures, contributes to the observed nonuniversality. In the case of polystyrene/oligostyrene blends, demixing increases the effective glass transition temperature of the long chain, leading to an apparent friction enhancement. On the other hand, the opposite case is found for the polystyrene/poly(α-methylstyrene) blend. These results highlight the important influence of deformation-induced concentration fluctuations on polymer segmental friction.

Pressure drop non-linearities in material extrusion additive manufacturing: A novel approach for pressure monitoring and numerical modeling

Fused Filament Fabrication is an additive manufacturing technique in which molten thermoplastic polymers are extruded through a nozzle. Therefore, the interplay between the viscoelastic nature of the polymer melt, temperature, printing conditions and nozzle shape may lead to inconsistent extrusion. To improve the extrusion control and optimize the print-head performance, a better understanding of the flow process of the polymer melt both in the nozzle and the liquefier is needed. However, several challenges need to be overcome due to the complexity of gathering experimental data on the melt pressure in the nozzle and the lack of numerical models able to capture the full rheology of the molten polymer. This research introduces an innovative approach for monitoring the pressure within a material extrusion 3D printer’s nozzle. This method involves utilizing a pin in direct contact with the molten material, which then transmits the applied force from the material to an externally mounted load cell. The setup provides reliable, repeatable pressure data in steady-state conditions for two nozzle geometries and at different extrusion flows and temperatures. Moreover, the Giesekus model enabled capturing the viscoelastic rheometric features of the melt, and the numerical predictions have been compared with the experimental data. Results show that the numerical model accurately describes the flow conditions in the nozzle and allows the estimation of the behavior of the melt in the liquefier zone, the area of the print-head where the filament is molten. It could be concluded that the backflow, which is the backward flow of the molten polymer in the gap between the filament and the liquefier towards the cold end, caused significant non-linearities in the total pressure drop measured in the feeders, which were related to normal forces induced by shear in that region.

Role of additive size in the segmental dynamics and mechanical properties of cross-linked polymers.

Thermoset materials often involve the addition of molecular and nanoparticle additives to alter various chemo-physical properties of importance in their ultimate applications. The resulting compositional heterogeneities can lead to either enhancement or degradation of thermoset properties, depending on the additive chemical structure and concentration. We tentatively explore this complex physical phenomenon through the consideration of a model polymeric additive to our coarse-grained (CG) thermoset investigated in previous works by simply varying the size of additive segments compared to those of polymer melt. We find that the additive modified thermoset material becomes chemically heterogeneous from additive aggregation when the additive segments become much smaller than those of the thermoset molecules, and a clear evidence is observed in the spatial distribution of local molecular stiffness estimated from Debye-Waller factor 〈u2〉. Despite the non-monotonic variation trends observed in dynamical and mechanical properties with decreasing additive segmental size, both the structural relaxation time and moduli (i.e., shear modulus and bulk modulus) exhibit scaling laws with 〈u2〉. The present work highlights the complex role of additive size played in the dynamical and mechanical properties of thermoset polymers, which should provide a better understanding for the glass formation process of cross-linked polymer composites.

Simulation of fiber-induced melt pressure fluctuations within large scale polymer composite deposition beads

The process-structure-property relationship in Large Area Additive Manufacturing (LAAM) technology is an ongoing area of research as the inherent microstructural properties (chiefly fibers and voids) affect the performance of printed parts. Unfortunately, we currently lack adequate understanding of micro void nucleation and evolution during the LAAM and fused deposition modelling (FDM) processes. Modeling of the polymer melt flow during the extrusion process is important in understanding the underlying microstructural formation and associated properties of the print, that determines the part performance in service conditions. In this paper we compute fiber-induced local pressure fluctuations which may promote void formation in the bead’s microstructure. On a macro-scale, we determine flow fields of a purely viscous, Newtonian planar polymer deposition flow through a LAAM nozzle which are utilized on a micro-scale model where we simulate the evolution of a single ellipsoidal fiber along streamlines obtained from the macro-model. On the micro-scale, we determine instantaneous values of the translational and rotational velocities of the rigid ellipsoidal fiber that satisfies a balance of hydrodynamic forces and couples on the fiber’s surface based on a Newton Raphson algorithm and we track the fiber’s motion along the flow path via an explicit numerical iterative algorithm. Model verification is achieved by benchmarking results with solutions from well-known Jeffery’s equation of motion of a particle in homogeneous simple shear flow. We account for rotary diffusivity due to short-range fiber-fiber interaction in the FEA simulation by determining an effective fluid domain size representative of the interaction coefficient of the melt flow through a correlation analysis that yields an equivalent steady state orientation based on the Advani-Tucker equation. We also consider different possible motions of the fiber along individual LAAM flow paths from a given set of random initial fiber conditions to determine pressure bounds on the fiber surface along each streamline. For improved computational efficiency, calculations are carried out with respect to the fiber’s local coordinate axes to overcome the rigor of adaptive remeshing during the quasi-transient analysis. Results show low pressure extremes near the fiber’s surface which varies across the printed bead as well as through its thickness. Discussion is provided to gain insight into the effect of low-pressure extremes on micro void formation, particularly at the nozzle exit and during die swell/expansion.