Unfilled Polymer Research Articles

Corrosion-Resistant Polymer Composite Tubes with Enhanced Thermal Conductivity for Heat Exchangers

The heat transfer surfaces of heat exchangers are usually made of metals which may suffer from severe corrosion. When corrosive fluids are present, highly corrosion-resistant metals, graphite or ceramics are used, resulting in high costs. This study presents measured data on the thermophysical and mechanical properties of recently developed corrosion-resistant polymer composite tubes for use in heat exchangers. Extruded polymer composite tubes based on polypropylene or polyphenylene sulfide filled with graphite flakes were investigated. The anisotropic thermal conductivities of the polymer composite tubes were measured at various temperatures. The through-wall thermal conductivity of the tubes made of polypropylene filled with 50 vol.% graphite is increased by a factor of 30 compared to pure polypropylene, resulting in a thermal conductivity of 6.5 W/(m K) at 25 °C. The tubes composed of polyphenylene sulfide filled with 50 vol.% graphite have a through-wall thermal conductivity of 4.5 W/(m K) at 25 °C. The mechanical properties of the polymer composites were measured using tensile and flexural tests at different temperatures. The composite materials are more rigid and keep their mechanical properties up to a higher temperature level compared to the unfilled polymers. Surface roughness measurements show the very smooth and sealed surface of the composite tubes. The results contribute to establishing the viability of using polymer composites for heat exchanger applications with corrosive fluids.

Graphene Nanoplatelet Induced Microphase Separation in Poly(ether-block-amide)s

The inclusion of graphene nanoplatelets (GNP) in segmented block copolymers offers a route to manipulate microphase separation for tailoring the mechanical properties of thermoplastic elastomers. GNP loading, lateral size, surface chemistry, interactions with the copolymer hard (HS) and soft (SS) segments and the relative ratio of HS:SS determine the mechanical properties achievable. To test this hypothesis, two different GNPs with similar surface chemistry but which differed in lateral dimensions by one order of magnitude (GNP1, ∼2μm and GNP2, ∼20μm) were melt mixed with three different poly(ether-block-amide)s (PE-b-A)s with variable HS and SS content from high to low. The inclusion of the larger lateral sized GNP2 had a more pronounced effect on PE-b-A morphology as it was more effective at hindering SS chain mobility resulting in microphase separation and suppression of the glass transition temperature (Tg) of the PE-b-A with the largest SS content. At low loadings GNP2 preferentially locates to the HS region, inducing reorganisation of this phase resulting in increased microphase separation. Strain induced crystallisation (SIC) phenomena were also observed for the lowest HS content PE-b-A, behaviour not evident for the PE-b-A with the largest HS content as the SS are not long enough to allow SIC. Inclusion of GNP2 to the PE-b-A with the largest HS content resulted in the largest increase in Young’s modulus (E) of 46%, tensile strength (σ) of 37% and elongation at break (ε) of 53% relative to the unfilled polymer.

Determination of elastic moduli of polymeric materials using microhardness indentation

Young's modulus of elasticity (or stiffness, E) is an important material property for many applications of polymers and polymer-matrix composites. The common methods of measuring E are by measuring the velocity of ultrasonic pulses through the material or by resistance to flexure, but it is difficult for ultrasound to penetrate polymers that contain filler particles, and flexural measurements require large specimens that may not mimic the clinical case. Thus, it may be difficult to determine E using conventional techniques. It would be useful to have a relatively rapid technique that could be applied to small specimens, highly filled materials, and even specimens cured in situ. We suggest using a microhardness indentation technique that was originally developed for ceramic materials. We tested two unfilled rigid polymers, four resin composites, and four unfilled polymers with lesser hardness for this study. The study found that greater Vickers hardness loads yielded more consistent results than lesser loads. We developed a modified equation for E based on Knoop microhardness indentations. We concluded that laboratories may use a microhardness indenter to estimate the elastic moduli of polymers and resin composites. The results support our initial hypotheses that the slope of the equation relating the indentation parameter and the hardness/elastic modulus ratio was different for polymers and resin composites than for ceramics; however, the intercept is the same irrespective of the material tested.

Improving the Tribological Performance of POM through the Incorporation of Bio-Based Materials.

