Composite polymer electrolytes based on electrospun thermoplastic polyurethane membrane and polyethylene oxide for all‐solid‐state lithium batteries

To improve the electrochemical properties and enhance the mechanical strength of solid polymer electrolytes, series of composite polymer electrolytes (CPEs) were fabricated with hybrids of thermoplastic polyurethane (TPU) electrospun membrane, polyethylene oxide (PEO), SiO₂ nanoparticles and lithium bis(trifluoromethane)sulfonamide (LiTFSI). The structure and properties of the CPEs were confirmed by SEM, XRD, DSC, TGA, electrochemical impedance spectroscopy and linear sweep voltammetry. The TPU electrospun membrane as the skeleton can improve the mechanical properties of the CPEs. In addition, SiO₂ particles can suppress the crystallization of PEO. The results show that the TPU‐electrospun‐membrane‐supported PEO electrolyte with 5 wt% SiO₂ and 20 wt% LiTFSI (TPU/PEO‐5%SiO₂‐20%Li) presents an ionic conductivity of 6.1 × 10^?4 S cm^?1 at 60 °C with a high tensile strength of 25.6 MPa. The battery using TPU/PEO‐5%SiO₂‐20%Li as solid electrolyte and LiFePO₄ as cathode shows an attractive discharge capacity of 152, 150, 121, 75, 55 and 26 mA h g^?1 at C‐rates of 0.2C, 0.5C, 1C, 2C, 3C and 5C, respectively. The discharge capacity of the cell remains 110 mA h g^?1 after 100 cycles at 1C at 60 °C (with a capacity retention of 91%). All the results indicate that this CPE can be applied to all‐solid‐state rechargeable lithium batteries. © 2018 Society of Chemical Industry     

A novel electrospun TPU/PVdF porous fibrous polymer electrolyte for lithium ion batteries

Novel blend-based gel polymer electrolyte (GPE) films of thermoplastic polyurethane (TPU) and poly(vinylidene fluoride) (PVdF) (denoted as TPU/PVdF) have been prepared by electrospinning. The electrospun thermoplastic polyurethane-co-poly (vinylidene fluoride) membranes were activated with a 1M solution of LiClO₄ in EC/PC and showed a high ionic conductivity about 1.6 mS cm⁻¹ at room temperature. The electrochemical stability is at 5.0 V versus Li⁺/Li, making them suitable for practical applications in lithium cells. Cycling tests of Li/GPE/LiFePO4 cells showed the suitability of the electrospun membranes made of TPU/PVdF (80/20, w/w) for applications in lithium rechargeable batteries. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Soft segmental effect of methylene bis(p‐cyclohexyl isocyanate) based thermoplastic polyurethane impregnated with lithium perchlorate/propylene carbonate on ionic conductivity

Thermoplastic polyurethane (TPU) was employed as the polymer matrix for ion conduction as gelled electrolytes with lithium perchlorate (LiClO₄) in propylene carbonate (PC) solution. The TPU was prepared by methylene bis(p‐cyclohexyl isocyanate) as the hard segment while employing both poly(ethylene glycol) (PEG) and poly(tetramethylene glycol) (PTMG) as the soft segments. The copolymer comprising both PEG and PTMG was prepared such that it possessed the combined characteristics of good conductivity from the former and good mechanical properties from the latter. All the polymers were characterized by gel permeation chromatography, differential scanning calorimetry, and Fourier transform IR spectroscopy. The conductivity data were obtained from alternating current impedance experiments. The results revealed that the copolymer containing both PEG and PTMG as the soft segments showed better performance than TPU containing either PEG or PTMG. The copolymer TPU(PEG/PTMG) proved to be a good gelled electrolyte from 5 to 85°C. This copolymer, impregnated with 150% LiClO₄/PC, possessed good mechanical strength and conductivity as high as 10^?3 S/cm. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 935–942, 2001     

