Polyurethane Composites Research Articles

Preparation of liquid metal/thermoplastic polyurethane composites with enhanced thermal conductivity via rolling regulation

Abstract This work reports a method for preparing liquid metal/thermoplastic polyurethane (LM/TPU) elastic composite materials through melt blending, and enhancing the thermal conductivity of the composites using a rolling regulation process. Through observation of the microstructure of the composite material, it is found that the vane mixer can effectively disperse LM uniformly, which leads to a significant enhancement in thermal conductivity from 0.21 W m−1 K−1 of pure TPU to 2.12 W m−1 K−1 for composite with 50 vol % LM. After rolling regulation, SEM images reveal the formation of interconnected thermal conduction pathways within the composites. The thermal conductivity of the composite material with 30 vol % LM increases from 1.74 W m−1 K−1 to 2.50 W m−1 K−1, which is higher than the pre-regulation thermal conductivity of the composite with 50 vol % LM. Moreover, the thermal conductivity of the composite material with 50 vol % LM increases even further to 3.16 W m−1 K−1. The rheological behavior of the composite further substantiates the establishment of a network configuration after the rolling regulation that facilitates heat transfer. This implies that the melt blending-rolling regulation process can achieve the fabrication of composite materials with high thermal conductivity, offering a reliable strategy for industrial development of flexible thermal conductive materials.

Analysis of Post-Treatment Heating of Stretchable Piezoelectric Electrospun Nanofibers

Electrospun piezoelectric nanofibrous membrane developed from Polyvinylidene fluoride (PVDF) embedded with thermoplastic polyurethane (TPU) composites found to have superior stretchability and piezoactivity. The piezoresponse behavior of different in-situ bended PVDF/TPU, up to 15wt.% of TPU, is examined using various blending ratios of PVDF and TPU. It has been shown that adding TPU with PVDF at certain specific concentration increased the nanofiber's piezo-efficiency.The generated nanomembranes are annealead at different temperatures up to 100°C. An extensive analysis of the effects of annealing is conducted on these nanomats, and it is thought to be a crucial post-treatment method for improving the piezoresponse of the manufactured nanomats. Nanofibers annealed at 100°C showed best effective response compared to all other samples and this revealed the effectiveness of annealing treatment in the enhancement of piezoactivity. The best effective composition of PVDF with 15 wt% TPU after an annealing treatment of 100°C generated a maximum voltage of 3.2 V under the effect of an applied force of 3 N, where unannealed sample of the same PVDF-TPU composition generated only a voltage of 2.2 V. This annealed piezo nanogenerator (PNG), can be considered an optimum option for electromechanical energy harvesting applications that require flexibility and self-power.

Camelina sativa (L.) Crantz straw and pomace as a green filler for integral skin polyurethane foam

The development of efficient methods for obtaining cellular materials with improved functional properties is a constant challenge for the plastics industry, including the polyurethane industry. In recent years, efforts have been made to obtain cheap and easily available raw materials that can be used as foam fillers. In addition to commercially used synthetic fillers, more and more attention is paid to materials of natural origin, in particular to agricultural and industrial waste. This solution not only meets the assumptions of the "Green Chemistry" concept but also creates the opportunity to improve the properties of plastics while reducing their production costs. This study focuses on the use of naturally derived materials as fillers in flexible integral polyurethane foams (Integral Skin Foams, ISFs) to produce economically advantageous and ecologically sustainable composite materials. Waste materials such as Camelina sativa (L.) Crantz straw and pomace were used as biofillers. The obtained samples were used to determine the processing parameters and functional properties of the foams: hardness, tensile strength, elongation at break and permanent deformation after compression. In the case of both straw and pomace, an increase in growth time and an increase in the free density of the foams were observed with an increase in the amount of added plant material. The analysis of morphology and chemical structure of the obtained composites led to the conclusion that the cellular structure, skin thickness, and functional groups present in biofillers had a direct impact on the functional properties of ISF. For most composites, a significant improvement in mechanical parameters was observed compared to the reference foam. The obtained results confirmed the utility potential of Camelina sativa (L.) Crantz straw and pomace. The main research assumption has been fully implemented that focused on obtaining innovative polyurethane composites with improved functional properties.