Polyoxymethylene (POM), an engineering polymer commonly used in tribological applications, is often reinforced with fossil-based fibers such as carbon and/or glass fibers to improve its properties. To find more sustainable solutions, in this study, the tribological performance of POM/short cellulose fiber composites at different sliding conditions is investigated. An improvement in the wear coefficient of roughly 69% is observed at the harshest conditions of 5 MPa and 1 m · s-1 with only 10 wt.% cellulose fibers. The friction behavior is furthermore stabilized through fiber addition, as the unfilled polymer did not show a steady state. No signs of thermo-oxidative degradation are found after tribological testing. This study presents promising results for sustainable wear-resistant polymer materials in tribological applications.

Rheological Changes in Bio-Based Filaments Induced by Extrusion-Based 3D Printing Process.

In this work, the authors investigated the impact of extrusion-based printing process on the structural characteristics of bio-based resins through rheological measurements. Two commercially available filaments made from unfilled and wood-filled polylactide (PLA) polymers were considered. Three-dimensional specimens were prepared by printing these filaments under various operating conditions, i.e., changing the extruder temperature and printing rate, and examined using time sweep tests. Specific cycle rheological testing was conducted on pelletized filaments to simulate temperature changes in the printing process. The rheological characteristics of unprocessed materials, in terms of storage (G') and loss (G″) moduli, were found to be slightly affected by temperature changes. For a pure polymer, the G' slope at a low frequency decreased over time, showing that the polymer chains evolved from a higher to a lower molecular weight. For wood-filled materials, the G' slope rose over the testing time, emphasizing the formation of a percolated network of structured filler within the matrix. On the other side, the rheological parameters of both materials were strongly impacted by the printing extrusion and the related conditions. At lower nozzle temperatures (200 °C), by decreasing the printing speed, the G' and G″ curves became increasingly different with respect to unprocessed resin; whereas at higher nozzle temperatures (220 °C), the influence of the printing speed was insignificant, and all curves (albeit distant from those of unprocessed matrix) mainly overlapped. Considerations on degradation kinetics of both materials during the printing process were also provided by fitting experimental data of complex viscosity with linear correlation over time.

Achieving Long‐Range Arbitrary Uniform Alignment of Nanostructures in Magnetic Fields

AbstractFor magnetic field orientation of nonstructures to become a viable method to create high performance multifunctional nanocomposites, it is of paramount importance to develop a method that is easy to implement and that can induce long‐range uniform nanostructural alignment. To overcome this challenge, inspired by low field nuclear magnetic resonance (NMR) technology, a highly uniform, high field strength, and compact magnetic‐field nanostructure orientation methodology is presented for polymeric nanocomposites using a Halbach array, for the first time. Potential new advances are showcased for applications of graphene polymer composites by considering their electro‐thermal and antibacterial properties in highly oriented orthogonal morphologies. The high level of anisotropy induced in the graphene nanocomposites studied stands out through: 1) up to four decades higher electrical conductivities recorded in comparison to their randomly oriented counterparts, at concentrations where the latter show minimal improvements compared to the unfilled polymer; 2) over 1200% improvement in thermal conductivity, 3) antibacterial surfaces at field benchmark levels with lower filler content and with the added versatility of arbitrary orientation of the nanofillers. Overall, the new method and variations thereof can open up new horizons for tailoring nanostructure and performance for virtually all major nanocomposite applications based on graphene and other types of fillers.

Investigation of the Effectiveness of Silicon Nitride as a Reinforcement Agent for Polyethylene Terephthalate Glycol in Material Extrusion 3D Printing.

Polyethylene terephthalate glycol (PETG) and silicon nitride (Si3N4) were combined to create five composite materials with Si3N4 loadings ranging from 2.0 wt.% to 10.0 wt.%. The goal was to improve the mechanical properties of PETG in material extrusion (MEX) additive manufacturing (AM) and assess the effectiveness of Si3N4 as a reinforcing agent for this particular polymer. The process began with the production of filaments, which were subsequently fed into a 3D printer to create various specimens. The specimens were manufactured according to international standards to ensure their suitability for various tests. The thermal, rheological, mechanical, electrical, and morphological properties of the prepared samples were evaluated. The mechanical performance investigations performed included tensile, flexural, Charpy impact, and microhardness tests. Scanning electron microscopy and energy-dispersive X-ray spectroscopy mapping were performed to investigate the structures and morphologies of the samples, respectively. Among all the composites tested, the PETG/6.0 wt.% Si3N4 showed the greatest improvement in mechanical properties (with a 24.5% increase in tensile strength compared to unfilled PETG polymer), indicating its potential for use in MEX 3D printing when enhanced mechanical performance is required from the PETG polymer.