Solid-state dye-sensitized hierarchically structured ZnO solar cells

A novel solid-state hierarchically structured ZnO dye-sensitized solar cell (DSC) was assembled by using TiO₂ as filler in polyethylene oxide (PEO)/polyethylene glycol (PEG) electrolytes and ZnO nanocrystalline aggregates as photoanode film. Under optimized composite polyelectrolyte containing PEO/oligo-PEG/TiO₂/LiI/I₂ the photovoltaic performance of the solid-state ZnO DSCs was significantly better, with an overall conversion efficiency (η) of 1.8% under irradiation of 100 mW/cm², which was higher than those of the cells with PEO/TiO₂/LiI/I₂ (η = 1.1%) or PEO/oligo-PEG/LiI/I₂ electrolyte (η = 1.5%). Further, the hierarchically structured ZnO-based cell showed a higher η value of 2.0% under 60 mW/cm² radiation. The morphologies, ionic conductivity of three different composite electrolytes and their performance to the DSCs were also studied by FESEM, I–V data, IPCE and EIS.     

A thermoplastic polyurethane/rare earth composite film with adjustable fluorescence colors and optimal low-temperature flexibility

In this study, a unique series of luminous polymeric rare earth (RE) composite films was produced by loading RE ions into thermoplastic polyurethane (TPU) using solution blending. Compared to RE ions, luminous polymeric RE composites had greater luminescence intensity, indicating that the introduction of polymer polyurethane as the polymer matrix was advantageous for the luminescence intensity and efficiency of RE ions, with the polymer matrix's absorbed energy being transferred to the RE ions. Furthermore, the findings of the optical transmittance, UV–visible absorption and fluorescence emission spectra suggest that TPU-RE composite films possess exceptional fluorescence luminescence properties and optical transparency. Surprisingly, the fluorescence colors of TPU-RE fluorescent films could be adjusted between red and green by varying the ratios of Eu³⁺ and Tb³⁺ in the films and can be any mixture of red and green hues. In addition, the temperature at 5% weight loss (T_5%) for the TPU-RE composite film composition reached 250 °C. In addition, pure TPU and all TPU-RE hybrid films demonstrated a glass transition temperature (T_g) of about −30 °C. Simultaneously, the tensile strength of the TPU-T₀E₁₀ film reached its maximum (43.6 MPa). Consequently, the TPU-RE composite films will be utilized as photoluminescent functional materials. © 2022 Society of Industrial Chemistry.     

The Effect of Glycol Type,Glycol Mixture,and Isocyanate/Glycol Ratio on Flexural Properties of Oil Palm Empty Fruit Bunch-Polyurethane Composites

Abstract

Oil palm empty fruit bunch (EFB)-polyurethane (PU) composites were produced. The effects of the isocyanate (NCO)/glycol (OH) ratio, glycol type, and mixtures (polyethylene glycol PEG 400 (M _w 400) and polypropylene glycol PPG 400 (M _w 400)) on the flexural properties were investigated. The NCO/OH ratio had a significant effect on the flexural properties of the EFB-PU composites. Composites made with PEG 200 exhibited higher flexural properties than with PEG 400 and PPG 400. The flexural properties were also found to be influenced by the PPG 400/PEG 400 ratio.     

Synthesis and characterization of PES/PSF/PEG by immersion precipitation for Mediterranean seawater desalination by FO membrane

In the present study, a simple, inexpensive, nontoxic, and environmentally friendly polyethylene glycol (PEG) polymer was used to enhance the hydrophilicity of the forward osmosis (FO) membrane using various PEG concentrations as a pore forming agent in the casting solution of polyethersulfone/polysulfone (PES/PSF) blend membranes. A nonwoven PES/PSF FO blend membrane was fabricated via the immersion precipitation phase inversion technique. The membrane dope solution was cast on polyethylene terephthalate (PET) nonwoven fabric. The results revealed that PEG is a pore forming agent and that adding PEG promotes membrane hydrophilicity. The membrane with 1 wt% PEG (PEG1) had about 27% lower contact angle than the pristine blend membrane. The PEG1 membrane has less tortuosity (which reduces from 3.4–2.73), resulting in a smaller structure parameter (S value) of 277 μm, due to the presence of open pores on the bottom surface structure, which results in diminished ICP. Using 1 M NaCl as the draw solution and distilled water as the feed solution, the PEG1 membrane exhibited higher water flux (136 L m⁻² h⁻¹) and lower reverse salt flux (1.94 g m⁻² h⁻¹). Also, the selectivity of the membrane, specific reverse salt flux, (J_s/J_w) showed lower values (0.014 g/L). Actually, the PEG1 membrane has a 34.6% higher water flux than the commercial nonwoven-cellulose triacetate (NW-CTA) membrane. By means of varied concentrations of NaCl salt solution (0.6, 1, 1.5, and 2 M), the membrane with 1 wt% PEG showed improved FO separation performance with permeate water fluxes of 108, 136, 142, and 163 L m⁻² h⁻¹. In this work, we extend a promising gate for designing fast water flux PES/PSF/PEG FO blend membranes for water desalination.     