Multiscale study on the synergistic effect of interface heat transfer and filler structure on enhancing the thermal conductivity of boron nitride/alumina/polyurethane composites

The design and preparation of polymer composites for microelectronic package with high thermal conductivity is an important route to solve the thermal problem of electronic devices. The synergistic effect of interface heat transfer and hybrid filler structure on the enhancement of thermal conductivity in polyurethane composites was analyzed using a multiscale approach. Firstly, the interface heat transfer characteristics and strengthening mechanism of BN-TPU and Al2O3-TPU regulated by functionalization were analyzed by atomic scale calculation. Then, the thermal conductivity of BN/Al2O3/TPU composites under different interface thermal resistance, filler distribution, filler ratio and contents were studied through representative volume elements with interface layer structure. The results indicate that, due to the functionalized molecules increasing the phonon vibration overlap between the filler and matrix and thereby reducing the interface thermal resistance, the thermal conductivity of the composite materials shows an increasing trend with interface functionalization. Moreover, under the combined effects of constructing oriented BN structures, optimizing the ratio between BN and Al2O3, and regulating interface functionalization, the composites showed excellent thermal conductivity at low filler content. The research can provide important guidance for the preparation of highly thermal conductive polymer composites.

Stretchable liquid metal grid/metallized polyurethane composites with switchable electromagnetic interference shielding and efficient infrared stealth performance

Intelligent electromagnetic interference (EMI) shielding materials with tunable electromagnetic shielding properties becomes a significant and urgent concern for information society. Hence, a switchable and low-reflectivity EMI shielding composite is fabricated by electroless nickel plating on the surface of polyurethane nonwoven fabric (Ni@TPU), and followed by combining with liquid metal (LM) grid. The synergistic combination of Ni@TPU and LM grid effectively facilitates the rational construction of hierarchical impedance matching. Meanwhile, it promotes destructive interference between electromagnetic waves reflected from Ni@TPU and the LM grid. As a result, an excellent low-reflectivity EMI shielding performance can be achieved. More importantly, the switchable EMI shielding performance can be easily realized by repeatedly stretching Ni@TPU/LM. In addition, the fluffy nonwoven fabric and LM grid with low infrared emissivity endow it with an outstanding infrared stealth performance. Such excellent low-reflectivity EMI shielding switch performance incorporated with flexible infrared stealth makes it possible to become smart EMI shielding material with a great promise to be employed in the application scenario of window in camouflage container.

Airflow sensing and energy harvesting applications of PVDF-TPU piezoelectric nanofibers

Wind energy is one of the abundant potential power sources that can be found both indoors and outdoors. Recently, the focus has been placed on the potential of ambient energy gathering using natural airflow as a small-scale wind energy source. Here, highly piezoelastic nanofiber mats were fabricated from a pure polyvinylidene fluoride (PVDF) and PVDF-TPU (thermoplastic polyurethane) composites via the electrospinning approach. They have exceptional electrical energy harvesting and airflow sensing capabilities. The potential of these composite nanomats for piezoelectric energy harvesting was studied, depending on airflow perturbations in the surrounding environment. PVDF blended with 15 weight percent (wt.%) TPU exhibited the optimum sensitivity, clearly demonstrating the scope of these developed prototypes in the field of airflow sensing and energy harvesting technology.

Bio-Based Polyurethane Composites with Adjustable Fluorescence and Ultraviolet Shielding for Anti-Counterfeiting and Ultraviolet Protection.

Polyurethane and its composites play an important role in innovative packing materials including anticounterfeiting and ultraviolet protection, however, they are mainly derived from petroleum resources that are not sustainable. In this study, a 100% biobased thermoplastic polyurethane (Bio-TPU) was synthesized using biobased poly(trimethylene ether) glycol, pentamethylene disocyanate, and 1,4-butanediol. Subsequently, biobased tannic acid (TA) was employed to prepare biobased composites. The structures and properties of Bio-TPU and its composites were systematically evaluated. The results showed that the Bio-TPU/TA composite films had excellent and controllable fluorescence and UV-shielding properties. The fluorescence colors of the Bio-TPU/TA composite films could be adjusted to blue, green, and yellow by varying the TA content and adding coupling agents. Moreover, the UV transmittance of the Bio-TPU/TA composites decreased from 79.25 to 5.43% below 400 nm with an increasing TA content, indicating an excellent ultraviolet-barrier performance. Consequently, biobased TPU/TA composite films can be utilized as innovative anticounterfeiting materials and UV-shielding protection films. This study is expected to facilitate sustainable development in the polyurethane industry and broaden the high-end applications of polyurethane such as fashion, electronics, food manufacturing, pharmaceuticals, and finance.