Mapping 3D printed part density and filament flow characteristics in the material extrusion (MEX) process for filled and unfilled polymers

ABSTRACT Material extrusion (MEX) 3D printing offers a promising avenue for fabricating metal and ceramic components, where highly loaded polymer filaments are 3D-printed and sintered. Achieving nearly 100% 3D-printed part density is critical in this process, as porosity during printing compromises part properties after sintering. However, challenges arise due to the unfavourable mechanical and rheological properties of MEX metal filaments, leading to slow print-speeds, filament breakage, and inconsistent extrusion. This work explores these process-property correlations by developing process maps for bound metal filaments and unfilled polymer systems. This study throws light on the significance of back-flow and back-pressure in calculating the pressure drop across the nozzle, especially in a diverse set of material systems represented by hard and stiff PLA, soft and flexible TPU, and brittle and fragile bronze filaments. Additionally, ANOVA identified the effect of print conditions on measured variables, while regression models helped predict the behaviour of a given material under different process conditions. Therefore, this study enables material design and discovery for bound-metal filaments while addressing critical knowledge gaps, thereby paving the way for high-density 3D-printed components.

Enhancement of dielectric properties of the La2NiO4-CuO terpolymer nanocomposites by modified SiC nanofiller

This work investigates the enhancement of dielectric properties of La2NiO4-CuO terpolymer nanocomposites using surface modified SiC nanoparticles as fillers. SiC nanoparticles were subjected to acid treatment and annealing at 1000 °C to tailor the surface chemistry. Acid treatment involved immersing the SiC powder in a mixture of H2SO4 and HNO3 acids and sonicating for 30 min, followed by stirring at 60 °C for 6 h. Annealing was carried out at 1000 °C for 2 h in an inert argon atmosphere. La2NiO4 and CuO nanoparticles were synthesized by sol-gel and precipitation techniques respectively, with average particle sizes of 20–40 nm and 10–15 nm confirmed by XRD and FESEM. Nanocomposites were fabricated by dispersing 2–10 wt% of untreated, acid treated and annealed SiC nanoparticles in a La2NiO4-CuO mixture solution, using PVDF as the polymer matrix. Impedance spectroscopy revealed that addition of 5 wt% acid treated SiC resulted in the highest dielectric constant of 42 at 1 kHz, in comparison to 25 for the unfilled polymer. This was attributed to increased interfacial polarization arising from uniform dispersion of nanoparticles and abundant charge trapping sites introduced by the SiC filler.

Wall Slip-Free Viscosity Determination of Filled Rubber Compounds Using Steady-State Shear Measurements.

The high-pressure capillary rheometer (HPCR) represents a state-of-the-art instrument for the determination of rheological properties for plastics and rubber compounds. Rubber compounds have an increased tendency to exhibit flow anomalies depending on the compound ingredients and the processing parameters. Combined with non-isothermal effects due to dissipative material heating, this causes rheological material measurements and the resulting material parameters derived from them to be affected by errors, since the fundamental analytical and numerical calculation approaches assume isothermal flow and wall adhesion. In this paper, the applicability of the empirical rheological transfer function of the Cox-Merz rule, which establishes a relationship between shear viscosity measured with a HPCR and complex viscosity measured with a closed cavity rheometer (CCR), is investigated. The Cox-Merz relation could not be verified for an unfilled EPDM raw polymer or for filled, practical rubber compounds. Using a closed cavity rheometer, a methodology based on ramp tests is then introduced to collect wall slip-free steady-state shear viscosity data under isothermal conditions. The generated data show high agreement with corrected viscosity data generated using the HPCR, while requiring less measurement effort.