Porous biodegradable polyesters. I. Preparation of porous poly(L‐lactide) films by extraction of poly(ethylene oxide) from their blends

Porous poly(L ‐lactide) (PLLA) films were prepared by water extraction of poly(ethylene oxide) (PEO) from solution‐cast PLLA and PEO blend films. The dependence of blend ratio and molecular weight of PEO on the porosity and pore size of films was investigated by gravimetry and scanning electron microscopy. The film porosity and extracted weight ratio were in good agreement with the expected for porous films prepared using PEO of low molecular weight (M_w = 1 × 10³), but shifted to lower values than expected when high molecular weight PEO (M_w = 1 × 10⁵) was utilized. The maximum pore size was larger for porous films prepared from PEO having higher molecular weight, when compared at the same blending ratio of PLLA and PEO before water extraction. Differential scanning calorimetry of as‐cast PLLA and PEO blend films revealed that PLLA and PEO were phase‐separated at least after solvent evaporation. On the other hand, comparison of blend films before and after extraction suggested that a small amount of PEO was trapped in the amorphous region between PLLA crystallites even after water extraction and hindered PLLA crystallization during solvent evaporation. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 629–637, 2000     

Valorization of bio-calcium carbonate based Chamelea gallina shell waste fillers in shape memory polymer composites

In recent years, the focus has been on the use of calcium carbonate-based seashell wastes in the production of new thermoplastic and thermoset polymer materials, paving the way for their use as biofillers in polymeric composites. In this study, it is aimed to obtain a new polymeric composite material by doping Chamelea gallina shells, on polylactic acid (PLA)/polyethylene glycol (PEG) blend. Structural characterization of the obtained PLA/PEG blend/C. gallina composite films was performed with attenuated total reflection infrared spectroscopy (ATR-IR). When the thermal properties of composite materials were examined by thermogravimetric analysis (TGA), it was determined that the thermal stability of polymeric composites increased with the addition of C. gallina. SEM images showed that the polymer blend films, which appeared to have a porous structure, filled the pores with increasing C. gallina ratio. It was observed that the biodegradability of PLA/PEG blend composite films decreased with increasing C. gallina shells addition. However, C. gallina had a positive effect on the swelling and water absorption capacities of polymeric composites. The increase in tensile strength and elongation at break values of PLA/PEG blend/C. gallina composite films with increasing C. gallina means that the mechanical properties of the polymer are improved.     

Synthesis and properties of polyurethane‐urea‐based liquid bandage materials

To obtain ideal liquid bandage polymer materials, a series of polyurethane‐urea dispersions were synthesized from 4,4′‐diisocyanato dicyclohexylmethane (H₁₂MDI) and ethylene diamine with different molar ratio of polyol blend [polyethylene glycol (PEG, M_n = 2000 g/mol)/hydroxy terminated poly(dimethylsiloxane) (PDMS, M_n = ～ 550 g/mol)] and acetone/ethanol as a solvent. The effect of PDMS content in PEG/PDMS on the viscosity, mechanical properties, water contact angle/surface energy, insolubility in water (%), water absorption (%), equilibrium water content (%), and water vapor transmission rate (g m^?2 day^?1) of polyurethane‐urea films was investigated. As PDMS content increased, the water contact angle, insolubility in water, and tensile strength/elastic recovery of film sample increased; however, the surface energy, water absorption (%), equilibrium water content (%), and water vapor transmission rate (g m^?2 day^?1) of film sample decreased. By a wound‐healing evaluation using a full‐thickness rat model experiment, it was found that a wound covered with a typical polyurethane‐urea liquid bandage film (PD2 sample) was filled with new epithelium without any significant adverse reactions. These results suggest that the polyurethane‐urea‐based liquid bandages (samples: PD2 and PD3) prepared in this study may have high potential as new wound dressing materials, which provide and maintain the adequate wet environment required to prevent scab formation and dehydration of the wound bed. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Thermoplastic polyurethane elastomer induced shear piezoelectric coefficient enhancement in bismuth sodium titanate – PVDF composite films