Thermally conductive, mechanically robust alumina-incorporated polyurethane films prepared by ultraviolet light curing

Abstract The development of heat dissipating composite materials for electronic systems can be expedited using alumina particles as modifiable polymer-matrix fillers. However, these composites are difficult to synthesize given the tradeoffs between thermal conductivity, insulating characteristics, and conduciveness to processing. To that end, the present study is focused on synthesizing environmentally friendly polyurethane films that could be cured by ultraviolet light within minutes, without requiring high-temperature heat treatment. Through the optimization of alumina modification, hybridization of thermally conductive fillers, filler content, and stirring time on the thermal conductivity of the polyurethane composites, this study improves the process for sustainability, low-cost, and convenient preparation. The experimental results confirmed that the use of surface modification and hybrid fillers is effective for enhancing the thermal conductivity, with the value of the polyurethane integrated with 50 wt% Al2O3 and 5 wt% Al2O3–poly (catechol/polyamine) being 76.40 wt% higher than that of pure PU (0.44 W/mK). Additionally, the use of hybrid fillers resulted in superior mechanical and thermal properties (such as tensile strain, tensile strength, thermal expansion coefficient, and temperature resistance) compared with those of pure PU and films incorporated with only a single filler.

Improvement of Mechanical and Acoustic Characteristics of Halloysite Nanotube-Reinforced Polyurethane Elastomer Composites and Their Applications.

Polyurethane incorporated with nanofillers such as carbon nanotubes, basalt fibers, and clay nanoparticles has presented remarkable potential for improving the performance of the polymeric composites. In this study, the halloysite nanofiller-reinforced polyurethane elastomer composites were prepared via the semi-prepolymer method. The impact of different halloysites (halloysite nanotubes and halloysite nanoplates) in polyurethane composites was investigated. Scanning electron microscopy, X-ray diffraction, infrared spectroscopy, electronic universal tensile testing, and acoustic impedance tube testing were employed to characterize the morphology, composition, phase separation, mechanical properties, and sound insulation of the samples. The composite fabricated with 0.5 wt% of halloysite nanotubes introduced during quasi-prepolymer preparation exhibited the highest tensile strength (22.92 ± 0.84 MPa) and elongation at break (576.67 ± 17.99%) among all the prepared samples. Also, the incorporation of 2 wt% halloysite nanotubes into the polyurethane matrix resulted in the most significant overall improvements, particularly in terms of tensile strength (~44%), elongation at break (~40%), and sound insulation (~25%) within the low-frequency range of 50 to 1600 Hz. The attainment of these impressive mechanical and acoustic characteristics could be attributed to the unique lumen structure of the halloysite nanotubes, good dispersion of the halloysites in the polyurethane, and the interfacial bonding between the matrix and halloysite fillers.

Synergistic Reinforcing Effect of Hazelnut Shells and Hydrotalcite on Properties of Rigid Polyurethane Foam Composites.

Recently, the development of composite materials from agricultural and forestry waste has become an attractive area of research. The use of bio-waste is beneficial for economic and environmental reasons, adapting it to cost effectiveness and environmental sustainability. In the presented study, the possibility of using hazelnut shell (HS) and hydrotalcite (HT) mineral filler was investigated. The effects of fillers in the amount of 10 wt.% on selected properties of polyurethane composites, such as rheological properties (dynamic viscosity, processing times), mechanical properties (compressive strength, flexural strength, hardness), insulating properties (thermal conductivity), and flame-retardant properties (e.g., ignition time, limiting oxygen index, peak heat release), were investigated. Polyurethane foams containing fillers have been shown to have better performance properties compared to unmodified polyurethane foams. For example, the addition of 10 wt% of hydrotalcite filler leads to PU composite foams with improved compression strength (improvement by ~20%), higher flexural strength (increase of ~38%), and comparable thermal conductivity (0.03055 W m-1 K-1 at 20 °C). Moreover, the incorporation of organic fillers has a positive effect on the fire resistance of PU materials. For example, the results from the cone calorimeter test showed that the incorporation of 10 wt% of hydrotalcite filler significantly reduced the peak of the heat release rate (pHRR) by ca. 30% compared with that of unmodified PU foam, and increased the value of the limiting oxygen index from 19.8% to 21.7%.