A Composite of Polyether Ether Ketone and Silica‐Coated Copper Particles for Creating Tailored Conductive Tracks via Laser Printing

AbstractConventional substrates for optoelectronic systems include inorganic or organic carrier materials; however, these systems are typically subjected to environmentally harmful multistep processes to prepare printed circuit boards. To mitigate these issues, the present article reports a polyether ether ketone (PEEK)‐based composite densely filled with copper microparticles, prepared using a simple, cost‐effective, and sustainable synthesis method. The material exhibits high thermal conductivity but is electrically nonconductive prior to undergoing laser treatment. To prevent the composite from exhibiting electrical conductivity, the copper particles are coated with a thin silica layer through a sol–gel reaction. The thermal stability of PEEK and the Cu–PEEK composites with Cu contents of up to 70 vol%, which are prepared via heat melding, is investigated by thermogravimetric analysis, differential scanning calorimetry, and Fourier‐transform infrared spectroscopy to clarify the manner in which copper affects the chemical structure of the polymer. The developed composite exhibits a significantly higher thermal conductivity than that of the unfilled PEEK polymer. This paper also describes the effects of laser treatment on the surface morphology. Overall, this study suggests that conductive tracks with low electrical resistance can be created on electrically insulating substrates with high thermal conductivity.

Hemp hurd filled PLA‐PBAT blend biocomposites compatible with additive manufacturing processes: Fabrication, rheology, and material property investigations

AbstractA co‐continuous 50:50 blend of poly(lactic acid) (PLA) and poly(butylene adipate‐co‐terephthalate) (PBAT) was compounded with 10–40 wt% hemp hurd microparticles (<250 μm) to achieve balanced material properties for additive manufacturing (3D printing) applications. The blend and composites were further compatibilized with maleic anhydride via an in situ reactive extrusion process to enhance the adhesion between the polymers and the fillers and subsequently improve stress transfer between the components. All composite samples were processed further via injection molding and 3D printing processes to analyze and compare the rheology, morphology, thermal, mechanical properties, and other physio‐chemical properties. For the unfilled polymer blends, the injection molded and 3D printed sample specimens displayed similar mechanical properties. However, in the hemp filled composites, the injection molded specimens demonstrated enhanced mechanical properties. This indicates that the 3D printing process requires further parameter optimization to eliminate potential gaps between the printing layers and enhance mechanical properties. Overall, the PLA:PBAT blends filled with hemp hurd microparticles provided balanced composite properties in addition to their sustainability attribute, which makes them an appealing alternative for the fabrication of compostable and tough materials via additive manufacturing processes.Highlights Upon maleation, the blend components formed a co‐continuous morphology. Sustainable plastic filament with up to 40 wt% hemp hurd micro particles. 3D printing can compete with injection molding in filled composites. Successfully 3D printed model furniture with 30 wt% hemp filler.

Using Thermomechanical Properties to Reassess Particles' Dispersion in Nanostructured Polymers: Size vs. Content.

Nanoparticle-filled polymers (i.e., nanocomposites) can exhibit characteristics unattainable by the unfilled polymer, making them attractive to engineer structural composites. However, the transition of particulate fillers from the micron to the nanoscale requires a comprehensive understanding of how particle downsizing influences molecular interactions and organization across multiple length scales, ranging from chemical bonding to microstructural evolution. This work outlines the advancements described in the literature that have become relevant and have shaped today's understanding of the processing-structure-property relationships in polymer nanocomposites. The main inorganic and organic particles that have been incorporated into polymers are examined first. The commonly practiced methods for nanoparticle incorporation are then highlighted. The development in mechanical properties-such as tensile strength, storage modulus and glass transition temperature-in the selected epoxy matrix nanocomposites described in the literature was specifically reviewed and discussed. The significant effect of particle content, dispersion, size, and mean free path on thermomechanical properties, commonly expressed as a function of weight percentage (wt.%) of added particles, was found to be better explained as a function of particle crowding (number of particles and distance among them). From this work, it was possible to conclude that the dramatic effect of particle size for the same tiny amount of very small and well-dispersed particles brings evidence that particle size and the particle weight content should be downscaled together.