A series of ester-based thermoplastic polyurethane elastomer (TPU) and bismuth sodium titanate polycrystalline oxide (Bi_0.5Na_0.5TiO₃, BNT) co-blended poly (vinylidene fluoride) (PVDF) composite films were prepared. Mechanical test confirms the optimum BNT blending content (25 wt%) and further reveals a linear growth of tensile elongation by increasing TPU content. Microstructure modifications including strengthened hydrogen bond and valence band edge elevation are evidenced to be highly correlated to the dielectric and piezoelectric properties. Significant enhancement (7–13 times) in face shear piezoelectric coefficient (d₃₆) is achieved by adjusting the blending content of TPU. Cross-section image presents a featuring multilayer structure with improved dispersity of BNT particle under a transverse tensile force which effectively increases the interfacial contact area between BNT and polymer blends. This work reveals the significance of band structure modification and anisotropic texture construction on influencing the transfer of piezoelectric charge in TPU blended BNT-PVDF composite film.     

Selective Laser Sintering 3D Printing: A Way to Construct 3D Electrically Conductive Segregated Network in Polymer Matrix

Selective laser sintering (SLS), which can directly turn 3D models into real objects, is employed to prepare the flexible thermoplastic polyurethane (TPU) conductor using self‐made carbon nanotubes (CNTs) wrapped TPU powders. The SLS printing, as a shear‐free and free‐flowing processing without compacting, provides a unique approach to construct conductive segregated networks of CNTs in the polymer matrix. The electrical conductivity for the SLS processed TPU/CNTs composite has a lower percolation threshold of 0.2 wt% and reaches ≈10⁻¹ S m⁻¹ at 1 wt% CNTs content, which is seven orders of magnitude higher than that of conventional injection‐molded TPU/CNTs composites at the same CNTs content. The 3D printed TPU/CNTs specimen can maintain good flexibility and durability, even after repeated bending for 1000 cycles, the electrical resistance can keep at a nearly constant value. The flexible conductive TPU/CNTs composite with complicated structures and shapes like porous piezoresistors can be easily obtained by this approach.     

4,4'/2,4'-二苯基甲烷二异氰酸酯/多元醇本体聚合流变动力学

采用转矩流变仪模拟双螺杆挤出反应条件,分别在无催化剂和铋/锌复合催化剂作用下进行4,4'/2,4'-二苯基甲烷二异氰酸酯/聚四氢呋喃醚二醇/1,4-丁二醇本体聚合,结合二维流动简化假设、黏度/分子量关联式和Arrhenius方程,建立了热塑性聚氨酯(TPU)重均分子量与反应体系转矩、温度的流变动力学方程,分别拟合得到无催化剂和催化剂作用时体系转矩与重均分子量的关联式;发现采用流变动力学方程模拟的TPU平均分子量与实时取样后采用凝胶渗透色谱法测定的结果吻合良好,采用流变动力学方法测量方便迅速,能提供整个反应过程中TPU平均分子量的变化情况。     

Self-cleaning antireflected surfaces based on treated PEO/SiO2 nanocomposite films