Study on the tribological properties of MXene reinforced polyurethane composites under dry conditions

The mechanical properties of the polymer matrix are crucial for forming a stable and dense transfer film between the friction pairs, facilitating friction reduction and wear resistance. This work introduces a novel polyurethane composite (PUC) system, prepared by incorporating the MXene (Ti3C2Tx) into a polyurethane elastomer, which exhibits a robust strength of ∼ 64 MPa and an excellent toughness of ∼ 155.8 MJ/m3. The PUC containing 0.5 wt% MXene (PUC0.5) exhibited excellent tribological properties, with the friction coefficient and wear rate (66 N, 0.54 m/s) reduced by 45.1 % and 206 % in comparison to pure PU, respectively. The excellent tribological properties of PUC0.5 are attributed to exceptional mechanical properties and low shear of MXene.

Effect of the filler content on some physical and mechanical properties of virgin- and recycled thermoplastic polyurethane composites

Effects of thermoplastic polyurethane (TPU) types (Recycled (R) and Virgin (V)) composites with 15 wt% and 30 wt% oakwood flour addition were studied. Selected physical, mechanical, morphological, and thermal properties of resulting polymer composites were analyzed. Test samples were manufactured using injection molding, except that abrasion resistance specimens were manufactured using a compression molding process. The findings indicated that the types of TPU and filler contents played a significant role in the density and mechanical properties of the TPU test samples. The increased oak wood flour contents in both TPU types showed improvement in density, tensile modulus, hardness, flexural strength flexural modulus, dynamic impact strength, and yield strength of the composite while decreasing the elongation at break values. In addition, both TPU types and filler contents significantly affected the densities of V-TPU and R-TPU. The TPUs type, filler content, and cycle-rpm affected Taber’s abrasion resistance values. Weight loss, which increased with the number of cycles for the control samples, decreased with increasing wood flour content. This study aimed to provide an overview of the effect of the wood flour content in the manufacturing of thermoplastic-reinforced composites and to provide a basis for further research and development efforts.

Development and 4D printing of magneto-responsive PMMA/TPU/Fe3O4 nanocomposites with superior shape memory and toughness properties

This paper introduces 4D printing of composites of polymethyl methacrylate (PMMA) and thermoplastic polyurethane (TPU) reinforced with Fe3O4 particles for the first time. PMMA/TPU blends with 70/30 wt% are selected as matrix with the best compatibility based on dynamic mechanical thermal analysis. Fe3O4 nanoparticles are added to the blends with 10 %, 15 % and 20 % weight ratios. Their addition enables remote actuation of the materials in a high frequency alternating magnetic field. Field emission scanning microscopic images confirms a full dispersion of nanoparticles inside the polymeric matrix. Nanocomposites with 20 wt% of Fe3O4 can perfectly recover the permanent shape within 1.5 min in the magnetic field. They also reveal perfect shape memory properties in the hot water. Moreover, all samples display a perfect shape fixity ratio. The addition of TPU significantly enhances the toughness and flexibility of the PMMA matrix. It is found that Fe3O4 nanoparticles further enhance the mechanical strength by 10 % to 15 %, although they reduce the strain at break from 17 % to 14 %. Finally, a gripper is 4D printed and its excellent performance in the magnetic field is demonstrated.

Activated Carbon and Biochar Derived from Sargassum sp. Applied in Polyurethane-Based Materials Development.

Activated carbon (AC) and biochar (BC) are porous materials with large surface areas and widely used in environmental and industrial applications. In this study, different types of AC and BC samples were produced from Sargassum sp. by a chemical activation and pyrolysis process and compared to commercial activated carbon samples. All samples were characterized using various techniques to understand their structure and functionalities. The metal content of the samples was characterized by using an inductively coupled optical emission spectrometer (ICP-OES). A toxicity test was applied to investigate the effect of AC/BC on organisms, where Sinapis alba seed and Escherichia coli bacteria-based toxicity tests were used. The results revealed that the samples did not negatively affect these two organisms. Thus, it is safe to use them in various applications. Therefore, the samples were tested as fillers in polyurethane composites and, thus, polyurethane-AC/BC samples were prepared. The amounts of AC/BC mixed into the polyurethane formulation were 1%, 2%, and 3%. Mechanical and acoustic properties of these composites were analyzed, showing that by adding the AC/BC to the system an increase in the compression strength for all the samples was achieved. A similar effect of the AC/BC was noticed in the acoustic measurements, where adding AC/BC enhanced the sound adsorption coefficient (α) for all composite materials.