Investigation of Mechanical and Dimensional Features in Unfilled Polyketone Polymer

Investigation of Mechanical and Dimensional Features in Unfilled Polyketone Polymer

The Effect of Nano Zirconium Dioxide (ZrO2)-Optimized Content in Polyamide 12 (PA12) and Polylactic Acid (PLA) Matrices on Their Thermomechanical Response in 3D Printing.

The influence of nanoparticles (NPs) in zirconium oxide (ZrO2) as a strengthening factor of Polylactic Acid (PLA) and Polyamide 12 (PA12) thermoplastics in material extrusion (MEX) additive manufacturing (AM) is reported herein for the first time. Using a melt-mixing compounding method, zirconium dioxide nanoparticles were added at four distinct filler loadings. Additionally, 3D-printed samples were carefully examined for their material performance in various standardized tests. The unfilled polymers were the control samples. The nature of the materials was demonstrated by Raman spectroscopy and thermogravimetric studies. Atomic Force Microscopy and Scanning Electron Microscopy were used to comprehensively analyze their morphological characteristics. Zirconium dioxide NPs showed an affirmative reinforcement tool at all filler concentrations, while the optimized material was calculated with loading in the range of 1.0-3.0 wt.% (3.0 wt.% for PA12, 47.7% increase in strength; 1.0 wt.% for PLA, 20.1% increase in strength). PA12 and PLA polymers with zirconium dioxide in the form of nanocomposite filaments for 3D printing applications could be used in implementations using thermoplastic materials in engineering structures with improved mechanical behavior.

Running-In Effects of Lubricated Polyether Ether Ketone on Steel for Different Spreading and Sorption Tendencies

Polyether ether ketone is a highly resilient thermoplastic that can withstand as an unfilled or filled polymer tribological high loads in high-temperature applications, as it has a high glass and melting temperature. Currently, it attracts interest as a lubricated material for drive systems to minimize noise, as a lightweight solution improving the CO2 balance, or in combination with novel lubricants. We have produced friction and wear maps with pin-on-disk tests on steel axial bearing rings and investigated the interaction and running-in behavior with different lubricants, such as different polyalkylene glycols, polyalphaolefin, and various esters. In general, the behavior of polyether ether ketone is hardly influenced by the frictional heat when loaded at room temperature. It shows a lubricant-specific polymer transfer and surface softening. This running-in impact is enhanced if a loading strategy with initial high friction power is applied. The beneficial transfer forms on the track in mixed lubrication on the rough counterpart until an increasing adhesive contact limits this effect. The appearance of a minimal wear coefficient was found below the glass temperature with lubricants strongly sorbing in polyether ether ketones, such as polar polyalkylenglycol or trimellitic acid ester-based lubricants. Using the interfacial energy of the system to derive an energy term describing the tendency to form a stable transfer, systematic trends in the tribological behavior of polyether ether ketone and polyketone could be identified that can be projected on other systems.

The influence of natural shungite on the properties and structure of polytetrafluoroethylene

The paper presents the results of physical-mechanical and tribological studies of composites based on polytetrafluoroethylene and natural shungite. It has been established that the introduction of shungite leads to an increase in the wear resistance of the material by 114 times compared to an unfilled polymer. Electron microscopy has shown that a secondary layer is formed on the friction surface of the composites, which protects the material from wear. Using IR spectroscopy, it has been established that during the wear of composites, tribochemical reactions occur with the formation of oxygen-containing functional groups and subsequent structuring of the surface layer. The results of the study obtained by differential scanning calorimetry show that the presence of natural shungite in the PTFE matrix leads to ordering of the structure of the composites.

Thermal and Dielectric Properties of 3D Printed Parts Based on Polylactic Acid Filled with Carbon Nanostructures