In this study, the polyethylene oxide (PEO)/SiO₂ nanoparticles (NPs) nanocomposite films with various SiO₂ NPs concentrations were prepared using an in situ formation of NPs in the polymer matrix for self-cleaning antireflected surface applications. The effect of SiO₂ NPs in PEO/SiO₂ NPs nanocomposite films on the structural, morphological, chemical, thermal, optical, and electrical properties of PEO/SiO₂ NPs nanocomposite films was performed. According to the x-ray diffraction and the differential scanning calorimetry analysis, the crystallinity degree of the nanocomposite films decreases by increasing the SiO₂ NPs concentrations. The bandgap energy of PEO/SiO₂ NPs nanocomposite films decreases from 3.95 to 3.55 eV as the SiO₂ NPs concentration increases up to 10 wt.%. The average electrical conductivity of the PEO/SiO₂ NPs nanocomposite films increases from 5.1 × 10⁻⁷ to 2.0 × 10⁻⁶ S/cm as the SiO₂ NPs concentration increases up to 10 wt.%. The refractive index decreases to 1.64 at 550 nm for the PEO/SiO₂ NPs nanocomposite films with 10 wt.% of SiO₂ NPs, and the water contact angle decreases to around 0° after thermal treatment, which confirms that the PEO/SiO₂ NPs nanocomposite films can be used as self-cleaning antireflected surfaces.     

Modification of zein films by incorporation of poly(ethylene glycol)s

The thermal and mechanical properties of corn (maize) (CZ) films plasticized with poly(ethylene glycol) (PEG) of two different molar masses (400 and 1000 g mol⁻¹) were studied using differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA), tensile strength, moisture absorption isotherms and water vapour transmission rate measurements. The glass transition temperature (T_g) of plasticized films is determined primarily by the amount of moisture contained in the film. DMTA data show contraction of films with loss of absorbed water during heating/cooling cycles. The moisture absorption behaviour of films plasticized with PEG400 and PEG1000 is similar at low relative humidities but significantly different at higher relative humidities. Incorporation of up to about 30 wt% PEG substantially enhances the tensile strength and the resistance to water vapour transmission of the protein film, and PEG1000 is more effective than PEG400. © 2000 Society of Chemical Industry     

Syntheses and properties of urethane prepolymers and their corresponding crosslinked films

Trimethylol propane (TMP), polyglycol (PG), and toluene diisocyanate (TDI) were reacted in various molar ratios to produce TMP–TDI–PG–urethane prepolymers and then mixed with equivalent isocyanate generator (Desmodur AP-Stable) in a mixture of m-cresol and naphtha to give polyurethane varnishes which finally became crosslinked films by the casting method. The mechanical properties and viscoelasticities of the PG-modified and PG-free polyurethane crosslinked films and the practicability of magnet wires coated with them were studied in this article. Three different PGs used in this experiment were polyethylene glycol, PEG(#400), polypropylene glycols, PPG(#1000) and PPG(#2000). In the case of adding PEG(#400) for modification, strength at break increased but elongation did not change. Meanwhile, glass transition temperature (T_g) shifted to lower temperature with increasing molar ratio. In the case of adding PPG(#1000) and PPG(#2000) for modification, the samples changed their mechanical properties from hard and brittle to soft and tough. With increasing molar ratios, strength at break initially increased and then decreased gradually, and elongation varied a lot and was consistently contrary to strength at break. T_g occurred at two regions: one at high temperature above 100°C for small molar ratios and the other at low temperature below 100°C for high molar ratios. Besides, for all PG-modified polyurethane crosslinked films, strength at break showed a local maximum at TMP/TDI/PG = 1/1/0.5, which indicated their homogeneous structures. The molar ratios of PG-modified urethane prepolymers, which are suitable for manufacturing practical magnet wires according to testing method JIS-C-3211, are as follows: TMP/TDI/PPG(#100) = 1/1/0.15–0.35 and TMP/TDI/PPG(#2000) = 1/1/0.10. PEG(#400)-modified magnet wires were not accepted on the aging test. The properties of crosslinked films of practical magnet wires are generally as follows: strength at break at 200–700 kg/cm², elongation less than 41%, and T_g at 100–200°C.     

Electromagnetic interference shielding behavior of chemically and thermally reduced graphene based multifunctional polyurethane nanocomposites: A comparative study

This article presents the effect of exfoliation, dispersion, and electrical conductivity of graphene sheets onto the electrical, electromagnetic interference (EMI) shielding, and gas barrier properties of thermoplastic polyurethane (TPU) based nanocomposite films. The chemically reduced graphene (CRG) and thermally reduced/annealed graphene (TRG) having Brunauer–Emmett–Teller surface areas of 18.2 and 159.6 m²/g, respectively, when solution blended with TPU matrix using N,N-dimethylformamide as a solvent. Graphene sheets based TPU nanocomposites have been evaluated and compared for EMI shielding in Ku band, electrical conductivity, and gas barrier property. TRG/TPU nanocomposite films showed excellent gas barrier against N₂ gas as compared to CRG/TPU. The EMI shielding effectiveness for neat CRG and TRG graphene sheets is found to be −80, −45 dB, respectively, at 2 mm thickness. The EMI shielding data revealed that TRG/TPU nanocomposites showed better shielding at lower concentration (10 wt %), while CRG displayed better attenuation at higher concentrations. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47666.     