Impact performance of egg‐box core sandwich panels made from sisal fibers and castor‐oil‐based polymer

AbstractDeveloping sustainable composites for engineering applications is essential for minimizing environmental impacts and ensuring the long‐term viability of infrastructure and technological advancements. In this context, this work focuses on the manufacture and evaluation of the structural integrity of a sandwich structure composed of aluminum faces and egg‐box‐shaped, sisal fiber‐reinforced epoxy (SFE) or castor‐oil polyurethane (SFC‐O) composites. The sandwich panel is filled with a biobased foam and subjected to dynamic load (drop‐tower) test. For comparison, the base materials SFE and SFC‐O molded into the egg‐box‐shaped cores are also evaluated using Charpy impact tests to establish a potential correlation between their Charpy performance and the drop‐tower behavior of egg‐box sandwich structures. The findings reveal that SFC‐O laminates demonstrate superior Charpy impact resistance (~49%) compared to SFE laminates. Similarly, sandwich structures composed of egg‐box‐castor‐oil composite cores absorb approximately 42.5% more energy than those made with egg‐box‐epoxy cores. The impact behavior of the sandwich structures correlates directly with the impact resistance of the sisal fiber laminates. Overall, the results indicate that the castor‐oil polymer can effectively replace the epoxy polymer matrix phase, enhancing impact absorption and providing an environmentally correct and sustainable solution for fabricating sandwich panels.Highlights Castor‐oil polymer provides laminates with lower density relative to epoxy. Sisal‐castor‐oil‐based laminates possess higher impact resistance than those based on epoxy. Sisal‐castor‐oil‐based panels achieve higher absolute and specific drop‐tower impact properties. Panels subjected to drop‐tower impact tests reveal skin delamination, wrinkling and indentation. Debonding between the foam and egg‐box core is a typical failure mode for epoxy sandwich panels.

Enhanced thermal conductivity of UHMWPE by coating boron nitride and polyurethane composites

The development of textile wearable electronics has increased demands and requirements for thermal management materials due to integrated and miniaturized soft equipment. In this work, the surface of ultrahigh molecular weight polyethylene (UHMWPE) fibers was first decorated by polydopamine (PDA) to improve the surface activity and construct a steady interface layer. Then the boron nitride/polyurethane coating surface modified UHMWPE composite yarns with good thermal conductivity were produced using a coaxial wet forming process. The thermally conductive composite yarns demonstrated great mechanical properties (5.09 % strain, 0.79 N/tex strength) and thermal conductivity (0.54 ± 0.02 W·mK−1) with the BN/PU weight ratio of 1. Furthermore, the resistance to failure cycles was taken place, and the composite yarns kept good thermal conductivity after multiple cycles twisting, bending, washing, cooling and heating cycles. By the coaxial wet fabrication, the thermally conductive composite yarns were constructed, offering a viable and trustworthy method for creating polymer-based thermal interface materials with high thermal conductivity.

Effect of size and loading of waste single-used plastic (SUP) aggregates on a bio-based high density polyurethane composite