AbstractPolylactic acid (PLA) containing 12 wt% of nanofillers, such as multi‐walled carbon nanotubes (MWCNTs), graphene nanoplates (GNPs), is considered to obtain a non‐conventional filament suitable for additive manufacturing (AM) process with enhanced thermal and electrical properties. In details, three‐dimensional (3D) printed specimens obtained by means of fused deposition modeling (FDM) are experimentally characterized in terms of thermal conductivity and relative permittivity. The results are interpreted on the basis of the different features of the fillers and their interaction with the PLA, as evidenced by a morphological analysis. It is found better thermal transport by using two‐dimensional (2D) shape nanoparticles (GNPs) with an improvement of about 260% respect to the unfilled polymer most likely due to its favorable arrangement and the lower thermal boundary resistance between the two phases, matrix, and fillers. Differently, mono‐dimensional filler like MWCNTs is to be preferred in order to obtain higher value for the relative permittivity, due to the enhancement of the interfacial polarization and the presence of functionalized groups. It is found a value of 5.35 × 103 much greater than that of 3.7 measured for pure PLA. Given the good combined thermal and dielectric properties, such materials are promising candidates for packaging applications with electromagnetic (EM) shielding capability.

Development of reduced Graphene oxide modified Ultrahigh molecular weight polyethylene (rGO/UHMWPE) based Nanocomposites for Biomedical Applications

Ultrahigh molecular weight polyethylene (UHMWPE) are widely used as a biomaterial for manufacturing of prostheses, implants and other biomedical components with complex geometry and shapes. Continuous loading of these components subject to heavy stress and deformation resistance should have enhanced mechanical and chemical properties. This paper aims to improve the mechanical and thermal aspects of the conventional UHMWPE by supplementing reduced Graphene oxide (rGO) in varying weight percentages to develop polymer bio nanocomposite samples. The effect of green synthesized GO nanoparticles in the UHMWPE polymer was investigated for biomedical application. The rGO was distributed in a UHMWPE matrix using a unique and optimized technique to create high-performance nanocomposites. The proposed UHMWPE filled with different loading (0, 0.5, 1.0,1.5, 2.0, and 3.0 wt.%) of rGO was produced by Ultrasonication in an acetone medium. The findings suggest that evenly distributed rGO layers were present throughout the polymer matrix. This, in turn, indicates a good connection between the fillers and matrix by Scanning electron microscopy (SEM) and Energy Dispersive X-Ray Analysis (EDAX), resulting in better composite capabilities. The layers of rGO-aided lamellar arrangements and microfibers between the crystals were observed in the results. The Microhardness of the bio nanocomposite (1 Wt.% rGO/UHMWPE) with 1wt.% rGO in the UHMWPE matrix increased by 2.8% compared to an unfilled polymer. At the same rGO concentration, the bio nanocomposite had a crystallization degree of 46.96%. To achieve optimal performance, rGO content of 1wt.% was added to the sample, which is ideal in many situations where good mechanical and thermal qualities are required during operation. The outcomes reveal that the rGO supplement primarily boosts the thermo-mechanical performances of the modified bio-nano composites for orthopedic products.

Comparative analysis of rheological properties indicators for thermoplastic melts

The introduction analyzes the state of the issue and substantiates the research relevance. The aim of the work is to determine and comparatively analyze the values of physically normalized indicators of rheological properties of typical representatives of thermoplastic melts. In the methodological part of the work, to ensure the comparability of the results, the physically normalized form of the Ostwald-de-Waele power empirical rheological equation proposed by McKelvey is used. The calculation scheme is based on the transition from an approximating power function with rheologically non-deterministic parameters to two dimensionless rheologically determined complexes characterizing the stress-strain state of a nonlinear-viscous medium. The first dimensionless complex is presented in the form as the ratio of the actual shear rate to a unit normalization base value, and the second is in the form as the ratio of shear stresses acting on the deformable medium to the base (reduced) value of these stresses, which are necessary to overcome viscous resistance at a unit normalization shear rate. A technique is described for determining physically normalized indicators of rheological properties using the thermoplastic melts flow curves available in the scientific and technical literature (dependence of shear stresses on shear rate) based on the processing of these graphical dependencies plotted in double logarithmic coordinates. In the main part of the work, the values of physically normalized indicators of rheological parameters (the reduced index of viscous resistance and the indicator of the rheological nonlinearity of the melt) are determined and presented in the form of tables for widely used types of filled and unfilled thermoplastic polymers. A comparative analysis of these indicators has been carried out. Conclusions are given on the work and it is noted that the results of the research can be used in engineering practice, as well as in the educational process when performing rheological calculations of the processes of processing thermoplastic polymeric materials.