Gas permeation properties of a composite membrane filled with poly(ethylene oxide) into a porous membrane

The permeability coefficients of O₂, N₂, and CO₂ gases at 25°C were examined for composite membranes that were prepared by filling poly(ethylene oxide)(PEO) with different molecular weights into a porous membrane. The permeability coefficients of O₂, N₂, and CO₂ were 2 × 10⁻¹⁰ – 4 × 10⁻¹⁰, 5 × 10⁻¹¹ – 9.5 × 10⁻¹¹, and 6 × 10⁻¹⁰ – 1 × 10⁻⁹ (cm³ STPcm/cm² s cmHg), respectively. The higher permeability coefficients of CO₂ are explained in terms of high solubility of CO₂ in filled PEO. The permeability coefficient of CO₂ was affected by the degree of crystallinity of PEO in the composite. On the other hand, there was little effect of crystallinity on O₂ and N₂ permeability coefficients. Some probable relationships between selectivities of O₂ to N₂ and CO₂ to N₂ and the degree of crystallinity of PEO were observed. The CO₂ gas permeability coefficients of the composite membrane for PEO50000 (M_w = 5 × 10⁴) showed a marked change due to melting or crystallization of PEO. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2733–2738, 1999     

Simultaneously improved solid particle erosion resistant and strength of graphene nanoplates/carbon nanotube enhanced thermoplastic polyurethane films

Up to now, it is a major challenge to protect leading edge of the blades from solid particle erosion. Herein, we propose a structure optimization strategy to fabricate non-woven (NW) enhanced thermoplastic polyurethane nanocomposite films (thermoplastic polyurethane [TPU] - NW@G/C_x) with “sandwich - like” structure by hot pressing technology. TPU NW/graphene nanoplates/carbon nanotube (NW@G/C_x) interlayer film were first fabricated by spraying method. Then the interlayer film was laminated between TPU films to fabricate nanocomposite films. Such prepared TPU - NW@G/C_x film shows excellent solid particle erosion resistance and high-tensile strength. For example, the “steel-and-mortar” structure of NW fabric in TPU film results in high-tensile strength of 45 MPa and storage modulus of 21.2 MPa for TPU - NW@G/C_1.0, increasing by 25% and 171% compared with original TPU film (35 MPa, 8 MPa), respectively. In addition, compared with pure TPU film, the “sandwich - like” structure endows TPU - NW@G/C_1.2 with excellent solid particle erosion resistance and the thermal conductivity (0.251 W/m·K). These superior properties extends application of the TPU - NW@G/C_x film on wind turbine blades.     

Flexible poly(styrene-ethylene-butadiene-styrene) hybrid nanofibers for bioengineering and water filtration applications

Among the thermoplastic elastomers that play important roles in the polymer industry due to their superior properties, styrene-based species and polyurethane block copolymers are of great interest. Poly(styrene-ethylene-butadiene-styrene) (SEBS) as a triblock copolymer seems to have the potential to meet many demands in different applications due to various industrial requirements where durability, biocompatibility, breaking elongation, and interfacial adhesion are important. In this study, the SEBS triblock copolymer was functionalized with natural (Satureja hortensis, SH) and synthetic (nanopowder, TiO₂) agents to obtain composite nanofibers by electrospinning and electrospraying methods for use in biomedical and water filtration applications. The results were compared with thermoplastic polyurethane (TPU) composite nanofibers, which are commonly used in these fields. Here, functionalized SEBS nanofibers exhibited antibacterial effect while at the same time improving cell viability. In addition, because of successful water filtration by using the SEBS composite nanofibers, the material may have a good potential to be used comparably to TPU for the application.