Abstract The utilization of waste single-use plastic (SUP) as fillers by containment in a polyurethane matrix was investigated as an alternative solution to the detrimental disposal of these waste materials. High-density bio-based rigid polyurethane composites were prepared by adding polyol, isocyanate, and additives, along with densified SUP, which served as aggregate fillers to enhance the bulk density and flexural strength of rigid polyurethane while increasing the thermal conductivity. The aggregated SUPs were prepared using agglomeration-densification machine and exhibited size variations of 12.44 mm (A), 14.12 mm (B), and 15.56 mm (C). The resulting aggregates were added to the rigid polyurethane matrix at varied loadings of 40%, 50%, and 60% v/v. The green composites were cured in heated hydraulic press at constant temperature and pressure. Based on the obtained results, it was found that the formulation with a SUP size of C and a loading of 60% produced the composite of highest bulk density due to relatively high density of agglomerated SUP as the size enlarges. Additionally, the SUP size of A and a loading of 50% (50A) exhibited the highest flexural strength value. This behaviour was attributed to the increased filler-matrix interfacial area achieved with the smallest size aggregates. However, a further increase in aggregate loading resulted in a decrease in this property as common attribute for composite materials. On the other hand, it was revealed that increasing the loading of SUP aggregates provided a lesser insulating effect due to the increase in thermal conductivity resulting from the presence of filled pores within the polyurethane foam. The findings of this study contributed to understanding the effects of aggregate size and loading on the mechanical and thermal properties of the composite material, providing valuable insights for the development of energy-efficient and environmentally-friendly polyurethane structures.

Hybrid lattice structure with micro graphite filler manufactured via additive manufacturing and growth foam polyurethane

The utilisation of lightweight structures is a common practice across a range of disciplines, including the construction of light steel frames, sandwich panels, and transportation infrastructure, among others. The advantages of lightweight structures include design flexibility, weight reduction, and the sustainability of materials that can be easily recycled. However, these advantages also present significant weaknesses. Compared to solid materials with compact weight, lightweight structures do not have the same characteristics. With the reduction in material weight, the strength of the lightweight structure decreases significantly compared to solid materials. In this study, the lightweight structure was made using additive manufacturing and reinforced with solid Composite Polyurethane Foam reinforced with graphite filler expanded into the lightweight structure. The results showed that in the compression test, the mixture with 2 % graphite filler had the highest value of 2.5 kN. The highest hardness test on the specimen with a 2 % graphite mixture was 19.8 HA. FT-IR testing showed that the carbon bonds from graphite in the 2 % specimen had the highest intensity. The test results showed that the addition of Polyurethane Foam into the structure could enhance material strength effectively without adding significant material weight.

Flame Retardancy and Thermal Stability of Rigid Polyurethane Foams Filled with Walnut Shells and Mineral Fillers.

Recently, the influence of the concept of environmental sustainability has increased, which includes environmentally friendly measures related to reducing the consumption of petrochemical fuels and converting post-production feedstocks into raw materials for the synthesis of polymeric materials, the addition of which would improve the performance of the final product. In this regard, the development of bio-based polyurethane foams can be carried out by, among other things, modifying polyurethane foams with vegetable or waste fillers. This paper investigates the possibility of using walnut shells (WS) and the mineral fillers vermiculite (V) and perlite (P) as a flame retardant to increase fire safety and thermal stability at higher temperatures. The effects of the fillers in amounts of 10 wt.% on selected properties of the polyurethane composites, such as rheological properties (dynamic viscosity and processing times), mechanical properties (compressive strength, flexural strength, and hardness), insulating properties (thermal conductivity), and flame retardant properties (e.g., ignition time, limiting oxygen index, and peak heat release) were investigated. It has been shown that polyurethane foams containing fillers have better performance properties compared to unmodified polyurethane foams.

Bio-Based Polyurethane Composites from Macauba Kernel Oil: Part 1, Matrix Synthesis from Glycerol-Based Polyol

Polyurethanes are the result of a reaction between an isocyanate and a polyol. The large variety of possible reagents creates many possible polyurethanes to be made, such as soft foams, rigid foams, coatings, and adhesives. This polymer is one of the most produced and consumed polymers in the world with an ever-increasing demand. Despite its usual petrochemical nature, research on bio-based polyurethanes flourishes due to the ease in creating bio-based polyols. This work covers the synthesis of a novel macauba kernel oil polyol by the epoxidation of the oil, followed by a ring-opening reaction of the epoxide with glycerol, used for the preparation of polyurethane foams using different NCO/OH ratios. The FTIR and H1 results confirm the formation of the epoxide and polyol, and the polymers in all NCO/OH ratios were confirmed by FTIR, showing great similarities between the samples, especially PU 1.0 and PU 1.2. Despite the TGs showing close behaviors for the three samples, their DTGs showed great difference between the samples, with PU 1.0 presenting a regular PU DTG profile with three degradation peaks while the other two sample presented five degradation peaks, indicating a higher crosslinking density in them.